Download Hi-Res ImageDownload to MS-PowerPointCite This:Ind. Eng. Chem. Res. 2020, 59, 14, 6589-6599
Enhancing the Performance of Poly(phthalazinone ether ketone)-Based Membranes Using a New Type of Functionalized TiO2 with Superior Proton Conductivity
- Hossein Beydaghi*Hossein Beydaghi*Email: [email protected]Graphene Labs, Istituto Italiano di Tecnologia, Via Morego 30, 16163 Genova, ItalyMore by Hossein Beydaghi,
- Ahmad BagheriAhmad BagheriDepartment of Chemistry, Amirkabir University of Technology, 1599637111 Tehran, IranMore by Ahmad Bagheri,
- Parisa SalarizadehParisa SalarizadehHigh-Temperature Fuel Cell Research Department, Vali-e-Asr University of Rafsanjan, 7718897111 Rafsanjan, IranMore by Parisa Salarizadeh,
- Sepideh KashefiSepideh KashefiDepartment of Chemical Engineering, Semnan University, 3513119111 Semnan, IranMore by Sepideh Kashefi,
- Khadijeh HooshyariKhadijeh HooshyariDepartment of Applied Chemistry, Faculty of Chemistry, Urmia University, 5756151818 Urmia, IranMore by Khadijeh Hooshyari,
- Ali AmoozadehAli AmoozadehDepartment of Chemistry, Semnan University, 3513119111 Semnan, IranMore by Ali Amoozadeh,
- Taiebeh ShamsiTaiebeh ShamsiDepartment of Chemistry, Semnan University, 3513119111 Semnan, IranMore by Taiebeh Shamsi,
- Francesco Bonaccorso*Francesco Bonaccorso*Email: [email protected]Graphene Labs, Istituto Italiano di Tecnologia, Via Morego 30, 16163 Genova, ItalyBeDimensional SpA, Via Albisola 121, 16163 Genova, ItalyMore by Francesco Bonaccorso, and
- Vittorio PellegriniVittorio PellegriniGraphene Labs, Istituto Italiano di Tecnologia, Via Morego 30, 16163 Genova, ItalyBeDimensional SpA, Via Albisola 121, 16163 Genova, ItalyMore by Vittorio Pellegrini
Copyright © 2020 American Chemical Society
Abstract
A novel, high-efficiency, and cost-effective series of sulfonated poly(phthalazinone ether ketone)/sulfonated titanium [email protected] [email protected] (SO3H−TiO2@[email protected]3H) nanocomposite membranes is designed to enhance the proton conductivity and methanol barrier of the proton exchange membrane (PEM). The nanocomposite membranes were prepared via a facile one-step process of the solution casting method. The presence of organic–inorganic SO3H–TiO2@[email protected]3H nanoparticles improved the performance of the nanocomposite membranes in terms of mechanical stability, proton conductivity, methanol permeability, and selectivity. We used toluene diisocyanate (TDI) as a linker to exploit the properties of sulfonated TiO2 and sulfonated ethylenediamine (EN-SO3H) nanoparticles. These nanoparticles act as Lewis and Brønsted acids simultaneously because of the presence of sulfonamide, TiO2, and SO3H groups, which increase the kinetics of the reaction between the membrane and electrode, improving the performance of the direct methanol fuel cell (DMFC). The DMFC, which is assembled using the nanocomposite membrane with 5 wt % SO3H–TiO2@[email protected]3H nanoparticle (MSN5) membrane, exhibited a maximum power density of 59.22 mW cm–2 during testing because of high proton conductivity and low methanol permeability. The MSN5 membrane is a promising PEM for DMFCs.
1. Introduction
ARTICLE SECTIONS
Recently, direct methanol fuel cells (DMFCs) have been widely used as promising power generation devices because of their simple structural design, low-temperature operation, and high efficiency. (1,2) Hydrogen or methanol are used as fuels, while air is used as an oxidant for portable applications. The consumption of methanol as the fuel in DMFC gives more advantages, compared to other fuels, such as flexibility of cell designing, reduced cost of the fuel management system, and the quick and safe refilling process of the fuel. (3) The slow kinetics of methanol oxidation reaction in the anode electrode and methanol cross-over through the membranes are important factors that could lead to a remarkable energy loss in DMFCs. (4,5) The proton exchange membrane (PEM), as the core component of DMFC, is required to have high proton conductivity, methanol barrier properties, suitable thermal, mechanical stability, and durability. (6−8) The most used PEM is the perfluorosulfonic acid (PFSA) ionomer (especially the Nafion membrane). (9,10) However, the environmental incompatibility, high cost production, high crossover of methanol, and decrease of proton conductivity with the increase of temperature have been critical challenges for the PFSA membranes. Therefore, in the past years, a strong research effort has been focused toward the preparation of new membranes with desirable properties as an alternative of the PFSA membrane (especially the Nafion membrane) for DMFCs.
In this context, some polymers have been processed to be sulfonated and used as alternative membranes to PFSA such as poly(vinylidene fluoride-co-hexafluoropropylene) (PVDF), (11,12) polysulfone, (13) poly(ether ether ketone) (PEEK), (14−17) poly(ether sulfone), (18) sulfonated biopolymer, (19) and poly(phthalazinone ether ketone) (PPEK). (20,21) The introduction of sulfonated groups into polymeric chains creates specific proton transport channels in the structure of the membrane, improving the proton conductivity of the as-prepared PEMs. However, the proton conductivity of the sulfonated polymer is lower than the one of the Nafion membrane because of the lower acidity of −SO3H and less distinct phase separation between hydrophobic and hydrophilic domains. (22) To improve the performances of membranes, the addition of nanoparticles with good conductivity properties was investigated for the preparation of nanocomposite membranes as an alternative to the Nafion membrane. (10) In this context, different nanoparticles and nanosheets such as graphene-based nanosheets, (23,24) perovskite nanoparticles, (25,26) sulfonated tungsten trioxide, (20) and sulfonated nonporous silica (27) have been used to prepare nanocomposite membranes by our group.
Poly(aryl ether ketone)s-based membranes belong to the class of high-performance PEMs in DMFCs. (28) Among the poly(aryl ether ketone) polymers, PPEK has been extensively studied for its use in DMFCs because of the low methanol cross-over linked with the low hydrophilic/hydrophobic separation in the structure of the polymer. (20) The introduction of the rigid phenyl phthalazinone moiety into the polymer increases the intermolecular H-bond, leads to polymers with very high glass-transition temperature (as a class of thermoplastics) (>200 °C), excellent mechanical properties, and thermo-oxidative stability, and results in high dimensional stability and lower membrane swelling (MS) in PEMs. (29) For applications in DMFCs, it is desirable to modify PPEK still maintaining their properties, such as good water uptake, low electrical conductivity, high ionic conductivity, low fuel permeability, suitable mechanical properties, and high selectivity. (11) Compared to other conventional polymers used as the polymeric base of PEMs, less work has been done on PPEK. Liu et al., prepared a series of cross-linked anion exchange membranes based on quaternized PPEK. (30) The membranes have shown low MS (∼7%) and conductivity (0.028 S cm–1 at 30 °C) because of the cross-linking reaction. Hongwei et al. developed SPPEK membranes by electrospinning for their use in PEM fuel cells. (31) Recently, our group prepared SPPEK/SPVDF/sulfonated trioxide (SWO3) as suitable PEMs for DMFCs. (20) The results show that the presence of the sulfonated groups in the structure of SWO3 nanoparticles increases proton conductivity and selectivity of the as-prepared membranes. Sulfonated PPEK with ionic exchange groups (SO3H) can be prepared by the postsulfonation of PPEK. The proton conductivity is the most important parameter in the preparation of PEMs for different types of the polymeric fuel cell. The final performance of DMFC strictly depends on the conductivity of the membrane. The sulfonation determines an increase of water uptake, proton conductivity, MS, and methanol permeability. Therefore, to increase the proton conductivity, while maintaining low methanol permeability and swelling, the addition of an inorganic additive and preparation of nanocomposite membranes is a promising experimental route. (32)
The sulfonated titanium [email protected] [email protected] (SO3H–TiO2@[email protected]3H) nanoparticle is a suitable additive for the synthesis of PEMs. In the literature, the properties of sulfonated TiO2 as an attractive additive were investigated for the use in PEM of different types of fuel cells. (33−35) The hygroscopic nature and high surface area of TiO2 nanoparticles coupled with the formation of hydrogen bonding between functionalized groups of sulfonated TiO2 and polymer chains help improve water uptake, mechanical properties, and thermal stability of the as-prepared membranes. (33) Sulfonated groups of SO3H–TiO2 nanoparticles can increase the hydrophilic nature of these nanoparticles and improves water uptake, which is beneficial in improving proton transfer in the membrane structure. (35) The simultaneous use of sulfonated TiO2 and sulfonated ethylenediamine (EN-SO3H) is possible using toluene diisocyanate (TDI) as a linker. The TDI was used to establish a bridge between the surface of SO3H–TiO2 and EN-SO3H. The sulfonated groups of EN-SO3H support the H+ transport through proton exchange channels in the membrane structure, enhancing the proton conductivity. The increase in proton conductivity has an important role in improving the final performance of the DMFC. (27) In fact, in addition to the mentioned improvements, the sulfonamides act as an additional source of protons, which can be beneficial for the proton transfer across the membrane. It is well known that sulfonamides are good Brønsted acids. (36) Thus, the acidic properties of these nanoparticles can positively impact the kinetics of the reaction in membrane–electrode assembly (MEA) by decreasing the activation energy and reducing the methanol cross-over. This, in turn, increases the catalytic activity of the cathode catalyst, improving the final performance of DMFCs. The SO3H–TiO2@[email protected]3H nanoparticles act as Lewis and Brønsted acid simultaneously because of the presence of amide, TiO2, and SO3H groups, improving proton conductivity and mechanical stability of the as-prepared membranes. (37) The organic–inorganic structure of SO3H–TiO2@[email protected]3H nanoparticles combines different properties of an organic (ductility and flexibility) and inorganic (rigidity and stability) moiety in the as-prepared nanocomposite membranes, leading to the preparation of the ideal membrane for DMFC. (38)
In this work, we report the fabrication of a novel nanocomposite PEM based on SPPEK as the polymer matrix and SO3H–TiO2@[email protected]3H nanoparticles as a suitable organic–inorganic additive for use in DMFCs. The different SPPEK/SO3H–TiO2@[email protected]3H nanocomposite membranes were synthesized using the solution casting method. The SO3H–TiO2@[email protected]3H nanoparticles provide proton conductivity because of its sulfonated groups and the Grotthuss mechanism and can act as fillers in the structure of the membrane to decrease methanol permeability. (27) These as-prepared membranes show excellent selectivity and DMFC performance because of the high proton conductivity of SO3H–TiO2@[email protected]3H nanoparticles.
2. Experimental Section
ARTICLE SECTIONS
2.1. Materials
Sulfonated PPEK (SPPEK) was purchased from the FuMa-Tech company. TDI was of industrial grade. All other chemicals and solvents were purchased from Merck and used without any purification.
2.2. Synthesis of Nanoparticles
First, 1 g of titanium dioxide and 1.4 g of TDI were dissolved in 50 mL of pure toluene and sonicated in an ultrasound bath for 20 min and stirred for 6 h at 95 °C. The obtained powder was centrifuged. To eliminate the possible presence of TDI, the product was washed using toluene. Then, the product was dried at 80 °C for 24 h to obtained n-TiO2–TDI nanoparticles. (37)n-TiO2–TDI (1 g) was added to EN and stirred at 50 °C. After 24 h, the precipitated powder was separated by centrifugation and washed using acetone followed by drying at 110 °C. For the sulfonation reaction, 1 g of modified nanoparticles was dispersed in 15 mL of dichloromethane and 0.06 mL of chlorosulfonic acid was added dropwise to the dispersion at room temperature. Afterward, the dispersion was stirred for 2 h to eliminate the produced HCl gas. Finally, the dispersion was centrifuged, and the collected sediment was dried at 80 °C for 24 h. The schematic of the SO3H–TiO2@[email protected]3H nanoparticle synthesis procedure is shown in Figure 1.
Figure 1
Figure 1. Scheme for the synthesis of SO3H–TiO2@[email protected]3H nanoparticles.
2.3. Membrane Preparation
Two types of membranes of SPPEK and SPPEK/SO3H–TiO2@[email protected]3H were prepared and named MS and MSNx, respectively, in which x is the weight percentage of SO3H–TiO2@[email protected]3H nanoparticles in the structure of the nanocomposite membranes. For the preparation of the MS membrane, the appropriate amount of SPPEK was dissolved in dimethylacetamide (DMAc) under stirring at 60 °C, for 4 h to form 10 wt % solution. Afterward, the resulting solution was cast on a clean flat glass using a doctor blade and drying at 70 °C for 12 h and 120 °C for 2 h to remove residual solvents. For the preparation of MSNx membranes, after dissolving an appropriate amount of SPPEK in DMAc, the different weight percentages of SO3H–TiO2@[email protected]3H nanoparticles was added to the abovementioned solution and ultrasonicated for 1 h. The final dispersion was cast on a glass plate and drying at the same temperatures.
2.4. Characterization
Fourier transform infrared (FTIR) characterization of the nanocomposite membranes was carried out using a Bruker Equinox 55 FTIR Spectrometer at room temperature. The samples were tested from the wavenumber of 400–4000 cm–1. The X-ray diffraction (XRD) analysis of the samples was carried out using an Equinox 3000, by applying (a) a detected diffraction angle of 2θ, (b) a range of 15–65°, and (c) a fixed scan rate of 3° min–1. Scanning electron microscopy (SEM) images of the as-prepared PEM cross-section were taken on a TESCAN SEM. Before the test, the membranes were fractured in liquid nitrogen and coated with gold. The mechanical properties [tensile strength (TS) and elongation at break] of the prepared PEMs were determined using a SANTAM DBBP-100 testing machine with a tensile rate of 1 mm·min–1 at room temperature.
The water uptake of the as-prepared membranes was obtained by measuring the weight difference in wet and dry PEMs. First, the membranes were placed in distilled water for 12 h, the surface water was removed using paper, and the wet membrane was weighed (Ww). Afterward, the wet PEM was dried in the oven for 12 h and weighed (Wd). The water uptake (WU) is calculated using the equation
in which Ww and Wd are the weight of the wet and dry membrasnes, respectively.
in which Ww and Wd are the weight of the wet and dry membrasnes, respectively.The swelling of the as-prepared membranes was measured using the same method and using the change of membrane area in the wet and dry membrane (Aw and Ad, respectively). The MS is calculated by
To investigate the oxidative stability of different membranes, the Fenton reagent (3 wt % H2O2 + 2 ppm FeSO4) was used at 80 °C. The prepared anhydrous membranes were placed in 30 mL of Fenton reagent until the membrane began to break.
The proton conductivity (σ) of different prepared membranes was calculated at different temperatures with a potentiostat/galvanostat electrochemical work station with four electrodes. The proton conductivity was calculated using a four-probe conductivity cell equipped with an AC impedance analyzer. The as-prepared membranes were soaked in deionized water for 12 h before the test. Bulk resistance (R) (Ω) was measured using the impedance plot obtained at an AC voltage of 50 mV in the frequency range of 0.1 Hz to 100 kHz. The proton conductivity of the samples was calculated as follows
in which, L (cm) and A (cm2) are the distance between two electrodes and the surface area, respectively.
in which, L (cm) and A (cm2) are the distance between two electrodes and the surface area, respectively.A diffusion cell containing two separate compartments, that were named A and B, was used for the calculation of methanol permeability (P, cm2 s–1). In order to calculate methanol permeability, the as-prepared membranes were placed between these two compartments. Methanol–water solution (1 M) was added to compartment A and also deionized water to compartment B. Methanol diffused through the thickness of the membrane from compartment A to B during stirring, and the methanol concentration in compartment B was measured using a density meter as a function of time because of concentration difference. The methanol permeability coefficient was calculated as follows
in which, VB (cm3), L (cm), A (cm2), CA (mol L–1), and CB (mol L–1) are the volume of compartment B, thickness of the sample, effective area of the sample, and the methanol concentration in compartments A and B, respectively.
For the calculation of proton conductivity and methanol permeability, the selectivity (S, S s cm–3) of prepared membranes was measured using the following equation
2.5. DMFC Performance
The MEA was prepared using the following procedure: the catalyst dispersion for the cathode was prepared by mixing the Pt/C catalyst (20 wt % of Pt), Nafion solution (5 wt %), deionized water, IPA, and glycerol. The obtained dispersion was then sonicated for 2 h to homogenize it. Pt–Ru/C (40:40:20) was used as the anode catalyst, mixed with a suitable amount of Nafion solution, IPA, and deionized water to get a homogeneous dispersion. The catalyst dispersions were painted onto carbon cloth (E-Tek, HT 2500-W) with the Pt and PtRu loading of 2 and 1 mg cm–2 for the anode and the cathode electrodes, respectively. Finally, the as-prepared PEM was hot-pressed between anode and cathode electrodes at 140 °C for 3 min to obtain MEA. Single active DMFC cell performance was carried out at room temperature, using 2 M methanol feed concentration.
3. Result and Discussion
ARTICLE SECTIONS
3.1. Characterization
The surface compositions and chemical structures of the nanoparticles and the different membranes were investigated via FTIR. Figure 2a shows the FTIR analysis for every step in the synthesis of SO3H–TiO2@[email protected]3H nanoparticles. In the spectrum of TiO2 nanoparticles, the characteristic peaks at 1622 and 3355 cm–1 confirm the presence of surface −OH stretching bands. Moreover, the wide peak below 1200 cm–1 may be attributed to Ti–O–Ti vibration in the structure of TiO2 nanoparticles. (39) The absorption bands at 1550 and 2243 cm–1 in the TDI spectrum is assigned to the existence of the phenyl ring and stretching vibration of N═C═O in the structure of TDI. (40) The successful synthesis of TiO2–TDI confirmed by the presence of the stretching vibration peaks of C═O and C–N in urethane bond at 1649 and 1595 cm–1 and two absorption peaks at 2266 and 1533 cm–1 assigned to the unreacted orthoisocyanate group and phenyl ring in the structure of TDI. (41) After adding EN to TiO2–TDI, the final structure was confirmed by the peak at 3260 cm–1, resulting from the presence of amino groups. Finally, sulfonation of nanoparticles with chlorosulfonic acid was verified using the wide band of the acidic group between 2800 and 3200 cm–1 and absorption peaks of 1033 and 1213 cm–1, which is assigned to O═S═O asymmetric and symmetric stretching and the stretching vibration of S═O on sulfonated groups, respectively. (42)
Figure 2
Figure 2. FTIR spectra of different prepared nanoparticles and membranes.
Chemical structures of the MS and MSN5 membranes were investigated, and the FTIR spectra are shown in Figure 2b. In the MS membrane, the peaks at around 1234 and 1479 cm–1 are related to the C–O–C and C–C bonds in the aromatic ring, respectively, and the peaks around 1585 and 1658 cm–1 represent the carbonyl groups and C═N bands in the structure of SPPEK, respectively. (43) Also, three absorption peaks at 1018, 1082, and 1144 cm–1 are related to the symmetric and asymmetric stretching vibration of O═S═O and stretching vibration of S═O, confirming the addition of sulfonated groups in the structure of the polymer. As shown in Figure 2b, after adding SO3H–TiO2@[email protected]3H nanoparticles to SPPEK, the intensity of sulfonated group-related peaks (1000–1150 cm–1) changed. This is related to the presence of sulfonated groups in the structure of SO3H–TiO2@[email protected]3H nanoparticles. In addition, the peak at ∼580 cm–1 in the MSN5 membrane may be assigned to the presence of Ti–O vibration in the structure of the nanocomposite membrane. (44)
The crystal nature of the SO3H–TiO2@[email protected]3H nanoparticles is verified using XRD analysis (Figure 3). Figure 3 shows diffraction peak (101), (103), (004), (112), (200), (105), (211), (204), (116), (220), (215), and (224) facets of the crystal planes of TiO2 nanoparticles which are in accordance with the JCPD 894921 standard for the crystalline phase of TiO2. As shown in Figure 3, the SO3H–TiO2@[email protected]3H nanoparticles show diffraction patterns similar to the ones of TiO2 nanoparticles. The addition of other organic materials (i.e., TDI and EN) and the sulfonate modification process do not change the phase of nanoparticles, and the crystal nature has been preserved.
Figure 3
Figure 3. Diffraction patterns of TiO2 (a) and SO3H–TiO2@[email protected]3H nanoparticles.
In order to illustrate the shape of SO3H–TiO2@[email protected]3H nanoparticles and the effect of adding organic materials and sulfonation reaction on the morphology of nanoparticles, SEM images of the nanoparticles were acquired, see Figure 4. Typically, some properties of small nanoparticles are determined by their size. (45)Figure 4a shows that the TiO2 nanoparticles have a spherical shape with an average particle size of 25 nm. According to the SEM image of TiO2@[email protected] nanoparticles, an increase in the average particle size to 80 nm is detected, which is due to the grafting of organic components onto the surface of TiO2 nanoparticles. The aggregation of SO3H–TiO2@[email protected]3H nanoparticles observed in Figure 4c is due to the functionalization process.
Figure 4
Figure 4. (a) SEM images of TiO2, (b) TiO2@[email protected], and (c) SO3H–TiO2@[email protected]3H nanoparticles.
Surface and cross-sectional images of MS and MSN5 membranes were shown in Figure 5a–d. The surface of the MS membrane (Figure 5a) is smoother than the nanocomposite membrane. This fact is due to the absence of SO3H–TiO2@[email protected]3H nanoparticles in the pristine membrane. From the cross-sectional SEM images, it is clear that both prepared membranes show homogeneous morphology without any cracks and holes. The uniform and homogeneous structure of the MSN5 membrane (Figure 5d) can be related to the high miscibility between SPPEK chains and SO3H–TiO2@[email protected]3H nanoparticles. EDX mapping images displayed in Figure 6 show the homogeneous distribution of nanoparticles in the as-prepared membranes. There is a more homogeneous dispersion of Ti in the MSN5 nanocomposite membrane compared to the other membranes. Also, the aggregation of SO3H–TiO2@[email protected]3H nanoparticles in the MSN5 membrane is evident in some regions.
Figure 5
Figure 5. Surface and cross-sectional images of (a,c) MS and (b,d) MSN5 membranes.
Figure 6
Figure 6. EDX mapping images of (a) MSN1, (b) MSN3, (c) MSN5, and (d) MSN7 membranes.
3.2. Water Uptake and Membrane Swelling
The water uptake and MS are two key parameters of membranes in DMFCs that have a huge impact on proton conductivity, mechanical stability, and durability of prepared membranes. It is desirable that prepared membranes should have high water uptake for proton conductivity and low MS for mechanical stability and durability. (46) In the as-prepared membranes, water molecules play the role of carriers, transferring proton and methanol by creating and breaking hydrogen bonding throughout the PEM. Figure 7 shows water uptake and MS of different prepared PEMs at temperatures in the 20–80 °C range. As shown in Figure 7a, the nanocomposite membranes have shown higher water uptake compared to the MS membrane. This behavior is ascribed to the hydrophilic nature of the SO3H–TiO2@[email protected]3H nanoparticles, absorption of water molecules with the formation of hydrogen bonding between functionalized groups of nanoparticles and free water molecules, and the creation of more acid sites to absorb free water. The results show that the water uptake on nanocomposite membranes increases with increasing the loading rate of nanoparticles from 1 to 7%. This is linked with the fact that the increase of the loading of SO3H–TiO2@[email protected]3H increases the hydrophilic region in the structure of nanocomposite membranes. Also the difference in morphology of the membrane influences the interconnections of the ionic cluster responsible for water retention. (47)
Figure 7
Figure 7. (a) Water uptake and (b) MS diagrams of different prepared PEMs at temperatures between 20 and 80 °C.
Dimensional stability is a vital parameter of the prepared membranes when used in MEA of DMFCs because it is critical for proper mass transfer and prevention of electrical contact in the MEA. (28) As shown in Figure 7b, unlike water uptake, the swelling of the different nanocomposite membranes are lower than pristine SPPEK, decreasing from 12.8 to 9.5% at room temperature with increasing the SO3H–TiO2@[email protected]3H nanoparticle content. This effect is likely due to the compact structure of nanocomposite membranes with the formation of hydrogen bonding between functionalized groups of nanoparticles and sulfonated groups of the polymer. Also, the complex structure of SO3H–TiO2@[email protected]3H nanoparticles could limit the motion of SPPEK chains, constraining the MS. (48) The results of Figure 7 show that both water uptake and MS increased with the temperature. These results may be due to the increase in mobility of free water molecules and SPPEK chains with increasing temperature from 20 to 80 °C, facilitating water absorption in the polymeric structure. (49) In general, the incorporation of SO3H–TiO2@[email protected]3H into the structure of nanocomposite membranes enhances water retention and dimensional stability, making the nanocomposite membranes more appealing for use in DMFCs.
3.3. Proton Conductivity
Proton conductivity is the most important property of PEM in DMFCs. According to the key role of water molecules on proton transfer in both the mechanism of Grotthuss and Vehicle, the water-friendly properties are the pillars of the movements of the protons in the structure of the membrane. The proton conductivity value of different PEMs in the absence and presence of SO3H–TiO2@[email protected]3H was measured at 20 °C and summarized in Table 1. As shown in Table 1, all nanocomposite membranes exhibited higher proton conductivity than the pristine SPPEK membrane. The addition of nanoparticles affects positively the structure of the membrane because of the improvement in the proton conductivity as a consequence of nanoparticle interaction (Figure 8). The transportation of the proton through the structure of PEM is via the hydrophilic regions, and thus, proton conductivity is directly linked with the water uptake. Thus, an increase of nanoparticles means more proton transfer, which is due to the hydrophilic nature of SO3H and TiO2 groups. (50) The hygroscopic nature of TiO2 nanoparticles leads to reserves of water molecules and creates water and proton conduction channels at the interface nanoparticles/polymeric chains. Also, according to the presence of TiO2, sulfamide, and SO3H groups in the structure of nanoparticles, the SO3H–TiO2@[email protected]3H nanoparticles act as Lewis and Brønsted acid simultaneously and improve proton conductivity of the nanocomposite membranes. Moreover, according to the key role of SO3H groups in the Grotthuss mechanism, the formation of hydrogen bonding between sulfonated groups of SO3H–TiO2@[email protected]3H nanoparticles and free water molecules available in the membrane leads to the more transfer of protons using the Grotthuss mechanism and increasing proton conductivity value in the membrane (Figure 8). (51) Furthermore, in the sulfonamide groups, there is an additional proton compared to sulfone ester and the hydrogen connected to nitrogen atom show acidic nature. Therefore, the proton transfer is easier at the presence of the prepared SO3H–TiO2@[email protected]3H nanoparticles. The reduction in proton conductivity of the MSN7 membrane may be due to the blocking of ion transport channels, resulting from aggregation tendency and the filling effect of nanoparticles on the polymer chains, see Figure 6d. (10)
Figure 8
Figure 8. Schematic of proton conductivity in the as-prepared nanocomposite membrane.
Table 1. Proton Conductivity, Methanol Permeability, and Selectivity of the Different Prepared Membranes at Room Temperature
| membrane | σ (S cm–1) | P (cm2 S–1) × 10–7 | S (S s cm–3) × 104 |
|---|---|---|---|
| MS | 0.049 | 7.2 | 6.9 |
| MSN1 | 0.059 | 5.6 | 10.6 |
| MSN3 | 0.070 | 5.1 | 13.8 |
| MSN5 | 0.091 | 3.1 | 29.3 |
| MSN7 | 0.078 | 2.8 | 27.9 |
According to the proton conductivity–temperature relationship, the activation energy (Ea) that is the minimum energy required to proton passes from one functional group to another one and obtained using Arrhenius equation σ = A exp(−Ea/RT) was calculated and plotted in Figure 9. In the Arrhenius equation, A is a pre-exponential factor, R is the universal gas constant (J mol–1 K–1), and T is the temperature in kelvin. According to Arrhenius plots shown in Figure 9, the as-prepared PEMs exhibited an upward trend of the proton conductivity with the temperature. Increasing the mobility of water molecules and polymer chains at high temperatures increases the vacant spaces for proton transfer in the membrane. (52) Also, increasing the proton mobility at high temperatures has an influence on proton jumping from SO3–H3O+ (Grotthuss mechanism). The results show that the PEM with 5 wt % SO3H–TiO2@[email protected]3H loading achieved the best proton conductivity at different temperatures. The MS, MSN1, MSN3, MSN5, and MSN7 membrane exhibits an ion transport Ea of 7.18, 6.32, 5.51, 4.49, and 5.19 kJ mol–1, respectively. The decay of Ea demonstrated the decreased energy barrier for proton transfer linked with the interaction between the sulfonamide and SO3H groups of nanoparticles and polymers. (53) Thus, the MSN5 nanocomposite membrane has the highest potential for use in higher temperature DMFC because of the lowest Ea value among all the different as-prepared membranes.
Figure 9
Figure 9. Arrhenius plots for proton conductivity at different temperatures.
3.4. Methanol Permeability and Selectivity
To demonstrate that the different as-prepared membranes can be used as the PEM for applications in DMFC, we investigated methanol permeability. The fuel cross-over through a membrane is an important challenge causing final performance degradation of DMFCs because the methanol can deteriorate the catalytic activity of the cathode toward oxygen reduction reaction, which determines a reduction in the DMFCs performance. (54) Then, the lower methanol cross-over of the membrane is a key requirement to improve the performance of DMFC. As aforementioned, SPPEK has attractive potential as a suitable PEM for DMFCs because of minimal hydrophilic/hydrophobic separation in the structure of the polymer that reduces methanol cross-over through the membrane. (20) The results of Table 1 show that the methanol permeability of nanocomposite membranes is lower than pristine SPPEK. The formation of hydrogen bonding between functionalized groups of nanoparticles and polymeric chains causes the compact structure of the membrane; subsequently, the methanol transport channels in the membrane are reduced, decreasing the methanol permeability of nanocomposite membranes. The formation of tighter hydrophilic domains with the addition of nanoparticles, which makes transport channels more obstructed, leads to the considerably lower methanol cross-over of nanocomposite membranes. (55) This is in good agreement with the results of MS of nanocomposite membranes. The methanol permeability of nanocomposite membranes was decreased from 5.6 × 10–7 to 2.8 × 10–7 cm2 S–1 with the addition of more SO3H–TiO2@[email protected]3H nanoparticles. The filling effect of SO3H–TiO2@[email protected]3H nanoparticles in the structure of polymeric chains that obstruct methanol transport channels upon nanocomposite membranes should be another reason for the decrease of methanol permeability.
To further investigate the performances of the different membranes, we measured, at room temperature, the selectivity of prepared membranes, see Table 1. High selectivity of the membrane represents a key performance parameter for DMFCs. (56) According to the results reported in Table 1, it is seen that compared to the MS membrane, the nanocomposite membranes show a significant improvement in selectivity. Among the different nanocomposite membranes, the MSN5 membrane shows the highest selectivity, that is, 4.5 times higher compared to the MS membrane because of their good proton conductivity and low methanol penetration. The combined analysis of three performance parameters (i.e., proton conductivity, methanol permeability, and MS) indicates that the MSN5 membrane can be considered as a potential candidate as the PEM of DFMC because of the high level of selectivity and improved mechanical/chemical stabilities.
3.5. Mechanical and Oxidative Stability
It was important for a prepared membrane to have favorable mechanical stability for the fabrication of the MEA and lifetime of DMFCs. The TS and elongation at break (Eb) of the MS membrane and different nanocomposite membranes were illustrated in Table 2. The SPPEK polymer with pendant phenyls and heterocyclic structures is rigid and has good mechanical properties. As shown in Table 2, the pristine SPPEK has TS of 45.5 MPa with Eb at 10.8% and with the addition of SO3H–TiO2@[email protected]3H nanoparticles, the nanocomposite membranes attained an improvement on the mechanical properties. The mechanical stability appeared to be very sensitive to the nanoparticle content, as the TS increased rapidly with the increase of the SO3H–TiO2@[email protected]3H percentage. This fact is due to the nanoparticles that are uniformly dispersed throughout the polymeric matrix, forming intermolecular hydrogen bonding with functionalized groups of the polymer. Therefore, the SO3H–TiO2@[email protected]3H content increase determined a more compact structure of the membrane and an increase in TS based on the interaction between the polymeric chains and functionalized groups of the nanoparticles. (57) Another explanation for the improvement of the TS in the nanocomposite membrane relies on the existence of the nitrogen moiety in the polymer structure that provides adhesion between the polymer and SO3H–TiO2@[email protected]3H nanoparticles. (31) Further increase in the 5 % wt of nanoparticle loading led to a slight decrease of the TS, which may be linked with the agglomeration of the SO3H–TiO2@[email protected]3H nanoparticles in the structure of the membrane. (58) According to the results reported in Table 2, an increase in the modulus of nanocomposite membranes is due to the formation of the rigid structure because of strong hydrogen bonding between SO3H–TiO2@[email protected]3H nanoparticles and SPPEK. (11) In addition, the results reported in Table 2 show that according to the rigid structure of nanoparticles, with the addition of SO3H–TiO2@[email protected]3H nanoparticles to SPPEK, the Eb of nanocomposite membranes decreases. The interactions between the nanoparticles and the polymer decrease the freedom of movement of the polymer chains in the structure of membranes and consequently cause to decrease flexibility and Eb of the nanocomposite membranes. By increasing the amount of the nanoparticles in the membrane, the Eb of the membrane decreases further.
Table 2. Tensile Strength, Elongation at Break, Modulus, and Oxidative Stability of the Prepared Membranes
| membrane | TS (MPa) | Eb (%) | modulus (MPa) | oxidative stability (h) |
|---|---|---|---|---|
| MS | 45.5 | 10.8 | 1045 | 2.4 |
| MSN1 | 48.6 | 10.4 | 1102 | 3.1 |
| MSN3 | 50.2 | 9.8 | 1154 | 3.5 |
| MSN5 | 53.6 | 9.1 | 1218 | 4.2 |
| MSN7 | 52.4 | 8.8 | 1267 | 4.5 |
The oxidative stability of the membranes is one of the biggest issues for DMFCs. During the operation of DMFCs, hydroxyl (•OH) and hydroperoxy (•OOH) radicals are generated on both electrode sides. This process is ascribed to the degradation of H2O2 because of the incomplete reduction of oxygen, causing membrane ruin. (59) The time that the PEM could take to retain its shape before breaking, was recorded. As shown in Table 2, different nanocomposite membranes have higher oxidative stability than pristine SPPEK. The increase of the weight percentage of SO3H–TiO2@[email protected]3H nanoparticles in the membranes determines an improvement of the oxidative stability. The latter is directly related to MS. The membranes with large MS provide more chance for oxidative radicals (•OH and •OOH) to attack the polar groups of the polymer. (60,61) Therefore, MSN7 nanocomposite membranes show the best oxidative stability compared to other prepared membranes.
3.6. DMFC Test
To investigate the practical applications of membranes in DMFC operating conditions, different prepared membranes were used to measure the final performance of membranes in DMFC. The polarization curves of the as-prepared membranes, carried out in 2 M methanol solution and room temperature, are shown in Figure 10. The nanocomposite membranes show higher open-circuit voltage compared to the MS membrane, reflecting the low fuel cross-over in the nanocomposite membrane. (62) Methanol permeation as the fuel into the fabricated membranes causes an initial drop in voltage in the DMFC test. As seen in previous sections, the nanocomposite membranes exhibit several advantages such as higher proton conductivity, lower methanol permeability, and better selectivity compared to the MS membrane. Then, the nanocomposite membranes can be expected to exhibit better final performance than the MS membrane. Figure 10 shows the maximum power density of the MS membrane increased from 37.18 to 59.22 mW cm–2 with adding 5 wt % SO3H–TiO2@[email protected]3H nanoparticles. Also, the maximum current density of the MSN5 membrane was 267.36 mA cm–2, which is higher than the MS membrane (198.87 mA cm–2). The higher proton transfer of the nanocomposite membrane and lower methanol permeability due to compact structure increases the final performance of the nanocomposite membrane than the MS membrane. Also, in SO3H–TiO2@[email protected]3H nanoparticles, the sulfonamide groups could act as an additional excellent source of protons which could help the proton transfer across the membrane. It is well known that sulfonamides are Brønsted acids. (36) Thus, these properties can facilitate proton transfer in MEA and consequently can determine an increase of the final power density of DMFC. The results have shown that the MSN5 membrane exhibited the best maximum power density compared to the other nanocomposite membranes, which is due to better selectivity of this membrane compared to other membranes. According to the results of selectivity and power density, the MSN5 nanocomposite membrane shows potentiality for its use in DMFCs.
Figure 10
Figure 10. Polarization curves of different prepared membranes in 2 M methanol solution and room temperature.
4. Conclusions
ARTICLE SECTIONS
In this work, we assessed the potential of SPPEK-based membrane, added with organic–inorganic sulfonated titanium [email protected]@ethylenediamine (SO3H–TiO2@[email protected]3H) nanoparticles, in DMFCs. We investigated the loading dependence of the nanoparticles on the key parameters, such as water uptake, MS, morphology, proton conductivity, mechanical stability, and methanol permeability of the SPPEK-based membrane. Water uptake, MS, and methanol uptake of the as-prepared membranes are influenced by the increase of SO3H–TiO2@[email protected]3H nanoparticles. The methanol permeability results show that the addition of SO3H–TiO2@[email protected]3H nanoparticles acts as the barrier on the methanol cross-over, improving the selectivity of the nanocomposite membranes. The MSN5 nanocomposite membrane with the highest selectivity was selected for the DMFC test, showing a peak maximum power density of 59.22 mW cm–2 at room temperature. This value is higher than the one of Nafion 117 and SPPEK-based membranes under the same experimental conditions (see Table 3). The data reported in Table 3 show that the MSN5 membrane is a promising candidate for applications in DMFC.
Table 3. Comparison of the Different Properties of the MSN5 Membrane with SPPEK-Based Membranes and Nafion 117 Used in DMFC at 25 °C
| membranes | σ (S cm–1) | P (cm2 s–1) | S (S s–1 cm–3) | PD (mW cm–2) | refs |
|---|---|---|---|---|---|
| MSN5 | 0.091 | 3.10 × 10–7 | 29.35 × 104 | 59.22 | this work |
| SPPEK-dPa | 0.014 | 3.50 × 10–8 | 42.40 × 104 | (63) | |
| SPPEK/PWAb | 0.013 | 1.02 × 10–7 | 11.76 × 104 | 3.79 | (64) |
| SPPEK/SGNFc | 0.054 | 2.79 × 10–7 | 19.35 × 104 | 115.00d | (32) |
| Nafion 117 | 0.090 | 2.40 × 10–6 | 3.75 × 104 | 24.00 | (9) |
a
3,5-Diphenyl phthalazinone moieties.
b
Phosphotungstic acid.
c
Sulfonated graphite nanofibers.
d
Measured at 60 °C.
Author Information
ARTICLE SECTIONS
- Hossein Beydaghi - Graphene Labs, Istituto Italiano di Tecnologia, Via Morego 30, 16163 Genova, Italy;
http://orcid.org/0000-0002-7590-590X;
- Francesco Bonaccorso - Graphene Labs, Istituto Italiano di Tecnologia, Via Morego 30, 16163 Genova, Italy; BeDimensional SpA, Via Albisola 121, 16163 Genova, Italy;http://orcid.org/0000-0001-7238-9420;
Acknowledgments
ARTICLE SECTIONS
MAECI (Minister of Foreign Affairs and International Cooperation) is gratefully acknowledged for the bilateral Italy–China GINSENG project.
References
ARTICLE SECTIONS
This article references 64 other publications.
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- 10Beydaghi, H.; Javanbakht, M.; Bagheri, A.; Salarizadeh, P.; Zahmatkesh, H. G.; Kashefi, S.; Kowsari, E. Novel nanocomposite membranes based on blended sulfonated poly(ether ether ketone)/poly(vinyl alcohol) containing sulfonated graphene oxide/Fe3 O4 nanosheets for DMFC applications. RSC Adv. 2015, 5, 74054– 74064, DOI: 10.1039/c5ra12941a[Crossref], [CAS], Google Scholar10https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC2MXhtlOgtrnF&md5=1806dc83d3a5965c07ef590b33419cf3Novel nanocomposite membranes based on blended sulfonated poly(ether ether ketone)/poly(vinyl alcohol) containing sulfonated graphene oxide/Fe3O4 nanosheets for DMFC applicationsBeydaghi, Hossein; Javanbakht, Mehran; Bagheri, Ahmad; Salarizadeh, Parisa; Zahmatkesh, Hossein Ghafarian-; Kashefi, Sepideh; Kowsari, ElahehRSC Advances (2015), 5 (90), 74054-74064CODEN: RSCACL; ISSN:2046-2069. (Royal Society of Chemistry)In this study, sulfonated graphene oxide (SGO)/Fe3O4 nanosheets were synthesized by hydrothermal method and incorporated into blend sulfonated poly(ether ether ketone) (SPEEK)/poly(vinyl alc.) (PVA) matrix with different wt. percent of (SGO)/Fe3O4 nanosheets. The performances of prepd. membranes were investigated by water uptake, membrane swelling, mech. and thermal stability, proton cond., methanol permeability and DMFC test. It was found that the water uptake and tensile strength of SPEEK membrane increased and proton cond. and power d. decreased by blending with PVA. Incorporation of SGO/Fe3O4 nanosheets into SPEEK/PVA matrix enhanced mech. stability, proton cond. and methanol barrier properties of membrane. The SPEEK/PVA/SGO/Fe3O4 nanocomposite membrane with optimal nanosheets content (5 wt%) exhibits low methanol permeability (8.83 × 10-7 cm2 s-1), high tensile strength (51.2 MPa), high proton cond. (0.084 S cm-1 at 25 °C) and high power d. (122.7 mW cm-2 at 80 °C) and suggests its potential application in DMFCs.
- 11Bagheri, A.; Javanbakht, M.; Hosseinabadi, P.; Beydaghi, H.; Shabanikia, A. Preparation and characterization of SPEEK/SPVDF-co-HFP/LaCrO3 nanocomposite blend membranes for direct methanol fuel cells. Polymer 2018, 138, 275– 287, DOI: 10.1016/j.polymer.2018.01.049[Crossref], [CAS], Google Scholar11https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC1cXisFehsrg%253D&md5=7fdc8e7c6604ac14ed10d50a8f06e630Preparation and characterization of SPEEK/SPVDF-co-HFP/LaCrO3 nanocomposite blend membranes for direct methanol fuel cellsBagheri, Ahmad; Javanbakht, Mehran; Hosseinabadi, Parisa; Beydaghi, Hossein; Shabanikia, AkbarPolymer (2018), 138 (), 275-287CODEN: POLMAG; ISSN:0032-3861. (Elsevier Ltd.)Here, nanocomposite blend membrane comprised of the sulfonated poly(ether ether ketone) (SPEEK), sulfonated poly(vinylidenefluoride-co-hexafluoropropylene) (SPVDF-co-HFP) and LaCrO3 was prepd. by the solvent casting method. The prepd. membranes exhibit a variety of advantages, such as desirable proton cond., good thermal and mech. stability, outstanding water and MeOH retention and oxidative stability. The increase in proton cond. from 32.7 mS/cm in SPEEK/SPVDF-co-HFP blend membrane to 75.3 mS/cm in nanocomposite membrane is achieved at the nanoparticle content of 1.5 wt.% at 20°, stemming from enhanced connectivity of the ionic groups which facilitates the proton transportation through the membrane. The MeOH permeability of the nanocomposite membranes was altered from 2.11 × 10-7 to 1.90 × 10-7 cm2/s, by addn. of 1.5 wt.% LaCrO3 nanoparticles, which show this membrane can act as effective barrier against MeOH permeation. The max. power d. of blend membrane was increased from 43.0 to 61.5 mW/cm2 with addn. of 1.5 wt.% nanoparticles and this results show that the nanocomposite membranes could be applied as a promising candidate as a proton exchange membrane for direct MeOH fuel cells.
- 12Selvakumar, K.; Ramesh Prabhu, M. Investigation on meta-polybenzimidazole blend with sulfonated PVdF-HFP proton conducting polymer electrolytes for HT-PEM fuel cell application. J. Mater. Sci.: Mater. Electron. 2018, 29, 15163– 15173, DOI: 10.1007/s10854-018-9658-z[Crossref], [CAS], Google Scholar12https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC1cXhtlalsbrK&md5=c3ae5687dce3a7e3b2fa0775d01acc14Investigation on meta-polybenzimidazole blend with sulfonated PVdF-HFP proton conducting polymer electrolytes for HT-PEM fuel cell applicationSelvakumar, Kanagaraj; Ramesh Prabhu, ManimuthuJournal of Materials Science: Materials in Electronics (2018), 29 (17), 15163-15173CODEN: JSMEEV; ISSN:0957-4522. (Springer)Sulfonated poly (Vinylidene Fluoride-co-hexafluoro propylene) (SPVdF-HFP) blended with varying concns. of m-poly (Benzimidazole) (PBI) were prepd. by soln. casting techinque. The sulfonation of PVdF-HFP was carried out with fuming chlorosulfonic acid at 60 °C and the degree of sulfonation was found to be 2.48%. The addn. of m-PBI into the hydrophilic sulfonated PVdF-HFP membrane has provided good chem. and thermal stability. And also the increases the physico-chem. characteristics such as the water uptake, ion exchange capacity and proton cond. An inter chain sepn. and specific interaction between the two polymers in the blends was obsd. by XRD and FT-IR analyses. The Fourier transform spectroscopy indicated the intense ionic bond between-SO3H and N-basic group. The 25% of m-PBI based blend polymer electrolyte gives high proton cond. (5.72 × 10-3 S/cm) at 160 °C and also the thermal stability. The temp. dependent proton cond. of the polymer electrolyte follows an Arrhenius relationship and Grotthuss mechanism and it shows hopping of ions in the polymer matrix. It is noticed that the addn. of m-PBI in the sulfonated PVdF-HFP enhances the mech., thermal and proton cond., which are sufficiently better for the use in HT-PEM fuel cell applications.
- 13Ozden, A.; Ercelik, M.; Devrim, Y.; Colpan, C. O.; Hamdullahpur, F. Evaluation of sulfonated polysulfone/zirconium hydrogen phosphate composite membranes for direct methanol fuel cells. Electrochim. Acta 2017, 256, 196– 210, DOI: 10.1016/j.electacta.2017.10.002[Crossref], [CAS], Google Scholar13https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC2sXhs1Chsb3J&md5=f812fea008b31e8bb2bd9d0c61a9e99dEvaluation of sulfonated polysulfone/zirconium hydrogen phosphate composite membranes for direct methanol fuel cellsOzden, Adnan; Ercelik, Mustafa; Devrim, Yilser; Colpan, C. Ozgur; Hamdullahpur, FeridunElectrochimica Acta (2017), 256 (), 196-210CODEN: ELCAAV; ISSN:0013-4686. (Elsevier Ltd.)Direct MeOH fuel cell (DMFC) technol. has advanced perceivably, but tech. challenges remain that must be overcome for further performance improvements. Thus, sulfonated polysulfone/Zr H phosphate (SPSf/ZrP) composite membranes with various sulfonation degrees (20%, 35%, and 42%) and a const. concn. of ZrP (2.5%) were prepd. to mitigate the tech. challenges assocd. using conventional Nafion membranes in DMFCs. The composite membranes were studied through SEM, Electrochem. Impedance Spectroscopy (EIS), Thermogravimetric Anal. (TGA), oxidative stability and H2O uptake measurements, and single cell testing. Comparison was also made with Nafion 115. Single cell tests were performed under various MeOH concns. and cell temps. Stability characteristics of the DMFCs under charging and discharging conditions were studied via 1200 min short-term stability tests. The response characteristics of the DMFCs under dynamic conditions were detd. at the start-up and shut-down stages. Composite membranes with sulfonation degrees of 35% and 42% are highly promising due to their advanced characteristics with respect to proton cond., H2O uptake, thermal resistance, oxidative stability, and MeOH suppression. For the whole range of parameters studied, the max. power d. obtained for SPSf/ZrP-42 (119 mW cm-2) is 13% higher than that obtained for Nafion 115 (105 mW cm-2).
- 14Amoozadeh, A.; Mazdarani, H.; Beydaghi, H.; Tabrizian, E.; Javanbakht, M. Novel nanocomposite membrane based on Fe3O4@[email protected]2–SO3H: hydration, mechanical and DMFC study. New J. Chem. 2018, 42, 16855– 16862, DOI: 10.1039/c8nj03646b[Crossref], [CAS], Google Scholar14https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC1cXhs1Cgtb%252FN&md5=bdb6c823e57294a09afbb29424d9c385Novel nanocomposite membrane based on [email protected]@TiO2-SO3H: hydration, mechanical and DMFC studyAmoozadeh, Ali; Mazdarani, Hourieh; Beydaghi, Hossein; Tabrizian, Elham; Javanbakht, MehranNew Journal of Chemistry (2018), 42 (20), 16855-16862CODEN: NJCHE5; ISSN:1144-0546. (Royal Society of Chemistry)In this paper, a sulfonated poly(ether ether ketone)/SO3H-functionalized magnetic-titania (SPEEK/[email protected]@TiO2-SO3H) nanocomposite membrane is synthesized with the aim of reducing methanol permeability as well as improving the proton cond. and selectivity of pristine polymer to be used instead of Nafion in a direct methanol fuel cell (DMFC). The introduced nanocomposite membrane is prepd. by soln. casting of SPEEK in di-Me acetamide (DMAc) solvent and dispersing various percentages of [email protected]@TiO2-SO3H in the polymer matrix. The different properties of the membranes were investigated by ion exchange capacity, water uptake, mech. stability, proton cond., methanol permeability, selectivity and a DMFC test. The catalytic properties of [email protected]@TiO2-SO3H nanoparticles improve the power d. of DMFC with increasing reaction kinetics in the membrane electrode assembly (MEA). According to the obtained results, a nanocomposite membrane (with optimum 5 wt% nanoparticles) has low methanol permeability (3.35 × 10-7 cm2 s-1), high proton cond. (0.081 S cm-1), high mech. stability (34.87 MPa) and high power d. (51.27 mW cm-2), which makes it a suitable membrane for DMFCs.
- 15Selvakumar, K.; Rajendran, S.; Ramesh Prabhu, M. Influence of barium zirconate on SPEEK-based polymer electrolytes for PEM fuel cell applications. Ionics 2019, 25, 2243– 2253, DOI: 10.1007/s11581-018-2613-4[Crossref], [CAS], Google Scholar15https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC1cXhtFWiu7bF&md5=2135540e1b979a84f4957e363ca6e754Influence of barium zirconate on SPEEK-based polymer electrolytes for PEM fuel cell applicationsSelvakumar, K.; Rajendran, S.; Ramesh Prabhu, M.Ionics (2019), 25 (5), 2243-2253CODEN: IONIFA; ISSN:0947-7047. (Springer)The sulfonated poly(ether ether ketone) (SPEEK)-barium zirconate (BaZrO3)-based polymer nanocomposite membranes are prepd. by solvent casting technique. The composite membranes have been characterized by X-ray diffraction (XRD), Fourier transform IR spectroscopy (FTIR), NMR (NMR), water uptake, swelling, and ion exchange capacity (IEC). The NMR, IEC, and CHNSO analyses confirmed the degree of sulfonation level of SPEEK as 65%. Addn. of 6 wt% BaZrO3 filler improved the proton cond. of the polymer electrolyte considerably with 3.12 × 10-1 S/cm at 90 °C. SEM and AFM studies indicated that the BaZrO3 nanofillers are well distributed in the polymer up to 8 wt%. The max. power and c.d. are 183 mW cm-2 and 280 mA cm-2 for 94 wt% SPEEK and 06 wt% BaZrO3. It is concluded that the above composite membrane is a potential candidate for PEM fuel cell applications.
- 16Raja, K.; Raja Pugalenthi, M.; Ramesh Prabhu, M. Investigation on SPEEK/PAI/SrTiO3-based nanocomposite membrane for high-temperature proton exchange membrane fuel cells. Ionics 2019, 25, 5177– 5188, DOI: 10.1007/s11581-019-03100-7[Crossref], [CAS], Google Scholar16https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC1MXht1WqsbjN&md5=704a118e96aeb3b2f72e2e00b9c31c9aInvestigation on SPEEK/PAI/SrTiO3-based nanocomposite membrane for high-temperature proton exchange membrane fuel cellsRaja K; Raja Pugalenthi M; Ramesh Prabhu MIonics (2019), 25 (11), 5177-5188CODEN: IONIFA; ISSN:0947-7047. (Springer)Optimization of an alternative proton exchange membrane fuel cell (PEMFC) instead of Nafion membrane electrolyte with sulfonated poly(ether ether ketone) (SPEEK) is regarded as the most promising alternative to com. membranes. In this work, facile composite membranes consisting of SPEEK/poly (amide imide) (PAI) and SrTiO3-based nanocomposite electrolyte are prepd. by solvent casting technique. The prepd. samples are characterized by FT-IR, thermo-mech. stability, electrochem. impedance spectroscopy (EIS), water uptake capacity, swelling ratio, and ion transport capacity tests. The incorporation of PAI in the membrane structure has increased the mech. strength, increased water uptake, and restricted swelling ratio. Incorporation of SrTiO3 nanoparticle fillers are easily bounded into the polymer membrane matrix via ionic interaction due to presence of sulfonic acid groups moieties in SPEEK. The addn. of SrTiO3 filler in the blend membranes provided enhanced protonic cond., ion exchange capacity with restricted swelling capacity, and inhibit water loss at high temps. The highest proton cond. of 10.78 × 10-3 S cm-1 at 150°C is obtained by the SPEEK (90 wt%)/PAI (10 wt%)/SrTiO3 (06 wt%) coded membrane in electrochem. impedance spectroscopy. This study shows that nanocomposite blend membrane seems to be a promising alternative membrane for PEMFC application.
- 17Raja, K.; Raja Pugalenthi, M.; Ramesh Prabhu, M. The effect of incorporation of ferrous titanate nanoparticles in sulfonated poly(ether ether ketone)/poly (amide imide) acid-base polymer for cations exchange membrane fuel cells. J. Solid State Electrochem. 2019, 24, 35, DOI: 10.1007/s10008-019-04453-9
- 18Bagheri, A.; Salarizadeh, P.; Sabooni Asre Hazer, M.; Hosseinabadi, P.; Kashefi, S.; Beydaghi, H. The effect of adding sulfonated SiO2 nanoparticles and polymer blending on properties and performance of sulfonated poly ether sulfone membrane: Fabrication and optimization. Electrochim. Acta 2019, 295, 875– 890, DOI: 10.1016/j.electacta.2018.10.197[Crossref], [CAS], Google Scholar18https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC1cXit1aqt7jM&md5=b829957c1a25b643d7d0f40ea5b09147The effect of adding sulfonated SiO2 nanoparticles and polymer blending on properties and performance of sulfonated poly ether sulfone membrane: Fabrication and optimizationBagheri, Ahmad; Salarizadeh, Parisa; Sabooni Asre Hazer, Maryam; Hosseinabadi, Parisa; Kashefi, Sepideh; Beydaghi, HosseinElectrochimica Acta (2019), 295 (), 875-890CODEN: ELCAAV; ISSN:0013-4686. (Elsevier Ltd.)Sulfonated poly(phthalazinone ether ketone) and modified silica nanoparticles by poly (2-acrylamido-2-methyl-1-propanesulfonic acid) were prepd. and their impact investigated on the physicochem. and transport properties of sulfonated poly ether sulfone. To optimize the wt. percentage of incorporated components in sulfonated poly ether sulfone nanocomposite membranes and predict their performance, the central composite design (CCD) of the response surface method (RSM) was utilized. The independent parameters (wt. percentage of added sulfonated poly (phthalazinone ether ketone) (SPPEK) and nanoparticles) and the responses (water uptake (WU), swelling ratio (SR), δ value, proton cond., methanol permeability and selectivity) were developed and verified with exptl. data. The optimum parameters for achieving the highest performance represented by proton cond. of 57.9 mS cm-1, methanol permeability of 3.21 × 10-7 cm2 s-1, and membrane selectivity of 18.03 × 104 s S cm-3 obtained at contents of SPPEK and nanoparticles of 23.07 and 3.9 wt%, resp. The membrane with optimum additives demonstrated favorable direct methanol fuel cell (DMFC) characteristics such as reduced methanol permeability, high selectivity, and improved mech. integrity as well as power d.
- 19Kalaiselvimary, J.; Prabhu, M. R. Influence of sulfonated GO/sulfonated biopolymer as polymer electrolyte membrane for fuel cell application. J. Mater. Sci.: Mater. Electron. 2018, 29, 5525– 5535, DOI: 10.1007/s10854-018-8521-6[Crossref], [CAS], Google Scholar19https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC1cXhtl2qtr0%253D&md5=9d44c3c081f36f3cd6c1d81eba1ab6a8Influence of sulfonated GO/sulfonated biopolymer as polymer electrolyte membrane for fuel cell applicationKalaiselvimary, J.; Prabhu, M. RameshJournal of Materials Science: Materials in Electronics (2018), 29 (7), 5525-5535CODEN: JSMEEV; ISSN:0957-4522. (Springer)Graphene oxide is well known as a advanced functional material because of its super high sp. surface area, as well as excellent amphipathicity. Sulfonated graphene oxide bio nanocomposite membranes are presented as a potential proton exchange membrane for fuel cell applications. The GO nanopowder was produced from graphite powder by the modified Hummers method and then sulfonated by chlorosulfonic acid as a sulfonic reagent. The s-GO-based s-CS/PEO composite membranes were prepd. by soln. casting technique. The synthesized electrolytes are studied by different characterization to check the elec. and thermal properties of the membrane. FTIR and Raman showed the formation of GO, s-GO and prepd. electrolytes interaction between the functional groups resp. The max. ionic cond. of s-Chitosan (s-CS)/PEO/s-GO nanocomposite membranes at 6 wt% of s-GO in the order of 10-2 S/cm. Moreover, the existence of the intermol. interactions between sulfonated-CS/PEO and s-GO can improve the thermal stability and interfacial compatibility between nanofiller and polymer matrixes.
- 20Beydaghi, H.; Javanbakht, M.; Salarizadeh, P.; Bagheri, A.; Amoozadeh, A. Novel proton exchange membrane nanocomposites based on sulfonated tungsten trioxide for application in direct methanol fuel cells. Polymer 2017, 119, 253– 262, DOI: 10.1016/j.polymer.2017.05.026[Crossref], [CAS], Google Scholar20https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC2sXos1Sls78%253D&md5=9a0fad9a4df0518575e7e79ba5fe7ec8Novel proton exchange membrane nanocomposites based on sulfonated tungsten trioxide for application in direct methanol fuel cellsBeydaghi, Hossein; Javanbakht, Mehran; Salarizadeh, Parisa; Bagheri, Ahmad; Amoozadeh, AliPolymer (2017), 119 (), 253-262CODEN: POLMAG; ISSN:0032-3861. (Elsevier Ltd.)Novel sulfonated poly (phthalazinone ether ketone) (SPPEK)/sulfonated poly (vinylidene fluoride-co-hexafluoropropylene) (SPVdF-co-HFP)/sulfonated tungsten trioxide (SWO3) nanocomposite blend membranes were fabricated as alternative proton exchange membranes (PEM) for application in direct methanol fuel cell (DMFC). PPEK and PVdF-co-HFP were sulfonated using sulfuric acid and chlorosulfonic acid, resp. The degree of sulfonation (DS) of produced SPPEK and SPVdF-co-HFP were detd. by titrn. method and found to be 68% and 30%, resp. The dominant characteristics of the prepd. membranes, such as water uptake, membrane swelling, proton cond., methanol permeability, selectivity and DMFC performance were investigated. The membranes contg. SWO3 nanoparticles indicated higher proton cond. and lower methanol permeability compared with pristine SPPEK and blend membranes. This improvement is attributed to presence of the sulfonated groups of nanoparticles that increases proton cond. with Grotthus and vehicle mechanisms. The catalytic properties of SWO3 nanoparticles increase kinetic of reaction in interface surface of membrane and electrode and improve performance of DMFCs. Well optimized nanocomposite blend membrane (MSSW5) showed proton cond. of 0.071 S cm-1, methanol permeability of 9.5 × 10-8 cm2 S-1 and power d. of 63.60 mW cm-2 at room temp., thus it can be a suitable candidate for DMFC application.
- 21Hooshyari, K.; Heydari, S.; Javanbakht, M.; Beydaghi, H.; Enhessari, M. Fabrication and performance evaluation of new nanocomposite membranes based on sulfonated poly(phthalazinone ether ketone) for PEM fuel cells. RSC Adv. 2020, 10, 2709– 2721, DOI: 10.1039/c9ra08893h[Crossref], [CAS], Google Scholar21https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BB3cXptlahtQ%253D%253D&md5=08d8c2c38e1999e1d15d12c1d4779f2fFabrication and performance evaluation of new nanocomposite membranes based on sulfonated poly(phthalazinone ether ketone) for PEM fuel cellsHooshyari, Khadijeh; Heydari, Samira; Javanbakht, Mehran; Beydaghi, Hossein; Enhessari, MortezaRSC Advances (2020), 10 (5), 2709-2721CODEN: RSCACL; ISSN:2046-2069. (Royal Society of Chemistry)The purpose of this work is to enhance the proton cond. and fuel cell performance of sulfonated poly(phthalazinone ether ketone) (SPPEK) as a proton exchange membrane through the application of SrTiO3 perovskite nanoparticles. Nanocomposite membranes based on SPPEK and SrTiO3 perovskite nanoparticles were prepd. via a casting method. The highest proton cond. of nanocomposite membranes obtained was 120 mS cm-1 at 90°C and 95% RH. These enhancements could be related to the hygroscopic structure of SrTiO3 perovskite nanoparticles and the formation of hydrogen bonds between nanoparticles and water mols. The satisfactory power d., 0.41 W cm-2 at 0.5 V and 85°C, of the nanocomposite membrane (5 wt% content of nanoparticles) confirms their potential for application in the PEM fuel cells.
- 22Luo, T.; Zhang, Y.; Xu, H.; Zhang, Z.; Fu, F.; Gao, S.; Ouadah, A.; Dong, Y.; Wang, S.; Zhu, C. Highly conductive proton exchange membranes from sulfonated polyphosphazene-graft-copolystyrenes doped with sulfonated single-walled carbon nanotubes. J. Membr. Sci. 2016, 514, 527– 536, DOI: 10.1016/j.memsci.2016.04.071[Crossref], [CAS], Google Scholar22https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC28XovVaitrc%253D&md5=d1112a8fb67d1044fe563082ea480935Highly conductive proton exchange membranes from sulfonated polyphosphazene-graft-copolystyrenes doped with sulfonated single-walled carbon nanotubesLuo, Tianwei; Zhang, Yanxia; Xu, Hulin; Zhang, Zeyu; Fu, Fengyan; Gao, Shuitao; Ouadah, Amina; Dong, Yan; Wang, Shan; Zhu, ChangjinJournal of Membrane Science (2016), 514 (), 527-536CODEN: JMESDO; ISSN:0376-7388. (Elsevier B.V.)As polymer electrolyte candidates, a series of composite membranes CF3-PSx-PSBOSy-SCNT of copolymer poly[(4-trifluoromethylphenoxy)(4-methylphenoxy)phosphazene]-g-poly{(styrene)x-r-[4-(4-sulfobutyloxy)styrene]y} (CF3-PSx-PSBOSy) doped with sulfonated single-walled carbon nanotubes (S-SWCNTs) were prepd. Most of them showed higher proton cond. than that of Nafion 117. Compared with native membranes, the composite membranes exhibited higher proton cond. but also a significantly reduced methanol permeability, suggesting a great enhancement effect of S-SWCNTs on the proton conduction and methanol resistance. Specifically, membranes CF3-PS11-PSBOS33-SCNT and CF3-PSBOS45-SCNT showed proton cond. at 0.46 S/cm and 0.55 S/cm under fully hydrated conditions at 100 °C, resp., which were 2.2-2.6 times as much as that of Nafion 117. Excellent selectivity much more than that of Nafion 117 were also obtained for the composite membranes.
- 23Beydaghi, H.; Javanbakht, M.; Kowsari, E. Synthesis and characterization of poly(vinyl alcohol)/sulfonated graphene oxide nanocomposite membranes for use in PEMFCs. Ind. Eng. Chem. Res. 2014, 53, 16621– 16632, DOI: 10.1021/ie502491d[ACS Full Text], [CAS], Google Scholar23https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC2cXhslahsrjN&md5=ff56c8d36efcca914494c48dbf895974Synthesis and Characterization of Poly(vinyl alcohol)/Sulfonated Graphene Oxide Nanocomposite Membranes for Use in Proton Exchange Membrane Fuel Cells (PEMFCs)Beydaghi, Hossein; Javanbakht, Mehran; Kowsari, ElahehIndustrial & Engineering Chemistry Research (2014), 53 (43), 16621-16632CODEN: IECRED; ISSN:0888-5885. (American Chemical Society)In this study, novel cross-linked nanocomposite membranes have been prepd. from poly(vinyl alc.) (PVA) and aryl sulfonated graphene oxide (SGO) and a way of crosslinking to improve the chem., thermal, and mech. stabilities of the nanocomposite was adopted. The surface of the graphene oxide nanoparticles was modified by aryl diazonium salt of sulfanilic acid. It was revealed that addn. of SGO (5 wt %) into the PVA matrix improves the thermal stability (melting temp., Tm = 223 °C), mech. stability (tensile strength, TS = 67.8 MPa) and proton cond. (σ = 0.050 S cm-1) of the nanocomposite proton exchange membranes. A proton exchange membrane fuel cell (PEMFC) fabricated with the PVA/SGO membrane showed a max. power d. of 16.15 mW cm-2 at 30 °C. As a result, the investigated PVA/SGO nanocomposite membranes have good potential for further studies and applications in PEMFCs.
- 24Beydaghi, H.; Javanbakht, M. Aligned nanocomposite membranes containing sulfonated graphene oxide with superior ionic conductivity for direct methanol fuel cell application. Ind. Eng. Chem. Res. 2015, 54, 7028– 7037, DOI: 10.1021/acs.iecr.5b01450[ACS Full Text], [CAS], Google Scholar24https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC2MXhtVOktr7K&md5=2fa4bb4809d51c6f672cb78b6b2f62c8Aligned Nanocomposite Membranes Containing Sulfonated Graphene Oxide with Superior Ionic Conductivity for Direct Methanol Fuel Cell ApplicationBeydaghi, Hossein; Javanbakht, MehranIndustrial & Engineering Chemistry Research (2015), 54 (28), 7028-7037CODEN: IECRED; ISSN:0888-5885. (American Chemical Society)In this work, iron oxide (Fe3O4) nanoparticles are deposited onto sulfonated graphene oxide (SGO) nanosheets using a solvothermal method. By applying a magnetic field on the soln. during casting, the SGO/Fe3O4 nanosheets are drawn to the through-plane direction of the membrane. The structures of the nanosheets and membranes are characterized. The aligned poly(vinyl alc.) (PVA)/SGO/Fe3O4 membrane shows higher proton cond., water uptake, thermal stability, methanol permeability, and selectivity compared to a nonaligned membrane. By orientation of nanosheets, 5.7% improvement in the tensile stress of the membranes is obsd. The aligned PVA/SGO/Fe3O4 nanocomposite membrane generates the highest power d. of 25.57 mW cm-1 at 30 °C. As a result, the aligned PVA/SGO/Fe3O4 nanocomposite membrane appears to be a good candidate for direct methanol fuel cell application.
- 25Javanbakht, M.; Hooshyari, K.; Enhessari, M.; Beydaghi, H. Novel PVA/La2Ce2O7 hybrid nanocomposite membranes for application in proton exchange membrane fuel cells. Iran. J. Hydrogen Fuel Cell 2014, 1, 105– 112Google ScholarThere is no corresponding record for this reference.
- 26Hooshyari, K.; Khanamiri, S. N.; Salarizadeh, P.; Beydaghi, H. Nanocomposite membranes with high fuel cell performance based on sulfonated poly (1, 4-phenylene ether ether sulfone) and ytterbium/yttrium doped-perovskite nanoparticles. J. Electrochem. Soc. 2019, 166, F976– F989, DOI: 10.1149/2.1521912jes[Crossref], [CAS], Google Scholar26https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BB3cXhs1ymsr4%253D&md5=c4ec937436d4455978b03993d76afd11Nanocomposite membranes with high fuel cell performance based on sulfonated poly (1,4-phenylene ether ether sulfone) and ytterbium/yttrium doped-perovskite nanoparticlesHooshyari, Khadijeh; Khanamiri, Sima Nazari; Salarizadeh, Parisa; Beydaghi, HosseinJournal of the Electrochemical Society (2019), 166 (13), F976-F989CODEN: JESOAN; ISSN:0013-4651. (Electrochemical Society)In the present study, new nanocomposite membranes based on sulfonated poly(1,4-phenylene ether-ether sulfone), BaZr0.9Y0.1O3-δ and SrCe0.9Yb0.1O3-δ doped-perovskite nanoparticles were prepd. The BaZr0.9Y0.1O3-δ and SrCe0.9Yb0.1O3-δ doped-perovskite nanoparticles enhance the thermal and mech. stability of the nanocomposite membranes. Besides, the water up-take of the nanocomposite membranes increases and so, the proton cond. increase. Substitution of Ce4+ by Yb3+ in the SrCe0.9Yb0.1O3-δ doped-perovskite nanoparticles and the substitution of Zr4+ by Y3+ in the BaZr0.9Y0.1O3-δ doped-perovskite nanoparticles produce oxygen vacancies and decrease the coulombic repulsion between protons and pos. ions. The oxygen vacancies in BaZr0.9Y0.1O3-δ and SrCe0.9Yb0.1O3-δ doped-perovskite nanoparticles act as water and protons trap, and so increase the rotational motion of the proton and the proton cond. in the nanocomposite membranes. The highest proton cond. for the nanocomposite membranes contg. the BaZr0.9Y0.1O3-δ and SrCe0.9Yb0.1O3-δ doped-perovskite nanoparticles are 126 mS cm-1 and 117 mS cm-1, resp., at 80° and 95% RH. The long lifetime of the proton cond. and considerable fuel cell performance, 0.61 W cm-2 power d. at 0.5 V, of the nanocomposite membranes confirm their high potential for application in the PEM fuel cells.
- 27Beydaghi, H.; Javanbakht, M.; Badiei, A. Cross–linked poly(vinyl alcohol)/sulfonated nanoporous silica hybrid membranes for proton exchange membrane fuel cell. J. Nanostruct. Chem. 2014, 4, 97, DOI: 10.1007/s40097-014-0097-y
- 28Ru, C.; Gu, Y.; Na, H.; Li, H.; Zhao, C. Preparation of a cross-linked sulfonated poly(arylene ether ketone) proton exchange membrane with enhanced proton conductivity and methanol resistance by introducing an ionic liquid-impregnated metal organic framework. ACS Appl. Mater. Interfaces 2019, 11, 31899– 31908, DOI: 10.1021/acsami.9b09183[ACS Full Text], [CAS], Google Scholar28https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC1MXhsFKlurvI&md5=178f40a0f7fbdc2eb81efe27a174e99cPreparation of a Cross-Linked Sulfonated Poly(arylene ether ketone) Proton Exchange Membrane with Enhanced Proton Conductivity and Methanol Resistance by Introducing an Ionic Liquid-Impregnated Metal Organic FrameworkRu, Chunyu; Gu, Yiyang; Na, Hui; Li, Haolong; Zhao, ChengjiACS Applied Materials & Interfaces (2019), 11 (35), 31899-31908CODEN: AAMICK; ISSN:1944-8244. (American Chemical Society)A novel ionic liq.-impregnated metal-org.-framework ([email protected]) was prepd. and introduced into sulfonated poly(arylene ether ketone) with pendent carboxyl groups (SPAEK) as the nanofiller for achieving hybrid proton exchange membranes. The nanofiller was anchored in the polymeric matrix by the formation of amido linkage between the pendent carboxyl group attached to the mol. chain of SPAEK and amino group belonging to the inorg. framework, thus leading to the enhancement in mech. properties and dimensional stability. Besides, the hybrid membrane ([email protected]) exhibits an enhanced proton cond. up to 0.184 S·cm-1 because of the incorporation of ionic liq. in the nanocages of NH2-MIL-101. Moreover, the special structure of NH2-MIL-101 contributes to a low leakage of ionic liq. so as to retain the stable proton cond. of hybrid membranes under fully hydrated conditions. Furthermore, as a result of a crosslinked structure formed by inorg. nanofiller, the [email protected] hybrid membrane shows a lower methanol permeability (7.53 × 10-7 cm2 s-1) and superior selectivity (2.44 × 105 S s cm-3) than the pristine SPAEK membrane. Esp., [email protected] performs high single-cell efficiency with a peak power d. of 37.5 mW cm-2, almost 2.3-fold to SPAEK. Electrochem. impedance spectroscopy and SEM indicated that the nanofiller not only contributed to faster proton transfer but also resulted in a tighter bond between the membrane and catalyst. Therefore, the incorporation of [email protected] to prep. the hybrid membrane is proven to be suitable for application in direct methanol fuel cells.
- 29Wang, N.; Yu, J.; Zhou, Z.; Fang, D.; Liu, S.; Liu, Y. SPPEK/TPA composite membrane as a separator of vanadium redox flow battery. J. Membr. Sci. 2013, 437, 114– 121, DOI: 10.1016/j.memsci.2013.02.053[Crossref], [CAS], Google Scholar29https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC3sXnslait7Y%253D&md5=48a57f9add5d931ad8222e9999827d46SPPEK/TPA composite membrane as a separator of vanadium redox flow batteryWang, Nanfang; Yu, Jingang; Zhou, Zhi; Fang, Dong; Liu, Suqin; Liu, YounianJournal of Membrane Science (2013), 437 (), 114-121CODEN: JMESDO; ISSN:0376-7388. (Elsevier B.V.)To improve the performance of a low cost sulfonated poly(phthalazinone ether ketone) (SPPEK) membrane in V redox flow battery (VRFB), composite membranes composed of SPPEK and tungstophosphoric acid (TPA) with 8-25% concn. were prepd. by soln. casting. The results of SEM, energy dispersive x-ray spectroscopy (EDS), and XRD of the SPPEK/TPA composite membrane revealed that TPA had excellent compatibility with SPPEK in the bulk of the membrane. The effect of the TPA concn. on the primary properties, permeability of V ions and ionic selectivity, and chem. stability of the composite membrane was studied. The single cell tests showed that the VRFB employing the SPPEK-TPA-17 membrane with 17% TPA exhibited a higher coulombic efficiency (98.75% vs. 92.81%) and energy efficiency (74.58% vs. 73.83%) than those of the Nafion system. Cycling and chem. stability tests indicated that the SPPEK/TPA composite membrane had high stability in the VRFB system.
- 30Liu, Z.; Zhu, X.; Wang, G.; Hou, X.; Liu, D. Novel crosslinked alkaline exchange membranes based on poly(phthalazinone ether ketone) for anion exchange membrane fuel cell applications. J. Polym. Sci., Part B: Polym. Phys. 2013, 51, 1632– 1638, DOI: 10.1002/polb.23377[Crossref], [CAS], Google Scholar30https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC3sXhsVeisr3O&md5=9783a1aefa5412e9c384c1aa341d09c6Novel crosslinked alkaline exchange membranes based on poly(phthalazinone ether ketone) for anion exchange membrane fuel cell applicationsLiu, Zhi; Zhu, Xiuling; Wang, Guangfu; Hou, Xixin; Liu, DezhiJournal of Polymer Science, Part B: Polymer Physics (2013), 51 (22), 1632-1639CODEN: JPBPEM; ISSN:0887-6266. (John Wiley & Sons, Inc.)Novel crosslinked anion exchange membranes based on poly(phthalazinone ether ketone) (PPEK) were successfully prepd. through chloromethylation, quaternization, membrane casting and OH- ionic exchange reaction from the quaternized PPEK (QPPEK) membrane. The quaternization was performed with N-methylimidazolium (MIm) as ammonium agent and tetramethylethylenediamine (TMEDA) as crosslinking agent. The ion-exchange capacity, swelling ratio (SR), water uptake (WU), and ionic cond. of the QPPEK alk. membranes have been systematically investigated. The results showed that QPPEK membranes have a high hydroxide cond. and very low SR. For the QPPEK-4 alk. membrane with ion-exchange capacity (IEC) 2.63 mmol/g, the WU was 35.8%, and the hydroxide cond. was 0.028 S/cm at 30 °C and 0.032 S/cm at 70 °C, while its SR was only 7.6%. The thermal properties of the QPPEK alk. membrane and CMPPEK were characterized using thermo-gravimetric anal. measurements in a nitrogen atm. The alk. resistance of membrane QPPEK -4 was also briefly investigated in 6 M KOH at 60 °C. © 2013 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys, 2013.
- 31Hongwei, Z.; Fei, Y.; Danying, Z. Fabrication and characterization of electrospun sulfonated poly(phthalazinone ether ketone) mats as potential matrix of reinforced proton exchange membranes. J. Appl. Polym. Sci. 2013, 130, 4581– 4586, DOI: 10.1002/app.39718
- 32Rambabu, G.; Sasikala, S.; Bhat, S. D. Nanocomposite membranes of sulfonated poly(phthalalizinone ether ketone)–sulfonated graphite nanofibers as electrolytes for direct methanol fuel cells. RSC Adv. 2016, 6, 107507– 107518, DOI: 10.1039/c6ra23510g[Crossref], [CAS], Google Scholar32https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC28XhslelsbrM&md5=9ad740dc4661a806af01c7098ec341a5Nanocomposite membranes of sulfonated poly(phthalalizinone ether ketone)-sulfonated graphite nanofibers as electrolytes for direct methanol fuel cellsRambabu, Gutru; Sasikala, S.; Bhat, Santoshkumar D.RSC Advances (2016), 6 (109), 107507-107518CODEN: RSCACL; ISSN:2046-2069. (Royal Society of Chemistry)Polymer nanocomposite membranes are prepd. by the dispersion of sulfonated graphite nanofibers (SGNF) in the sulfonated poly(phthalazinone ether ketone) (SPPEK) matrix. GNF are first functionalized with 4-benzene sulfonic acid, and the presence of sulfonic acid groups in GNF is confirmed by FT-IR and elemental anal. The GNF morphol. after functionalization is analyzed via SEM and TEM. Nanocomposite membranes are then prepd. by varying the content of SGNF in SPPEK using the solvent cast technique and characterized for their physico-chem. properties in terms of mech., thermal and dimensional stability, water sorption, proton and elec. cond. along with methanol permeability. Improved mech. stability for the nanocomposite membranes is obsd. due to interfacial interactions and good compatibility between SGNF and SPPEK. The nanocomposite membranes exhibit improved electrochem. selectivity, which in turn enhances the overall DMFC power output. The DMFC performance of the nanocomposite membrane is higher than pristine SPPEK and is on par with the Nafion-117 membrane. The stability of the nanocomposite membranes is examd. by operating membrane electrode assemblies (MEAs) in the open circuit voltage (OCV) condition for 50 h. In addn., the stability of the composite membranes is also confirmed by measuring the methanol crossover c.d. using linear sweep voltammetry (LSV) for MEAs comprising these membranes before and after an OCV test.
- 33Elakkiya, S.; Arthanareeswaran, G.; Ismail, A. F.; Das, D. B.; Suganya, R. Polyaniline coated sulfonated TiO2 nanoparticles for effective application in proton conductive polymer membrane fuel cell. Eur. Polym. J. 2019, 112, 696– 703, DOI: 10.1016/j.eurpolymj.2018.10.036[Crossref], [CAS], Google Scholar33https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC1cXitVyitbrJ&md5=b290e4c6ad9e8778f3e1e917afa3599ePolyaniline coated sulfonated TiO2 nanoparticles for effective application in proton conductive polymer membrane fuel cellElakkiya, S.; Arthanareeswaran, G.; Ismail, A. F.; Das, Diganta B.; Suganya, R.European Polymer Journal (2019), 112 (), 696-703CODEN: EUPJAG; ISSN:0014-3057. (Elsevier Ltd.)The sulfonated polyethersulfone (SPES) with modified TiO2 proton exchange membrane performance for the fuel cell application was reported. TiO2 nanoparticles investigated for the fuel cell performance were modified by sulfonation and surface coated using polyaniline (PANI). Fabricated membranes were analyzed in terms of water uptake, swelling ratio, methanol uptake, ion exchange capacity, chem. stability and thermal properties. Surface and structural properties of the membranes were characterized by Field Emission Scanning electron microscope (FESEM). To understand the interaction between polymer and nanoparticle, Fourier transform IR (FTIR) and X-ray diffraction (XRD) characterization for the membranes were performed. Highest proton cond. is 2.30 × 10-4 S/cm with SPES/STiO2-PANI (0.5%) composite membrane. The presence of modified TiO2 with amine group of PANI and sulfonic acid group were the main factors for the highest cond. value. The composite membrane with modified TiO2 shows excellent chem. stability and thermal properties. Thus, the composite membrane incorporated with STiO2-PANI is a promising proton conducting material for fuel cell application.
- 34Kumar, K. S.; Rajendran, S.; Prabhu, M. R. A Study of influence on sulfonated TiO2-Poly (Vinylidene fluoride-co-hexafluoropropylene) nano composite membranes for PEM Fuel cell application. Appl. Surf. Sci. 2017, 418, 64– 71, DOI: 10.1016/j.apsusc.2016.11.139[Crossref], [CAS], Google Scholar34https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC28XhvFOgs7fN&md5=a4320291cb3bb8c2ed50fdcd46027b3eA Study of influence on sulfonated TiO2-Poly (Vinylidene fluoride-co-hexafluoropropylene) nano composite membranes for PEM Fuel cell applicationkumar, K. Selva; Rajendran, S.; Prabhu, M. RameshApplied Surface Science (2017), 418 (Part_A), 64-71CODEN: ASUSEE; ISSN:0169-4332. (Elsevier B.V.)The present work describes the sulfonated Titania directly blended with Poly (Vinylidene fluoride-co-hexafluoropropylene) as a host polymer by solvent casting technique for PEM fuel cell application. Characterization studies such as FT-IR, SEM, EDX, AFM, Proton cond., contact angle measurement, IEC, TG, water uptake, tensile strength were performed by for synthesized proton conducting polymer electrolytes. The max. proton cond. value was found to be 3.6 × 10-3S/cm for 25 wt% sulfonated Titania based system at 80 °C. The temp. dependent proton cond. of the polymer electrolyte follows an Arrhenius relationship. Surface morphol. of the composite membranes was investigated by tapping mode. Thermal stability of the system was studied by TG anal. The fabricated composite membranes with high proton cond., good water uptake and IEC parameters exhibited a max. fuel cell power d. of 85 Mw/cm2for PEM fuel cell application.
- 35Ayyaru, S.; Dharmalingam, S. A study of influence on nanocomposite membrane of sulfonated TiO2 and sulfonated polystyrene-ethylene-butylene-polystyrene for microbial fuel cell application. Energy 2015, 88, 202– 208, DOI: 10.1016/j.energy.2015.05.015[Crossref], [CAS], Google Scholar35https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC2MXovVersrw%253D&md5=d754342e8a1885cd68ad452e1f2cb8e9A study of influence on nanocomposite membrane of sulfonated TiO2 and sulfonated polystyrene-ethylene-butylene-polystyrene for microbial fuel cell applicationAyyaru, Sivasankaran; Dharmalingam, SangeethaEnergy (Oxford, United Kingdom) (2015), 88 (), 202-208CODEN: ENEYDS; ISSN:0360-5442. (Elsevier Ltd.)Microbial fuel cell (MFC) is a device that uses bacteria as a catalyst to oxidize various substrates for simultaneous electricity generation and wastewater treatment. In the present work, (sulfonated TiO2 (S-TiO2)/polystyrene ethylene butylene polystyrene) SPSEBS nanocomposite membranes were prepd. by soln. casting. The IEC (ion exchange capacity), water uptake, proton cond. and MFC performance of the composite membranes were explored. SPSEBS-S-TiO2 membrane (7.5%) exhibited the highest IEC value, water uptake and proton cond. capacity. The results revealed that the incorporation of sulfonated TiO2 improved the proton cond. of the SPSEBS membrane effectively and exhibited the highest peak power d. of 1345 ± 17 mWm-2 for SPSEBS-S-TiO2 7.5%, when compared to 695 ± 7 mWm-2 and 835 ± 8 mWm-2 obtained for SPSEBS and SPSEBS-TiO2 membranes resp. in a (single chambered microbial fuel cell) SCMFC. In comparison to previously reported work with Nafion (300 ± 10 mWm-2) in MFCs, the composite membrane delivered more than 4-fold higher power d. The oxygen mass transfer coeff. (KO) of nanocomposite membranes decreased with incorporation of the sulfonated TiO2 which in turn increased the (columbic efficiency) CE.
- 36Cotton, F. A.; Stokely, P. F. Structural basis for the acidity of sulfonamides. Crystal structures of dibenzenesulfonamide and its sodium salt. J. Am. Chem. Soc. 1970, 92, 294– 302, DOI: 10.1021/ja00705a012[ACS Full Text], [CAS], Google Scholar36https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADyaE3cXmtVWktQ%253D%253D&md5=f73dc6d5d243606293dd633fd7174fd9Structural basis for the acidity of sulfonamides. Crystal structures of dibenzenesulfonamide and its sodium saltCotton, F. Albert; Stokely, P. F.Journal of the American Chemical Society (1970), 92 (2), 294-302CODEN: JACSAT; ISSN:0002-7863.To ascertain what role structural factors-and, hence, by implication , bonding factors-play in the pronounced acidity of dibenzenesulfonami de (pKa = 1.45), the structures of the acid itself, (PhSO2)2NH, and the Na salt, Na+-(C5H5SO2)2N-, have been detd. For (PhSO2)2NH: space group, P21/c; Z = 4; d0 = 1.470; dc = 1.468; a = 8.625 ± 0.004, b = 10.164 ± 0.004, c = 15.627 ± 0.004 Å; β = 101.09 ± 0.05°. Intensities of 2364 independent reflections were measured using Mo Kα radiation and employing an automated diffractometer. The 1276 reflections accepted as statistically reliable and nonzero were used to solve (by application of the Karle-Hauptman sigma-2 relation) and refine the structure. For Na+ (PhSO2)2N-: space group, Pbcn; Z = 8; d0 = 1.585; dc = 1.580; a = 15.218 ± 0.004, b = 17.210 ± 0.004, c = 10.252 ± 0.004 Å. Intensities of 1639 independent reflections were measured by using Cu Kα radiation and employing an automated diffractometer. Of these, 1251 reflections were used to solve the structure by the symbolic addn. procedure and to refine it. In (PhSO2)2NH, the Ph groups lie above and below the S-N-S plane, giving approx. mol. symmetry C2; in [PhSO2)2N]-, they lie on the same side of the S-N-S plane giving approx. Cs symmetry. This difference seems to be caused primarily by steric, electrostatic, and packing forces. The SNS angle, mean S-N distances, and mean S-O distance in (Ph-sO2)2NH and [(PhSO2)2N]- are, resp.: 127.7(3)°, 1.650(7) Å, an d 1.415 (18) Å; and 127.5(3)°, 1.580(9) Å, 1.446 (8) Å. Thus, the only major change attributable directly to deprotonation of (PhSO2)2NH is the decrease of 0.070(16) Å in the mean S-N bond length.
- 37Tabrizian, E.; Amoozadeh, A.; Shamsi, T. A novel class of heterogeneous catalysts based on toluene diisocyanate: the first amine-functionalized nano-titanium dioxide as a mild and highly recyclable solid nanocatalyst for the Biginelli reaction. React. Kinet., Mech. Catal. 2016, 119, 245– 258, DOI: 10.1007/s11144-016-1047-0[Crossref], [CAS], Google Scholar37https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC28XhtVyrtrnO&md5=6c9ff13ee9336f8c4bcf3fa83929d0c0A novel class of heterogeneous catalysts based on toluene diisocyanate: the first amine-functionalized nano-titanium dioxide as a mild and highly recyclable solid nanocatalyst for the Biginelli reactionTabrizian, Elham; Amoozadeh, Ali; Shamsi, TaiebehReaction Kinetics, Mechanisms and Catalysis (2016), 119 (1), 245-258CODEN: RKMCAJ; ISSN:1878-5190. (Springer)Amine-functionalized titania as a novel inorg.-org. hybrid heterogeneous basic nanocatalyst has been synthesized by the covalent grafting of toluene diisocyanate as a precursor of amine on the surface of titania. The prepd. nanocatalyst was characterized by Fourier transform IR spectroscopy, field emission SEM, X-ray diffraction and thermogravimetric anal. The catalytic activity of resultant nanocatalyst was effectively evaluated for the synthesis of 3,4-dihydopyrimidin-2(1H)-ones through a one-pot three components condensation reaction of various aldehydes, β-dicarbonyl compds. and urea (or thiourea) at 100°C under solvent-free conditions with good to excellent yields. Optimization of the reaction condition was investigated by central composite design under response surface methodol. The catalyst can be recovered easily by simple filtration and reused for eight consecutive runs without significant decrease of its catalytic efficiency.
- 38Xu, T.; Hou, W.; Shen, X.; Wu, H.; Li, X.; Wang, J.; Jiang, Z. Sulfonated titania submicrospheres-doped sulfonated poly(ether ether ketone) hybrid membranes with enhanced proton conductivity and reduced methanol permeability. J. Power Sources 2011, 196, 4934– 4942, DOI: 10.1016/j.jpowsour.2011.02.017[Crossref], [CAS], Google Scholar38https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC3MXjvVSgt78%253D&md5=6f6c26cc12f29f43bfba132f236ba7d9Sulfonated titania submicrospheres-doped sulfonated poly(ether ether ketone) hybrid membranes with enhanced proton conductivity and reduced methanol permeabilityXu, Tao; Hou, Weiqiang; Shen, Xiaohui; Wu, Hong; Li, Xicheng; Wang, Jingtao; Jiang, ZhongyiJournal of Power Sources (2011), 196 (11), 4934-4942CODEN: JPSODZ; ISSN:0378-7753. (Elsevier B.V.)Sulfonated titania submicrospheres (TiO2-SO3H) prepd. through a facile chelation method are incorporated into sulfonated poly(ether ether ketone) (SPEEK) to fabricate org.-inorg. hybrid membranes with enhanced proton cond. and reduced methanol permeability for potential use in direct methanol fuel cells (DMFCs). The pristine titania submicrospheres (TiO2) with a uniform particle size are synthesized through a modified sol-gel method and sulfonated using 4,5-dihydroxy-1,3-benzenedisulfonic acid disodium salt as the sulfonation reagent. The sulfonation process is confirmed by Fourier transform IR spectroscopy (FTIR) and X-ray photoelectron spectra (XPS). The hybrid membranes are systematically characterized in terms of thermal property, mech. property, ionic exchange capacity (IEC), swelling behavior, and microstructural features. The methanol barrier property and the proton cond. of the SPEEK/TiO2-SO3H hybrid membranes are evaluated. The presence of the fillers reduces methanol crossover through the membrane. Compared with the unsulfonated TiO2-doped membranes, the TiO2-SO3H-doped ones exhibit higher proton cond. due to the addnl. sulfonic acid groups on the surface of TiO2. The hybrid membrane doped with 15 wt. % TiO2-SO3H submicrospheres exhibits an acceptable proton cond. of 0.053 S cm-1 and a reduced methanol permeability of 4.19 × 10-7 cm2 s-1.
- 39Venkatachalam, N.; Palanichamy, M.; Murugesan, V. Sol–gel preparation and characterization of alkaline earth metal doped nano TiO2: Efficient photocatalytic degradation of 4-chlorophenol. J. Mol. Catal. A: Chem. 2007, 273, 177– 185, DOI: 10.1016/j.molcata.2007.03.077[Crossref], [CAS], Google Scholar39https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BD2sXntF2qsLw%253D&md5=45604d20cd5e19eb1929621fa6eaa9a9Sol-gel preparation and characterization of alkaline earth metal doped nano TiO2: Efficient photocatalytic degradation of 4-chlorophenolVenkatachalam, N.; Palanichamy, M.; Murugesan, V.Journal of Molecular Catalysis A: Chemical (2007), 273 (1-2), 177-185CODEN: JMCCF2; ISSN:1381-1169. (Elsevier B.V.)Magnesium- and barium doped TiO2 nanoparticles were synthesized by sol-gel method. The materials were characterized by XRD, BET, FT-IR, TGA, UV-vis, SEM and TEM techniques. The pure TiO2 nanoparticles contained both anatase and rutile phases together, but Mg2+ or Ba2+ metal ion doped nanosize TiO2 gave only anatase phase. The framework substitution of Mg2+ in TiO2 was established by XRD and FT-IR techniques. However, Ba2+ was retained only on the surface of TiO2 as BaCO3 and the absence of framework substitution of Ba2+ in TiO2 was evident from XRD and FT-IR anal. The band gap values of Mg2+ and Ba2+ doped TiO2 were higher than the pure TiO2. The presence of anatase type structure in TiO2 with high crystallinity and high phase stability even after annealing at 800° C substantially indicates that the dopants might inhibit densification and crystallite growth in nanosized TiO2 by providing dissimilar boundaries. The photocatalytic activity in the degrdn. of 4-chlorophenol was found to be higher for Mg2+ and Ba2+ doped TiO2 than both pure TiO2 and com. TiO2 (Degussa P-25). The influence of various parameters such as initial concn. of 4-chlorophenol, catalyst loading, pH and light intensity were optimized to obtain max. degrdn.
- 40Solymosi, F.; Raskó, J. An infrared study on the formation of isocyanate in the NO + CO reaction on supported Ir catalyst. J. Catal. 1980, 63, 217– 225, DOI: 10.1016/0021-9517(80)90074-3[Crossref], [CAS], Google Scholar40https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADyaL3cXktlagtrg%253D&md5=404284ca47b458bd5488017925c15040An infrared study on the formation of isocyanate in the nitric oxide + carbon monoxide reaction on supported iridium catalystSolymosi, F.; Rasko, J.Journal of Catalysis (1980), 63 (1), 217-25CODEN: JCTLA5; ISSN:0021-9517.The formation of isocyanate surface species in the NO + CO reaction was studied on supported Ir catalyst as a function of temp. and compn. of the reacting gas mixt. On reduced Ir/Al2O3 samples absorption bands due to isocyanate were obsd. at 2260-2240 cm-1. The isocyanate band was first detected at 200°, and its max. intensity was registered at 280-300°. It is stable at <200° but decomps. rapidly at >300° in vacuo to give CO2, CO, and N2. Isocyanate was also formed on oxidized surfaces but with considerably lower intensities. The reaction between preadsorbed NO and gaseous CO also resulted in the formation of isocyanate, but it was not identified when NO was admitted onto preadsorbed CO. During the surface interaction of NO and CO a large downscale shift of the NO band occurred which was explained by the perturbing effect of adsorbed CO. The primary step in the formation of isocyanate is the dissocn. of NO on the reduced centers. Isocyanate formed on the IR migrates to the acceptor sites of the support. This explanation is supported by the observations that the different supports markedly affect the location, formation, and stability of the isocyanate band.
- 41Ou, B.; Li, D.; Liu, Q.; Zhou, Z.; Liao, B. Functionalized TiO2 nanoparticle containing isocyanate groups. Mater. Chem. Phys. 2012, 135, 1104– 1107, DOI: 10.1016/j.matchemphys.2012.06.027[Crossref], [CAS], Google Scholar41https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC38XpvVSks7s%253D&md5=fcea8921d01642f68835c784cf89bd48Functionalized TiO2 nanoparticle containing isocyanate groupsOu, Baoli; Li, Duxin; Liu, Qingquan; Zhou, Zhihua; Liao, BoMaterials Chemistry and Physics (2012), 135 (2-3), 1104-1107CODEN: MCHPDR; ISSN:0254-0584. (Elsevier B.V.)Functionalized TiO2 nanoparticle contg. isocyanate groups can extend the TiO2 nanoparticle chem., and may promote their many potential applications such as in polymer composites and coatings. This paper describes a facile method to prep. functionalized TiO2 nanoparticle with highly reactive isocyanate groups on its surface, via the reaction between toluene-2,4-diisocyanate (TDI) and hydroxyl on TiO2 nanoparticle surface. The main effect factors on the reaction of TiO2 with TDI were studied by detg. the reaction extent of hydroxyl groups on TiO2 surface. Fourier-transformed IR spectroscopy (FTIR) and TGA confirmed that reactive isocyanate groups were covalently attached to the TiO2 nanoparticle surface. The dispersion of the TDI-functionalized TiO2 nanoparticle was studied by TEM. Owing to the TDI mols. covalently bonded on TiO2 nanoparticle surface, the TiO2 nanoparticle can be uniformly dispersed in toluene, thus indicating that this functionalization method can prevent TiO2 nanoparticle from agglomerating.
- 42Shaterian, H. R.; Ghashang, M.; Feyzi, M. Silica sulfuric acid as an efficient catalyst for the preparation of 2 H-indazolo[2,1- b]phthalazine-triones. Appl. Catal., A 2008, 345, 128– 133, DOI: 10.1016/j.apcata.2008.04.032[Crossref], [CAS], Google Scholar42https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BD1cXotFCksb0%253D&md5=285d10fc342a0917710773b13d4ea284Silica sulfuric acid as an efficient catalyst for the preparation of 2H-indazolo[2,1-b]phthalazinetrionesShaterian, Hamid Reza; Ghashang, Majid; Feyzi, MostafaApplied Catalysis, A: General (2008), 345 (2), 128-133CODEN: ACAGE4; ISSN:0926-860X. (Elsevier B.V.)Silica sulfuric acid as an efficient and reusable heterogeneous catalyst was used for the prepn. of the title compds. [I; Ar = (un)substituted phenyl] from the three-component condensation reaction of phthalhydrazide, dimedone, and arom. aldehydes under solvent-free conditions in good to excellent yields and short reaction times.
- 43Inan, T. Y.; Doğan, H.; Unveren, E. E.; Eker, E. Sulfonated PEEK and fluorinated polymer based blends for fuel cell applications: Investigation of the effect of type and molecular weight of the fluorinated polymers on the membrane’s properties. Int. J. Hydrogen Energy 2010, 35, 12038– 12053, DOI: 10.1016/j.ijhydene.2010.07.084[Crossref], [CAS], Google Scholar43https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC3cXht1emsrfM&md5=2631a913b7e9aef6d34fa2be142423c0Sulfonated PEEK and fluorinated polymer based blends for fuel cell applications: Investigation of the effect of type and molecular weight of the fluorinated polymers on the membrane's propertiesInan, Tuelay Y.; Dogan, Hacer; Unveren, Elif E.; Eker, ErsoyInternational Journal of Hydrogen Energy (2010), 35 (21), 12038-12053CODEN: IJHEDX; ISSN:0360-3199. (Elsevier Ltd.)This work clearly demonstrates the effect and mol. wt. of the fluorinated polymer of SPEEK/Fluorinated polymer blends for low temp. ( < 80°) Fuel Cell Applications. Comparisons with trademarks (e.g., Nafion) suggests that the membranes the authors prepd. in this study have good compatibility in all application respects. Membranes were prepd. by soln. casting method from four different fluorinated polymers; poly(vinylidene fluoride) with three different mol. wts. (PVDF, Mw: 180.000, Mw: 275.000, Mw: 530.000); Poly(vinylidene fluoride-co-Hexafluoro propylene) (PVDF-HFP Mn:130.000) and sulfonated poly(ether ether ketone) (SPEEK) with sulfonation degree (SD) of 70. The sulfonation degree (SD) of SPEEK was detd. by FTIR, 1H NMR and ion exchange capacity (IEC) measurements. Thermo-oxidative stability and proton cond. of the membranes were detd. by using TGA and BT-512 BekkTech membrane test systems, resp. Chem. degrdn. of SPEEK membranes was studied via Fenton test. The morphol. of the membranes were examd. by SEM and TEM. Water uptake and proton cond. values decreased with the addn. of fluorinated polymers (PVDF, PVDF-HFP) as expected, but proton cond. values were still comparable to that of Nafion 117 membrane. Addn. of fluorinated polymers improved chem. degrdn. of the blend membranes in all ratios while addn. of PVDF-HFP to the SPEEK70 caused phase sepns. in all ratios. Methanol permeability value of SPEEK70/PVDF(Mw = 275.000) blend membrane (3.13E-07 (cm2/s)) was much lower than Nafion 117 (1.21E-06 (cm2/s)). PVDF addn. to the SPEEK polymers caused increase in elongation of the membranes. Increase in the mol. wt. of the PVDF did not show any effect on the Young modulus, but resulted in high elongation values. However, increasing PVDF content of the blend membranes caused lower elongation values at break and didn't have any effect on the Young modulus. The gas permeability values of SPEEK70/PVDF type blend membranes were lower than that of the Nafion. Hydrogen and oxygen permeability values were 1-tenth and 1/5 of the Nafion, resp.
- 44Chi, L.; Qian, Y.; Guo, J.; Wang, X.; Arandiyan, H.; Jiang, Z. Novel g-C3N4/TiO2/PAA/PTFE ultrafiltration membrane enabling enhanced antifouling and exceptional visible-light photocatalytic self-cleaning. Catal. Today 2019, 335, 527– 537, DOI: 10.1016/j.cattod.2019.02.027[Crossref], [CAS], Google Scholar44https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC1MXks1yqu7w%253D&md5=2a435ff299acea4499bd7d5888cfc828Novel g-C3N4/TiO2/PAA/PTFE ultrafiltration membrane enabling enhanced antifouling and exceptional visible-light photocatalytic self-cleaningChi, Lina; Qian, Yingjia; Guo, Junqiu; Wang, Xinze; Arandiyan, Hamidreza; Jiang, ZhengCatalysis Today (2019), 335 (), 527-537CODEN: CATTEA; ISSN:0920-5861. (Elsevier B.V.)Membrane fouling due to superhydropobicity of polytetrafluoroethylene ultrafiltration membranes (PTFE UFMs) represents a grand challenge for their practical applications in diverse water treatment industries. Surface immobilization of hydrophilic and chem. stable inorg. metal oxides (TiO2, ZrO2, etc) has been developed to improve hydrophilicity of the PTFE UFMs, though they still suffer from expensive and repeating regenerations once fouled. To address such issues, we strive to firmly immobilize g-C3N4 modified TiO2 (g-C3N4/TiO2, hereafter CNTO) onto PTFE UFM via a facile plasma-enhanced surface graft technique using polyacrylic acid (PAA) as a bridging agent. As reported here, the obtained CNTO/PAA/PTFE UFM shows much smaller surface water contact angle (WCA) of 62.3° than that of bare PTFE UFM(115.8°), leading to enhanced water flux of 830 L m-2 h-1 in the initial ultrafiltration of modelled waste-water contg. methylene blue (MB). The CNTO/PAA/PTFE UFM is highly resistant to fouling in the prolonged filtration of 1000 mg/L bovine serum albumin (BSA) soln., while the fouled CNTO/PAA/PTFE UFM is able to regenerate rapidly under either UV or visible-light irradn. The enhanced performance of the novel CNTO/PAA/PTFE UFM is reasonably attributed to its high wettability and robust photocatalytic activity of the g-C3N4/TiO2 coating that follows different self-cleaning mechanisms under UV and visible light irradiations.
- 45Kermani, H.; Rohrbach, A. Orientation-control of two plasmonically coupled nanoparticles in an optical trap. ACS Photonics 2018, 5, 4660– 4667, DOI: 10.1021/acsphotonics.8b01145[ACS Full Text], [CAS], Google Scholar45https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC1cXhslGgu7bK&md5=a6571081b4669ed85cbd883f90cec8e2Orientation-Control of Two Plasmonically Coupled Nanoparticles in an Optical TrapKermani, Hamideh; Rohrbach, AlexanderACS Photonics (2018), 5 (11), 4660-4667CODEN: APCHD5; ISSN:2330-4022. (American Chemical Society)Optical monitoring of nanoparticle (NP) dynamics is typically beyond the spatial and temporal resoln. limit of light microscopy. However, the orientation and assembly of NPs can be controlled by various light scattering methods. Here we demonstrate how two 80 nm silver NPs form a dimer inside an optical trap and orient along the elec. field of the trapping laser, therefore allowing to rotate them stably in the horizontal plane. We built a dual-path spectrometer for two orthogonal polarization directions to det. the azimuthal dimer angle for different plasmonic coupling strengths by the difference in the measured spectral intensity maxima. The azimuthal angle of the dimer could be retrieved with an accuracy of a few degrees independent of the spectral frequency or the distance between the NPs. Our results coincide well with a developed theor. model predicting polarization-dependent scattering spectra for dimers with different orientations and NP distances. Our study points out another strategy for a highly controlled assembly of single NPs using optical tweezers and multimodal scattered light.
- 46Wang, L.; Deng, N.; Wang, G.; Ju, J.; Cheng, B.; Kang, W. Constructing amino-functionalized flower-like metal–organic framework nanofibers in sulfonated poly(ether sulfone) proton exchange membrane for simultaneously enhancing interface compatibility and proton conduction. ACS Appl. Mater. Interfaces 2019, 11, 39979– 39990, DOI: 10.1021/acsami.9b13496[ACS Full Text], [CAS], Google Scholar46https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC1MXhvFektLbE&md5=884cabdef9c72e24f3c29e61b2df4d7eConstructing Amino-Functionalized Flower-like Metal-Organic Framework Nanofibers in Sulfonated Poly(ether sulfone) Proton Exchange Membrane for Simultaneously Enhancing Interface Compatibility and Proton ConductionWang, Liyuan; Deng, Nanping; Wang, Gang; Ju, Jingge; Cheng, Bowen; Kang, WeiminACS Applied Materials & Interfaces (2019), 11 (43), 39979-39990CODEN: AAMICK; ISSN:1944-8244. (American Chemical Society)A novel flower-like MIL-53(Al)-NH2 nanofiber (MNF) was constructed, in which the electro-blown spinning Al2O3 nanofibers were introduced as Al precursors to coordinate with ligand in hydrothermal reaction for the formation of MOFs nanofibers. By incorporating the functional and consecutive MNFs fillers in sulfonated poly(ether sulfone) (SPES) matrix, high-performance [email protected] hybrid membranes were obtained. Specifically, the peak stress strength could be strengthened to 33.42 MPa and the proton cond. was remarkably improved to 0.201 S/cm as MNFs content increased to 5 wt.%, achieving a simultaneous improvement on proton conduction and membrane stability. The highly promoted performance could be ascribed to the synergy advantages of unique structure and amino modification of MNFs: (1) the flower-like nanofiber structure of MNFs with high surface area could be beneficial to construct long-range and compatible interfaces between MNFs and SPES matrix, leading to sufficient continuous proton pathways as well as strengthened stability for the hybrid membrane. (2) the hydrophilic MNFs rendered the hybrid membrane with sufficient water retention for proton transfer via Vehicle mechanism. (3) functional -NH2 groups of MNFs and -SO3H groups of SPES were consecutively and tightly bonded via acid-base electrostatic interactions, which further accelerated the proton conduction via Grotthuss hopping mechanism and effectively suppressed the MeOH penetration in the meanwhile for the [email protected] hybrid membranes.
- 47Muthumeenal, A.; Neelakandan, S.; Rana, D.; Matsuura, T.; Kanagaraj, P.; Nagendran, A. Sulfonated polyethersulfone (SPES)–charged surface modifying macromolecules (cSMMs) blends as a cation selective membrane for fuel cells. Fuel Cells 2014, 14, 853– 861, DOI: 10.1002/fuce.201400044[Crossref], [CAS], Google Scholar47https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC2cXitVamurbN&md5=ae90a5f3411720a0cc12f87727ff3781Sulfonated Polyethersulfone (SPES) - Charged Surface Modifying Macromolecules (cSMMs) Blends as a Cation Selective Membrane for Fuel CellsMuthumeenal, A.; Neelakandan, S.; Rana, D.; Matsuura, T.; Kanagaraj, P.; Nagendran, A.Fuel Cells (Weinheim, Germany) (2014), 14 (6), 853-861CODEN: FUCEFK; ISSN:1615-6846. (Wiley-Blackwell)Polyethersulfone (PES) was sulfonated by chlorosulfonic acid and concd. sulfuric acid. The pure sulfonated PES (SPES) and modified SPES membranes were prepd. by blending with different charged surface modifying macromols. (cSMMs) namely, SPES/DEG-HBS, SPES/PEG-HBS, and SPES/PPG-HBS. Membranes were characterized for their morphol., phys. properties, and electrochem. properties in order to evaluate these membranes as cation exchange membranes. The blended membranes showed an increase in hydrophilicity, water uptake, and proton cond. compared to the pure SPES membranes. The highest values of water uptake and proton cond. were obtained for the SPES/PPG-HBS blended membrane. Morphol. studies revealed that the nodule size and surface roughness also influenced the water uptake, apart from the addnl. -SO3H group. Among the modified membranes, the SPES/DEG-HBS blended membrane exhibited a lower methanol permeability value of 8.895 × 10-8 cm2 s-1 than the corresponding SPES membrane. The other two cSMM blended membranes showed higher methanol permeability values than SPES but still a smaller value than Nafion 117. The highest selectivity ratio (i.e., ratio of proton cond. to methanol permeability) was obtained with the SPES/DEG-HBS cSMM blended membrane. These results showed that the SPES/cSMM blended membranes have promise for possible use as a cation exchange membrane in fuel cells and electrolyzer applications.
- 48Rao, Z.; Feng, K.; Tang, B.; Wu, P. Construction of well interconnected metal-organic framework structure for effectively promoting proton conductivity of proton exchange membrane. J. Membr. Sci. 2017, 533, 160– 170, DOI: 10.1016/j.memsci.2017.03.031[Crossref], [CAS], Google Scholar48https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC2sXls1Kitb8%253D&md5=9ff48a75cde885eae9286970fff2c582Construction of well interconnected metal-organic framework structure for effectively promoting proton conductivity of proton exchange membraneRao, Zhuang; Feng, Kai; Tang, Beibei; Wu, PeiyiJournal of Membrane Science (2017), 533 (), 160-170CODEN: JMESDO; ISSN:0376-7388. (Elsevier B.V.)To obtain proton exchange membrane (PEM) with high proton conductivities under both high humidity and anhyd. condition, interconnected UiO-66-NH2 was tethered onto graphene oxide (GO) surfaces, and then incorporated into Nafion matrix. Thanks to tethering effect of GO surfaces and interconnection among MOF grains, well interconnected metal-org. framework (MOF) structures ([email protected]) were constructed. The structural advantage and mechanism of [email protected] in proton conduction were explored. It was found the synergistic effect between GO and UiO-66-NH2 with suitable particle size was esp. important for promoting proton transfer. Such interconnected structure of MOF on GO also made acid/base pair pathways between -SO3H of Nafion and -NH2 of [email protected] more consecutive. This was favorable to proton conduction via both vehicle mechanism and Grotthuss mechanism. The proton cond. of the as-prepd. composite membrane reached up to 0.303 S/cm under 90°, 95% RH, and 3.403 × 10-3 S/cm under anhyd. condition, which was about 1.57 and 1.88 times higher than that of the recast Nafion (0.118 S/cm and 1.182 × 10-3 S/cm), resp. Furthermore, the composite membrane showed a reduced methanol permeability, which was attributed to the barrier effect of the two-dimensional GO and the trapping of methanol by UiO-66-NH2 pores.
- 49Cele, N.; Ray, S. S. Recent progress on Nafion-based nanocomposite membranes for fuel cell applications. Macromol. Mater. Eng. 2009, 294, 719– 738, DOI: 10.1002/mame.200900143[Crossref], [CAS], Google Scholar49https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BD1MXhsVaju7bI&md5=eecc9bc56befa2efd0dbb6a5e560d474Recent Progress on Nafion-Based Nanocomposite Membranes for Fuel Cell ApplicationsCele, Nonhlanhla; Ray, Suprakas SinhaMacromolecular Materials and Engineering (2009), 294 (11), 719-738CODEN: MMENFA; ISSN:1438-7492. (Wiley-VCH Verlag GmbH & Co. KGaA)A review of recent progress in the field of Nafion-based nanocomposite membranes for proton exchange membrane fuel cells. The membranes exhibit a significant improvement in thermomech. and thermal stability as well as proton cond. at very low filler contents. Prepn., characterization, and properties of various types of Nafion-based nanocomposite membranes are critically discussed, and detailed examples are summarized. A large variety of nanoparticles of different natures and sizes can be blended with a Nafion matrix, generating a new class of nanostructured electrolyte membrane with interesting phys. properties.
- 50Shaari, N.; Kamarudin, S. K.; Zakaria, Z. Potential of sodium alginate/titanium oxide biomembrane nanocomposite in DMFC application. Int. J. Energy Res. 2019, 43, 8057– 8069, DOI: 10.1002/er.4801[Crossref], [CAS], Google Scholar50https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC1MXitVKgsbzI&md5=13b99032d8c65a6493a8b537e701cbcaPotential of sodium alginate/titanium oxide biomembrane nanocomposite in DMFC applicationShaari, Norazuwana; Kamarudin, Siti Kartom; Zakaria, ZulfirdausInternational Journal of Energy Research (2019), 43 (14), 8057-8069CODEN: IJERDN; ISSN:0363-907X. (John Wiley & Sons Ltd.)Summary : A proton exchange membrane was synthesized consuming a sodium alginate biopolymer as the matrix and titanium oxide as the nanofiller. The titanium oxide content varied from 5 to 25 wt%. The biomembrane nanocomposite performs better than the pristine sodium alginate membrane based on liq. uptake, methanol permeability, proton cond., ion exchange capacity, and oxidative stability outcomes. The unique properties of sodium alginate and titanium oxide lead to outstanding interconnections, thus producing new materials with great characteristics and enhanced performance. The highest proton cond. achieved in this study is 17.3 × 10-3 S cm-1, which performed by SAT5 (25 wt%) membranes at 70°C. An optimal content of titanium oxide enhances the cond. and methanol permeability of the membrane. Addnl., the hydrophilicity of pure sodium alginate is greatly reduced and achieves a good liq. uptake capacity and swelling ratio. The characteristics of the SA/TiO2 biomembrane nanocomposite were detd. with field emission scanning electron microscope, Fourier transform IR, X-ray diffraction, thermal gravimetric anal./differential scanning calorimetry, and mech. strength anal.
- 51Kim, D. S.; Liu, B.; Guiver, M. D. Influence of silica content in sulfonated poly(arylene ether ether ketone ketone) (SPAEEKK) hybrid membranes on properties for fuel cell application. Polymer 2006, 47, 7871– 7880, DOI: 10.1016/j.polymer.2006.09.001[Crossref], [CAS], Google Scholar51https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BD28XhtFSnurzO&md5=0bb091795fbdacd7a007dc5707cb61adInfluence of silica content in sulfonated poly(arylene ether ether ketone ketone) (SPAEEKK) hybrid membranes on properties for fuel cell applicationKim, Dae Sik; Liu, Baijun; Guiver, Michael D.Polymer (2006), 47 (23), 7871-7880CODEN: POLMAG; ISSN:0032-3861. (Elsevier Ltd.)Sulfonated poly(arylene ether ether ketone ketone) (SPAEEKK) copolymer with a pendant sulfonic acid group (sulfonic acid content (SC) = 0.67) was synthesized from the com. available monomers Na 6,7-dihydroxy-2-naphthalenesulfonate (DHNS), 1,3-bis(4-fluorobenzoyl)-benzene (BFBB), and hexafluorobisphenol A (6F-BPA). SPAEEKK/SiO2 hybrid membranes were prepd. using a sol-gel process under acidic conditions. SPAEEKK/SiO2 hybrid membranes were fabricated with different SiO2 contents and the membranes were modified to achieve improved p cond. incorporating P-OH groups through H3PO4 treatment. The SiO2 particles within the membranes blocked excessive MeOH cross-over and form a pathway for p transport due to H2O absorption onto the hydrophilic ≡SiOH surface. The p conductivities of H3PO4-doped membranes were somewhat higher than the un-doped membranes due to increasing hydrophilicity of the membranes. The presence of SiO2 particles within the org. polymer matrix, which decreases the ratio of free H2O to bound H2O due to the ≡SiOH on the surface of SiO2 derived from sol-gel reaction, results in hybrid membranes with reduced MeOH permeability and improved p cond.
- 52Liu, X.; Zhang, Y.; Chen, Y.; Li, C.; Dong, J.; Wang, J.; Yang, Z.; Cheng, H. Investigation of diamine cross-linker on semi-IPNs of BPPO/SPEEK membranes for direct methanol fuel cell. Energy Technol. 2018, 6, 2264– 2272, DOI: 10.1002/ente.201800274[Crossref], [CAS], Google Scholar52https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC1cXitlShsrfK&md5=b16d2f6f7737e108a4f7099d33610663Investigation of Diamine Cross-Linker on Semi-IPNs of BPPO/SPEEK Membranes for Direct Methanol Fuel CellLiu, Xupo; Zhang, Yunfeng; Chen, Yazhou; Li, Cuicui; Dong, Jiaming; Wang, Jiaying; Yang, Zehui; Cheng, HansongEnergy Technology (Weinheim, Germany) (2018), 6 (11), 2264-2272CODEN: ETNEFN; ISSN:2194-4296. (Wiley-VCH Verlag GmbH & Co. KGaA)Low methanol permeability is one of the most crit. factors for proton exchange membranes utilized in direct methanol fuel cells (DMFCs). Here, sulfonated poly(ether ether ketone) (SPEEK) polymer chains are interpenetrated into the semi-interpenetrating polymer networks (semi-IPNs) constructed by the alkylation reaction between bromobenzyl groups of bromomethylated poly(phenylene oxide) and amine groups of 2,2'-(ethylenedioxy)bis(ethylamine) cross-linker. The influences of crosslinking network contents on the key properties of SPEEK membranes are systematically investigated. Dimensional stability and methanol-permeability resistance are enhanced as the increase of the crosslinking network contents. The relative selectivity is significantly improved due to the largely reduced methanol permeability. The DMFC assembled by the membrane with 20 wt.% crosslinking networks demonstrates four times higher power output than the Nafion 117 DMFC in 5 M methanol soln.
- 53Salarizadeh, P.; Bagheri, A.; Beydaghi, H.; Hooshyari, K. Enhanced properties of SPEEK with incorporating of PFSA and barium strontium titanate nanoparticles for application in DMFCs. Int. J. Energy Res. 2019, 43, 4840– 4853, DOI: 10.1002/er.4635[Crossref], [CAS], Google Scholar53https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC1MXhsVamtLnO&md5=a2f4c5ec90e27e41d4ead0d478b06745Enhanced properties of SPEEK with incorporating of PFSA and barium strontium titanate nanoparticles for application in DMFCsSalarizadeh, Parisa; Bagheri, Ahmad; Beydaghi, Hossein; Hooshyari, KhadijehInternational Journal of Energy Research (2019), 43 (9), 4840-4853CODEN: IJERDN; ISSN:0363-907X. (John Wiley & Sons Ltd.)Summary : Novel blend nanocomposite proton-exchange membranes were prepd. using sulfonated poly (ether ether ketone) (SPEEK), perfluorosulfonic acid (PFSA), and Ba0.9Sr0.1TiO3 (BST) doped-perovskite nanoparticles. The membranes were evaluated by attenuated total reflection, X-ray diffraction spectroscopy, water uptake, proton cond., methanol permeability, and direct methanol fuel cell test. The effect of two additives, PFSA and BST, were investigated. Results indicated that both proton cond. and methanol barrier of the blend nanocomposite membranes improved compared with pristine SPEEK and the as-prepd. blend membranes. The methanol permeability and the proton cond. of the blend membrane contg. 6 wt% BST obtained 3.56 × 10-7 cm2 s-1 (at 25 °C) and 0.110 S cm-1 (at 80 °C), resp. The power d. value for the optimum blend nanocomposite membrane (15 wt% PFSA and 6 wt% BST) (54.89 mW cm-2) was higher than that of pristine SPEEK (31.34 mW cm-2) and SPF15 blend membrane (36.12 mW cm-2).
- 54Jiang, Z.; Zhao, X.; Manthiram, A. Sulfonated poly(ether ether ketone) membranes with sulfonated graphene oxide fillers for direct methanol fuel cells. Int. J. Hydrogen Energy 2013, 38, 5875– 5884, DOI: 10.1016/j.ijhydene.2013.02.129[Crossref], [CAS], Google Scholar54https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC3sXlt1aqt7g%253D&md5=2c8d299f7c23283383181fcef2c46b61Sulfonated poly(ether ether ketone) membranes with sulfonated graphene oxide fillers for direct methanol fuel cellsJiang, Zhongqing; Zhao, Xinsheng; Manthiram, ArumugamInternational Journal of Hydrogen Energy (2013), 38 (14), 5875-5884CODEN: IJHEDX; ISSN:0360-3199. (Elsevier Ltd.)Sulfonated organosilane functionalized graphene oxides (SSi-GO) synthesized through the grafting of graphene oxide (GO) with 3-mercaptopropyl trimethoxysilane and subsequent oxidn. have been used as a filler in sulfonated poly(ether ether ketone) (SPEEK) membranes. The incorporation of SSi-GOs greatly increases the ion-exchange capacity (IEC), water uptake, and proton cond. of the membrane. With well-controlled contents of SSi-GOs, the composite membranes exhibit higher proton cond. and lower methanol permeability than Nafion 112 and Nafion 115, making them particularly attractive as proton exchange membranes (PEMs) for direct methanol fuel cells (DMFC). The composite membrane with optimal SSi-GOs content exhibit over 38 and 17% higher power densities, resp., than Nafion 112 and Nafion 115 membranes in DMFCs, offering the possibilities to reduce the DMFC membrane cost significantly while keeping high-performance.
- 55Sun, H.; Tang, B.; Wu, P. Two-Dimensional zeolitic imidazolate framework/carbon nanotube hybrid networks modified proton exchange membranes for improving transport properties. ACS Appl. Mater. Interfaces 2017, 9, 35075– 35085, DOI: 10.1021/acsami.7b13013[ACS Full Text], [CAS], Google Scholar55https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC2sXhsFOjt7nE&md5=7ffb1094a39afb9c747648de7090c44aTwo-Dimensional Zeolitic Imidazolate Framework/Carbon Nanotube Hybrid Networks Modified Proton Exchange Membranes for Improving Transport PropertiesSun, Huazhen; Tang, Beibei; Wu, PeiyiACS Applied Materials & Interfaces (2017), 9 (40), 35075-35085CODEN: AAMICK; ISSN:1944-8244. (American Chemical Society)Metal-org. framework (MOF)/polymer composite proton exchange membranes (PEMs) are being intensively investigated due to their potentials for the systematic design of proton-conducting properties. However, the development of MOF/polymer composite PEMs possessing high selectivity remains exceedingly desirable and challenging for practical application. Herein, two-dimensional (2D) zeolitic imidazolate framework (ZIF-8)/carbon nanotube (CNT) hybrid cross-linked networks (ZCN) were synthesized via the rational design of the phys. form of ZIF-8, and then a series of composite PEMs were prepd. by hybridizing ZCN with sulfonated poly(ether ether ketone) (SPEEK) matrix. The effect of the incorporation of zero-dimensional (0D) raw ZIF-8 nanoparticles and 2D ZCN on the proton conduction and methanol permeability of the composite membranes was systemically studied. Benefiting from the morphol. and compositional advantages of ZCN, the SPEEK/ZCN composite membranes displayed a significant enhancement in proton cond. under various conditions. In particular, the proton cond. of SPEEK/ZCN-2.5 membrane was up to 50.24 mS cm-1 at 120 °C-30% RH, which was 11.2 times that of the recast SPEEK membrane (4.50 mS cm-1) and 2.1 times that of SPEEK/ZIF membrane (24.1 mS cm-1) under the same condition. Meanwhile, the methanol permeability of the SPEEK/ZCN composite membranes was greatly reduced. Therefore, novel MOF/polymer composite PEMs with high selectivity were obtained. Our investigation results reveal that the proton cond. and methanol permeability of the MOF/polymer composite membranes can be effectively tailored via creating more elaborate superstructures of MOFs rather than altering the chem. component. This effective strategy may provide a useful guideline to integrate with other interesting MOFs to design MOF/polymer composite membranes.
- 56Liu, D.; Xie, Y.; Li, S.; Han, X.; Zhang, H.; Chen, Z.; Pang, J.; Jiang, Z. High dimensional stability and alcohol resistance aromatic poly(aryl ether ketone) polyelectrolyte membrane synthesis and characterization. ACS Appl. Energy Mater. 2019, 2, 1646– 1656, DOI: 10.1021/acsaem.8b01557[ACS Full Text], [CAS], Google Scholar56https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC1MXjtVShtLc%253D&md5=e7ac011db44d1ceeb85640cfb9e5894cHigh Dimensional Stability and Alcohol Resistance Aromatic Poly(aryl ether ketone) Polyelectrolyte Membrane Synthesis and CharacterizationLiu, Di; Xie, Yunji; Li, Su; Han, Xiaocui; Zhang, Haibo; Chen, Zheng; Pang, Jinhui; Jiang, ZhenhuaACS Applied Energy Materials (2019), 2 (3), 1646-1656CODEN: AAEMCQ; ISSN:2574-0962. (American Chemical Society)Crystd. sulfonated poly(arylene ether ketone) (Cr-SPAEK) materials constructed from dense sulfonated hydrophilic segments and cryst. poly(ether ketone) (PEK) hydrophobic backbone were designed. The membrane exhibited considerable proton cond. and superb solvent resistance owing to its special phase morphol., the presence of a broad hydrophilic ion transport channel, and a cryst. hydrophobic matrix. The dense sulfonated hydrophilic segment provides excellent proton cond.; the Cr-SPAEK-20 membrane exhibits higher proton-conducting ability than Nafion 117 at of 20-100 °C; its proton cond. reaches about 168 mS cm-1 at 100 °C. The cryst. PEK hydrophobic segment ensures superior solvent resistance and dimensional stability, guaranteeing the durability of the membrane in practical applications. The methanol permeability of Cr-SPAEK-20 is only one-eighth that of Nafion 117 when the test conditions are the same. The direct methanol fuel cell (DMFC), which is assembled by Cr-SPAEK-20, exhibited satisfactory open circuit voltage and max. power d. during the testing process. The Cr-SPAEK membranes have shown potential for DMFCs as polymer electrolyte materials.
- 57Dong, F.; Li, Z.; Wang, S.; Xu, L.; Yu, X. Preparation and properties of sulfonated poly(phthalazinone ether sulfone ketone)/zirconium sulfophenylphosphate/PTFE composite membranes. Int. J. Hydrogen Energy 2011, 36, 3681– 3687, DOI: 10.1016/j.ijhydene.2010.12.014[Crossref], [CAS], Google Scholar57https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC3MXisFait78%253D&md5=4053924511f4dd7c3bb89f135b14d930Preparation and properties of sulfonated poly(phthalazinone ether sulfone ketone)/zirconium sulfophenylphosphate/PTFE composite membranesDong, Feilong; Li, Zhongfang; Wang, Suwen; Xu, Lijuan; Yu, XianjinInternational Journal of Hydrogen Energy (2011), 36 (5), 3681-3687CODEN: IJHEDX; ISSN:0360-3199. (Elsevier Ltd.)Porous polytetrafluoroethylene (PTFE) membranes were used as support material for sulfonated poly(phthalazinone ether sulfone ketone) (SPPESK)/zirconium sulfophenyl phosphate (ZrSPP)/PTFE composite membranes. The membranes were prepd. via a spray painting method. Membranes were characterized by thermal gravimetric anal. (TGA) and SEM. The composite membranes exhibited good thermal stabilities. SEM micrographs confirmed that the pores of the PTFE were filled entirely with SPPESK and ZrSPP. The resulting composite membranes were mech. durable, dimensionally stable in alternating wet/dry environments, and had lower methanol permeabilities compared with the unsupported SPPESK/ZrSPP composite membranes reported in our previous work. The water uptake of these membranes was also lower than previous SPPESK/ZrSPP composite membranes. The proton cond. of PTFE supported SPPESK (DS 81%)/ZrSPP(10 wt%) composite membrane was as high as 0.24 S/cm at 120 °C. Thus, the composite membranes exhibited good thermal stabilities, proton conductivities, and good methanol resistance, indicating that these composite membranes could serve as effective alternative membranes for direct methanol fuel cells (DMFCs).
- 58Zhen, D.; He, G.; Xu, X.; Yan, X.; Du, N.; Gong, X.; Li, T.; Dai, Y.; Wu, X. Simultaneous enhancement of proton conductivity and methanol resistance of sulfonated poly(phthalazinone ether sulfone ketone)/superacid sulfated zirconia composite membranes for direct methanol fuel cells. J. Appl. Polym. Sci. 2018, 135, 46758– 46769, DOI: 10.1002/app.46758
- 59Rambabu, G.; Bhat, S. D. Sulfonated fullerene in SPEEK matrix and its impact on the membrane electrolyte properties in direct methanol fuel cells. Electrochim. Acta 2015, 176, 657– 669, DOI: 10.1016/j.electacta.2015.07.045[Crossref], [CAS], Google Scholar59https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC2MXhsVajtbjE&md5=bddd2e811db2ef2199237f3f6948be2bSulfonated fullerene in SPEEK matrix and its impact on the membrane electrolyte properties in direct methanol fuel cellsRambabu, Gutru; Bhat, Santoshkumar D.Electrochimica Acta (2015), 176 (), 657-669CODEN: ELCAAV; ISSN:0013-4686. (Elsevier Ltd.)Composite membranes of sulfonated polyether ether ketone (SPEEK) are prepd. with sulfonated fullerene as an additive by soln. cast methodol. for its use as polymer electrolyte in direct methanol fuel cells (DMFCs). Fullerene is functionalized by attaching sulfonic acid groups by formed precursor (4-benzene diazonium sulfonic acid) through diazotization reaction route. Functionalized fullerene is extensively characterized by FT-IR, XPS, 1H-NMR and elemental anal. to confirm the sulfonation. Structural changes in sulfonated fullerene (Sfu) are obsd. through FE-SEM and TEM anal. The composite membranes prepd. with varying Sfu content in SPEEK are characterized in terms of their physico-chem. properties in conjunction with ionic cond. and methanol permeability. Oxidative stabilities of these composite membranes are compared with pristine SPEEK membrane. DMFC performance of these membranes is evaluated and the results are compared with pristine SPEEK and Nafion-117 membranes. Steady state polarization in DMFC for SPEEK-Sfu (0.5 wt. %) exhibits peak power d. of 103 mW/cm2 which is at par with Nafion-117 membrane. Membrane electrode assemblies comprising optimized SPEEK-Sfu (0.5 wt. %) and pristine SPEEK matrix are subjected for time evolution studies to evaluate steady state peak power densities.
- 60Liang, Y.; Gong, C.; Qi, Z.; Li, H.; Wu, Z.; Zhang, Y.; Zhang, S.; Li, Y. Intermolecular ionic cross-linked sulfonated poly(ether ether ketone) membranes containing diazafluorene for direct methanol fuel cell applications. J. Power Sources 2015, 284, 86– 94, DOI: 10.1016/j.jpowsour.2015.02.159[Crossref], [CAS], Google Scholar60https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC2MXjslClsL0%253D&md5=10dcee21b08a570597f64a46361cbe2aIntermolecular ionic cross-linked sulfonated poly(ether ether ketone) membranes containing diazafluorene for direct methanol fuel cell applicationsLiang, Yu; Gong, Chenliang; Qi, Zhigang; Li, Hui; Wu, Zhongying; Zhang, Yakui; Zhang, Shujiang; Li, YanfengJournal of Power Sources (2015), 284 (), 86-94CODEN: JPSODZ; ISSN:0378-7753. (Elsevier B.V.)A series of novel ionic crosslinking sulfonated poly(ether ether ketone) (SPEEK) membranes contg. the diazafluorene functional group are synthesized to reduce the swelling ratio and methanol permeability for direct methanol fuel cell (DMFC) applications. The ionic crosslinking is realized by the interaction between sulfonic acid groups and pyridyl in diazafluorene. The prepd. membranes exhibit good mech. properties, adequate thermal stability, good oxidative stability, appropriate water uptake, and low swelling ratio. Moreover, the ionic cross-linked membranes exhibit lower methanol permeability in the range between 0.56 × 10-7 cm2 s-1 and 1.8 × 10-7 cm2 s-1, which is lower than Nafion 117, and they exhibit higher selectivity than Nafion 117 at 30° on the basis of applicable proton cond.
- 61Bu, F.; Zhang, Y.; Hong, L.; Zhao, W.; Li, D.; Li, J.; Na, H.; Zhao, C. 1,2,4-Triazole functionalized poly(arylene ether ketone) for high temperature proton exchange membrane with enhanced oxidative stability. J. Membr. Sci. 2018, 545, 167– 175, DOI: 10.1016/j.memsci.2017.09.072[Crossref], [CAS], Google Scholar61https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC2sXhsF2gsr7L&md5=b8a3e643ba9e6e449804849093e21cac1,2,4-Triazole functionalized poly(arylene ether ketone) for high temperature proton exchange membrane with enhanced oxidative stabilityBu, Fanzhe; Zhang, Yurong; Hong, Lihua; Zhao, Wanchen; Li, Di; Li, Jialin; Na, Hui; Zhao, ChengjiJournal of Membrane Science (2018), 545 (), 167-175CODEN: JMESDO; ISSN:0376-7388. (Elsevier B.V.)A series of novel 1,2,4-triazole grafted poly(arylene ether ketone) membranes were prepd. to absorb phosphoric acid and used as high temp. proton exchange membranes. Poly(arylene ether ketone) is firstly bromomethylated, followed by nucleophilic substitution of bromomethylated poly(arylene ether ketone) with 3-mercapto-1,2,4-triazole. The structure and the degree of substitution were confirmed by their 1H NMR spectra. 1,2,4-Triazole functionalized poly(arylene ether ketone) membranes exhibited high thermal decompn. temp. (Td(5%) higher than 271 °C) and tensile strengths (higher than 78 MPa). After doping with phosphoric acid, these membranes showed enhanced abilities to phosphoric acid absorption with increasing the amt. of triazole groups on the side chains. Phosphoric acid doped MTZPAEK(2.15) showed the highest Wdoping value of 142% and the proton cond. of 51 mS cm-1 at 190 °C. Remarkably, all the membranes exhibited great oxidative stabilities and could retain their shapes for more than 50 h in Fenton's reagent (3 wt% H2O2, 4 ppm Fe2+) at 80 °C. This advantage could be ascribed to the unique sulfide groups, which were introduced by nucleophilic substitution reaction and acted as free radical scavengers. The supposed mechanism of enhancing oxidative stability by sulfide groups was confirmed via FT-IR.
- 62Zhang, Y.; Miyake, J.; Akiyama, R.; Shimizu, R.; Miyatake, K. Sulfonated phenylene/quinquephenylene/perfluoroalkylene terpolymers as proton exchange membranes for fuel cells. ACS Appl. Energy Mater. 2018, 1, 1008– 1015, DOI: 10.1021/acsaem.7b00162[ACS Full Text], [CAS], Google Scholar62https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC1cXivVCitr0%253D&md5=9840edbfb61e4dde2cbcbae8d3e5f64dSulfonated phenylene/quinquephenylene/perfluoroalkylene terpolymers as proton exchange membranes for fuel cellsZhang, Yaojian; Miyake, Junpei; Akiyama, Ryo; Shimizu, Ryo; Miyatake, KenjiACS Applied Energy Materials (2018), 1 (3), 1008-1015CODEN: AAEMCQ; ISSN:2574-0962. (American Chemical Society)A novel series of terpolymers (SQF) contg. sulfophenylene, quinquephenylene, and perfluoroalkylene groups in the polymer main chain were designed and synthesized as proton exchange membranes for fuel cells. The terpolymers with high mol. wt. (Mw = 179-207 kDa, Mn = 41-50 kDa) and different ion exchange capacity (IEC) values (1.70, 2.56, and 3.34 mequiv g-1) gave flexible self-standing membranes by soln. casting. Compared to the two-component (sulfophenylene and quinquephenylene segments) copolymer membranes, the incorporation of the third component, perfluoroalkylene groups, resulted in better water utilization for the proton conduction, while it did not alter the other properties such as gas permeability and mech. strength. The selected membrane (SQF-3 with IEC = 2.56 mequiv g-1) exhibited high fuel cell performance under high- and low-humidity conditions with max. power d. reaching 0.97 W cm-2 at 100% RH (relative humidity) and 0.82 W cm-2 at 30% RH, resp., at a c.d. of 1.51 A cm-2 with oxygen. A good interfacial compatibility between the SQF-3 membrane and catalyst layers resulted in mass activity of the cathode catalyst comparable to that obtained with the Nafion membrane NRE 211. During the open circuit voltage (OCV) hold test with air and hydrogen at 80°C and 30% RH for 1000 h, the OCV showed a slight decrease from 0.97 to 0.88 V. Post-test analyses revealed that the SQF-3 membrane retained its initial high fuel cell performance due to its high chem. stability as well as low gas permeability.
- 63Chen, L.; Zhang, S.; Jiang, Y.; Jian, X. Preparation and characterization of sulfonated poly(aryl ether ketone)s containing 3,5-diphenyl phthalazinone moieties for proton exchange membrane. RSC Adv. 2016, 6, 75328– 75335, DOI: 10.1039/c6ra14848d[Crossref], [CAS], Google Scholar63https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC28Xht1Kltb3J&md5=bfc0b3d988ec52531299bce80a8aa06dPreparation and characterization of sulfonated poly(aryl ether ketone)s containing 3,5-diphenyl phthalazinone moieties for proton exchange membraneChen, Liyun; Zhang, Shouhai; Jiang, Yiwen; Jian, XigaoRSC Advances (2016), 6 (79), 75328-75335CODEN: RSCACL; ISSN:2046-2069. (Royal Society of Chemistry)A series of sulfonated poly(phthalazinone ether ketone)s contg. 3,5-di-Ph phthalazinone moieties (SPPEK-dPs) were prepd. by the sulfonation of poly(aryl ether ketone)s contg. 3,5-di-Ph phthalazinone moieties (PPEK-dPs) which were synthesized via direct nucleophilic polycondensation from 4-(4-hydroxyphenyl)-2,3-phthalazin-1-ketone (DHPZ), 4-(3,5-diphenyl-4-hydroxyphenyl)-2,3-phthalazin-1-ketone (DHPZ-dP) and 4,4-difluorobenzophenone (DFB). The mol. structures were assessed by FTIR and 1H-NMR spectroscopy. The ion exchange capacity (IEC) of these sulfonated polymers were in the range of 0.99-1.81 mmol g-1. SPPEK-dP proton exchange membranes demonstrated good mech. properties as well as dimensional, thermal, and oxidative stability. The proton conductivities of SPPEK-dP membranes increased with DHPZ-dP content and temp. The proton cond. of SPPEK-dP-55 was 13.18 × 10-2 S cm-1 at 95 °C. Furthermore, the methanol diffusion coeffs. of SPPEK-dP membranes were 0.12 × 10-7 cm2 s-1 to 1.09 × 10-7 cm2 s-1 depending on the molar ratio of DHPZ-dP. Remarkably, the selectivity of SPPEK-dP membranes was 5-7 times higher than that of Nafion 117 membranes under the same conditions. All of the above properties indicate that SPPEK-dPs have potential applications in proton exchange membranes for direct methanol fuel cells.
- 64Zhang, H.; Zhou, Z. Modified poly(phthalazinone ether ketone) membranes for direct methanol fuel cell. Polym. Adv. Technol. 2008, 19, 425– 431, DOI: 10.1002/pat.1028[Crossref], [CAS], Google Scholar64https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BD1cXntlWku78%253D&md5=9f2d76a2ba803ccb40f2a533bdd00faaModified poly(phthalazinone ether ketone) membranes for direct methanol fuel cellZhang, Hongwei; Zhou, ZhentaoPolymers for Advanced Technologies (2008), 19 (5), 425-431CODEN: PADTE5; ISSN:1042-7147. (John Wiley & Sons Ltd.)Sulfonated poly(phthalazinone ether ketone) (SPPEK) was prepd. by modification of poly(phthalazinone ether ketone) (PPEK) with 98% concd. H2SO4 or 98% concd. H2SO4 and chlorosulfonic acid mixt. at 80-100°. The presence of sulfonic acid groups in SPPEKs was confirmed by FTIR anal. and NMR and the DSs were detd. by EDX. A blend membrane of No. 21 SPPEK and phosphotungstic acid was prepd. The MeOH permeabilities of SPPEK and blend membranes were ∼20 times lower than that of Nafion 117 at room temp. A direct MeOH fuel cell test with 2 M MeOH soln. and air breathing showed that the blend membrane had a better performance than that of the Nafion 117.
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- Zhen Li, Xiaofeng Hao, Geng Cheng, Sheng Huang, Dongmei Han, Min Xiao, Shuanjin Wang, Yuezhong Meng. In situ implantation of cross-linked functional POSS blocks in Nafion® for high performance direct methanol fuel cells. Journal of Membrane Science 2021, 640 , 119798. https://doi.org/10.1016/j.memsci.2021.119798
- Lili Liu, Yao Lu, Yangyang Pu, Na Li, Zhaoxia Hu, Shouwen Chen. Highly sulfonated carbon nano-onions as an excellent nanofiller for the fabrication of composite proton exchange membranes with enhanced water retention and durability. Journal of Membrane Science 2021, 640 , 119823. https://doi.org/10.1016/j.memsci.2021.119823
- Sara Barati, Mohsen Mehdipourghazi, Mahdi Abdollahi, Khadijeh Hooshyari, Behnam Khoshandam. Preparation, characterization and proton transport of new porous nanocomposite membranes based on polybenzimidazole, lignin and TiO 2 nanoparticles for high temperature PEM fuel cells. International Journal of Energy Research 2021, 45 (14) , 20057-20072. https://doi.org/10.1002/er.7083
- Mohammad Bagher Karimi, Khadijeh Hooshyari, Parisa Salarizadeh, Hossein Beydaghi, V.M. Ortiz- Martínez, A. Ortiz, I. Ortiz Uribe, Fereidoon Mohammadi. A comprehensive review on the proton conductivity of proton exchange membranes (PEMs) under anhydrous conditions: Proton conductivity upper bound. International Journal of Hydrogen Energy 2021, 46 (69) , 34413-34437. https://doi.org/10.1016/j.ijhydene.2021.08.015
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- Honghao Huang, Yefei Ma, Zhongqing Jiang, Zhong-Jie Jiang. Spindle-like MOFs-derived porous carbon filled sulfonated poly (ether ketone): A high performance proton exchange membrane for direct methanol fuel cells. Journal of Membrane Science 2021, 112 , 119585. https://doi.org/10.1016/j.memsci.2021.119585
- Hossein Beydaghi, Leyla Najafi, Sebastiano Bellani, Ahmad Bagheri, Beatriz Martín-García, Parisa Salarizadeh, Khadijeh Hooshyari, Sara Naderizadeh, Michele Serri, Lea Pasquale, Bing Wu, Reinier Oropesa-Nuñez, Zdeněk Sofer, Vittorio Pellegrini, Francesco Bonaccorso. Functionalized metallic transition metal dichalcogenide (TaS 2 ) for nanocomposite membranes in direct methanol fuel cells. Journal of Materials Chemistry A 2021, 9 (10) , 6368-6381. https://doi.org/10.1039/D0TA11137F
Abstract
Figure 1
Figure 1. Scheme for the synthesis of SO3H–TiO2@[email protected]3H nanoparticles.
Figure 2
Figure 2. FTIR spectra of different prepared nanoparticles and membranes.
Figure 3
Figure 3. Diffraction patterns of TiO2 (a) and SO3H–TiO2@[email protected]3H nanoparticles.
Figure 4
Figure 4. (a) SEM images of TiO2, (b) TiO2@[email protected], and (c) SO3H–TiO2@[email protected]3H nanoparticles.
Figure 5
Figure 5. Surface and cross-sectional images of (a,c) MS and (b,d) MSN5 membranes.
Figure 6
Figure 6. EDX mapping images of (a) MSN1, (b) MSN3, (c) MSN5, and (d) MSN7 membranes.
Figure 7
Figure 7. (a) Water uptake and (b) MS diagrams of different prepared PEMs at temperatures between 20 and 80 °C.
Figure 8
Figure 8. Schematic of proton conductivity in the as-prepared nanocomposite membrane.
Figure 9
Figure 9. Arrhenius plots for proton conductivity at different temperatures.
Figure 10
Figure 10. Polarization curves of different prepared membranes in 2 M methanol solution and room temperature.
References
ARTICLE SECTIONSThis article references 64 other publications.
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- 7Beydaghi, H.; Javanbakht, M.; Salar Amoli, H.; Badiei, A.; Khaniani, Y.; Ganjali, M. R.; Norouzi, P.; Abdouss, M. Synthesis and characterization of new proton conducting hybrid membranes for PEM fuel cells based on poly(vinyl alcohol) and nanoporous silica containing phenyl sulfonic acid. Int. J. Hydrogen Energy 2011, 36, 13310– 13316, DOI: 10.1016/j.ijhydene.2010.08.085[Crossref], [CAS], Google Scholar7https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC3MXhtFyktL%252FF&md5=f8612d10b191b6430f6943eb730082e6Synthesis and characterization of new proton conducting hybrid membranes for PEM fuel cells based on poly(vinyl alcohol) and nanoporous silica containing phenyl sulfonic acidBeydaghi, Hossein; Javanbakht, Mehran; Salar Amoli, Hossein; Badiei, Alireza; Khaniani, Yeganeh; Ganjali, Mohammad Reza; Norouzi, Parviz; Abdouss, MajidInternational Journal of Hydrogen Energy (2011), 36 (20), 13310-13316CODEN: IJHEDX; ISSN:0360-3199. (Elsevier Ltd.)Org.-inorg. hybrid proton exchange membranes were prepd. from poly(vinyl alc.) (PVA) and various amts. of nanoporous silica contg. Ph sulfonic acid groups. These hybrid membranes were prepd. via co-condensation of functionalized nanoporous SBA-15 (SBA-ph-SO3H) as hydrophilic inorg. modifier, glutaraldehyde (GLA) as crosslinking agent in a PVA matrix. These membranes were characterized for their morphol., thermal stability, electrochem. and physicochem. properties using SEM, Fourier transform IR spectroscopy (FTIR), differential scanning calorimetry (DSC), and water uptake studies. The SBA-ph-SO3H/PVA composite membranes have a higher water retention and thermal stability than that of Nafion 117, perhaps because of responsibility of both acidic groups and nanoporous structure of silica additive. This work demonstrates the promising potential of new composite membranes for the development of high-performance and high-stability PEM fuel cells with improved proton cond.
- 8Salarizadeh, P.; Javanbakht, M.; Pourmahdian, S.; Bagheri, A.; Beydaghi, H.; Enhessari, M. Surface modification of Fe2TiO5 nanoparticles by silane coupling agent: Synthesis and application in proton exchange composite membranes. J. Colloid Interface Sci. 2016, 472, 135– 144, DOI: 10.1016/j.jcis.2016.03.036[Crossref], [PubMed], [CAS], Google Scholar8https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC28XkvFSiurc%253D&md5=7be69f8b69ee65a83d8da5aafe29035bSurface modification of Fe2TiO5 nanoparticles by silane coupling agent: Synthesis and application in proton exchange composite membranesSalarizadeh, Parisa; Javanbakht, Mehran; Pourmahdian, Saeed; Bagheri, Ahmad; Beydaghi, Hossein; Enhessari, MortezaJournal of Colloid and Interface Science (2016), 472 (), 135-144CODEN: JCISA5; ISSN:0021-9797. (Elsevier B.V.)Fe2TiO5 nanoparticles (IT) were modified with 3-aminopropyltriethoxysilane (APTES) as a reinforcing filler for proton exchange membranes. The main operating parameters such as reaction time (R.T), APTES/IT and triethylamine (TEA)/IT ratios have been optimized for max. grafting efficiency. The optimum conditions for reaction time, APTES/IT, and TEA/IT ratios were 6 h, 4 and 0.3 resp. It was obsd. that the APTES/IT and TEA/IT ratios were the most significant parameters affecting the grafting percentage. Modified nanoparticles were characterized using FT-IR, TGA, SEM, TEM and XRD techniques. Effects of modified nanoparticles in proton exchange membrane fuel cells (PEMFC) were evaluated. The resulting nanocomposite membranes exhibited higher proton cond. in comparison with pristine SPPEK and SPPEK/IT membranes. This increase is attributed to connectivity of the water channels which creates more direct pathways for proton transport. Composite membrane with 3% AIT (6.46% grafting amt.) showed 0.024 S cm-1 proton cond. at 25 °C and 149 mW cm-2 power d. (at 0.5 V) at 80 °C which were about 243% and 51%, resp. higher than that of pure SPPEK.
- 9He, Q.; Zheng, J.; Zhang, S. Preparation and characterization of high performance sulfonated poly(p-phenylene-co-aryl ether ketone) membranes for direct methanol fuel cells. J. Power Sources 2014, 260, 317– 325, DOI: 10.1016/j.jpowsour.2014.03.028[Crossref], [CAS], Google Scholar9https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC2cXms1Ggsr4%253D&md5=6641886d967e40c8ca65370e7571c7dcPreparation and characterization of high performance sulfonated poly(p-phenylene-co-aryl ether ketone) membranes for direct methanol fuel cellsHe, Qingyi; Zheng, Jifu; Zhang, SuoboJournal of Power Sources (2014), 260 (), 317-325CODEN: JPSODZ; ISSN:0378-7753. (Elsevier B.V.)A series of sulfonated poly(p-phenylene-co-aryl ether ketone)s (SPP-co-PAEK) were designed as membrane materials for direct methanol fuel cell (DMFC) applications. The materials for such membranes were prepd. via the nickel (0) catalyzed coupling copolymn. of 2,5-dichloro-3-sulfobenzophenone and 2,6-bis(4-(4-chlorobenzoyl)phenoxy)benzonitrile. The SPP-co-PAEK membranes show the desired characteristics such as excellent thermal and mech. properties, good oxidative stability, low methanol permeability and well-defined micro-phase sepn. With an ion exchange capacity (IEC) ranging from 1.90-2.59 mequiv g-1, these membranes display comparable proton cond. (0.085-0.170 S cm-1) to Nafion 117 when fully hydrated at 80°. In addn., the passive direct methanol fuel cell with SPP-co-PAEK CN 1.86 (IEC = 1.90 mequiv g-1) membrane presents a max. power d. of 24.5 mW cm-2 at 25°, which is comparable to the value of Nafion 117 (24.3 mW cm-2).
- 10Beydaghi, H.; Javanbakht, M.; Bagheri, A.; Salarizadeh, P.; Zahmatkesh, H. G.; Kashefi, S.; Kowsari, E. Novel nanocomposite membranes based on blended sulfonated poly(ether ether ketone)/poly(vinyl alcohol) containing sulfonated graphene oxide/Fe3 O4 nanosheets for DMFC applications. RSC Adv. 2015, 5, 74054– 74064, DOI: 10.1039/c5ra12941a[Crossref], [CAS], Google Scholar10https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC2MXhtlOgtrnF&md5=1806dc83d3a5965c07ef590b33419cf3Novel nanocomposite membranes based on blended sulfonated poly(ether ether ketone)/poly(vinyl alcohol) containing sulfonated graphene oxide/Fe3O4 nanosheets for DMFC applicationsBeydaghi, Hossein; Javanbakht, Mehran; Bagheri, Ahmad; Salarizadeh, Parisa; Zahmatkesh, Hossein Ghafarian-; Kashefi, Sepideh; Kowsari, ElahehRSC Advances (2015), 5 (90), 74054-74064CODEN: RSCACL; ISSN:2046-2069. (Royal Society of Chemistry)In this study, sulfonated graphene oxide (SGO)/Fe3O4 nanosheets were synthesized by hydrothermal method and incorporated into blend sulfonated poly(ether ether ketone) (SPEEK)/poly(vinyl alc.) (PVA) matrix with different wt. percent of (SGO)/Fe3O4 nanosheets. The performances of prepd. membranes were investigated by water uptake, membrane swelling, mech. and thermal stability, proton cond., methanol permeability and DMFC test. It was found that the water uptake and tensile strength of SPEEK membrane increased and proton cond. and power d. decreased by blending with PVA. Incorporation of SGO/Fe3O4 nanosheets into SPEEK/PVA matrix enhanced mech. stability, proton cond. and methanol barrier properties of membrane. The SPEEK/PVA/SGO/Fe3O4 nanocomposite membrane with optimal nanosheets content (5 wt%) exhibits low methanol permeability (8.83 × 10-7 cm2 s-1), high tensile strength (51.2 MPa), high proton cond. (0.084 S cm-1 at 25 °C) and high power d. (122.7 mW cm-2 at 80 °C) and suggests its potential application in DMFCs.
- 11Bagheri, A.; Javanbakht, M.; Hosseinabadi, P.; Beydaghi, H.; Shabanikia, A. Preparation and characterization of SPEEK/SPVDF-co-HFP/LaCrO3 nanocomposite blend membranes for direct methanol fuel cells. Polymer 2018, 138, 275– 287, DOI: 10.1016/j.polymer.2018.01.049[Crossref], [CAS], Google Scholar11https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC1cXisFehsrg%253D&md5=7fdc8e7c6604ac14ed10d50a8f06e630Preparation and characterization of SPEEK/SPVDF-co-HFP/LaCrO3 nanocomposite blend membranes for direct methanol fuel cellsBagheri, Ahmad; Javanbakht, Mehran; Hosseinabadi, Parisa; Beydaghi, Hossein; Shabanikia, AkbarPolymer (2018), 138 (), 275-287CODEN: POLMAG; ISSN:0032-3861. (Elsevier Ltd.)Here, nanocomposite blend membrane comprised of the sulfonated poly(ether ether ketone) (SPEEK), sulfonated poly(vinylidenefluoride-co-hexafluoropropylene) (SPVDF-co-HFP) and LaCrO3 was prepd. by the solvent casting method. The prepd. membranes exhibit a variety of advantages, such as desirable proton cond., good thermal and mech. stability, outstanding water and MeOH retention and oxidative stability. The increase in proton cond. from 32.7 mS/cm in SPEEK/SPVDF-co-HFP blend membrane to 75.3 mS/cm in nanocomposite membrane is achieved at the nanoparticle content of 1.5 wt.% at 20°, stemming from enhanced connectivity of the ionic groups which facilitates the proton transportation through the membrane. The MeOH permeability of the nanocomposite membranes was altered from 2.11 × 10-7 to 1.90 × 10-7 cm2/s, by addn. of 1.5 wt.% LaCrO3 nanoparticles, which show this membrane can act as effective barrier against MeOH permeation. The max. power d. of blend membrane was increased from 43.0 to 61.5 mW/cm2 with addn. of 1.5 wt.% nanoparticles and this results show that the nanocomposite membranes could be applied as a promising candidate as a proton exchange membrane for direct MeOH fuel cells.
- 12Selvakumar, K.; Ramesh Prabhu, M. Investigation on meta-polybenzimidazole blend with sulfonated PVdF-HFP proton conducting polymer electrolytes for HT-PEM fuel cell application. J. Mater. Sci.: Mater. Electron. 2018, 29, 15163– 15173, DOI: 10.1007/s10854-018-9658-z[Crossref], [CAS], Google Scholar12https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC1cXhtlalsbrK&md5=c3ae5687dce3a7e3b2fa0775d01acc14Investigation on meta-polybenzimidazole blend with sulfonated PVdF-HFP proton conducting polymer electrolytes for HT-PEM fuel cell applicationSelvakumar, Kanagaraj; Ramesh Prabhu, ManimuthuJournal of Materials Science: Materials in Electronics (2018), 29 (17), 15163-15173CODEN: JSMEEV; ISSN:0957-4522. (Springer)Sulfonated poly (Vinylidene Fluoride-co-hexafluoro propylene) (SPVdF-HFP) blended with varying concns. of m-poly (Benzimidazole) (PBI) were prepd. by soln. casting techinque. The sulfonation of PVdF-HFP was carried out with fuming chlorosulfonic acid at 60 °C and the degree of sulfonation was found to be 2.48%. The addn. of m-PBI into the hydrophilic sulfonated PVdF-HFP membrane has provided good chem. and thermal stability. And also the increases the physico-chem. characteristics such as the water uptake, ion exchange capacity and proton cond. An inter chain sepn. and specific interaction between the two polymers in the blends was obsd. by XRD and FT-IR analyses. The Fourier transform spectroscopy indicated the intense ionic bond between-SO3H and N-basic group. The 25% of m-PBI based blend polymer electrolyte gives high proton cond. (5.72 × 10-3 S/cm) at 160 °C and also the thermal stability. The temp. dependent proton cond. of the polymer electrolyte follows an Arrhenius relationship and Grotthuss mechanism and it shows hopping of ions in the polymer matrix. It is noticed that the addn. of m-PBI in the sulfonated PVdF-HFP enhances the mech., thermal and proton cond., which are sufficiently better for the use in HT-PEM fuel cell applications.
- 13Ozden, A.; Ercelik, M.; Devrim, Y.; Colpan, C. O.; Hamdullahpur, F. Evaluation of sulfonated polysulfone/zirconium hydrogen phosphate composite membranes for direct methanol fuel cells. Electrochim. Acta 2017, 256, 196– 210, DOI: 10.1016/j.electacta.2017.10.002[Crossref], [CAS], Google Scholar13https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC2sXhs1Chsb3J&md5=f812fea008b31e8bb2bd9d0c61a9e99dEvaluation of sulfonated polysulfone/zirconium hydrogen phosphate composite membranes for direct methanol fuel cellsOzden, Adnan; Ercelik, Mustafa; Devrim, Yilser; Colpan, C. Ozgur; Hamdullahpur, FeridunElectrochimica Acta (2017), 256 (), 196-210CODEN: ELCAAV; ISSN:0013-4686. (Elsevier Ltd.)Direct MeOH fuel cell (DMFC) technol. has advanced perceivably, but tech. challenges remain that must be overcome for further performance improvements. Thus, sulfonated polysulfone/Zr H phosphate (SPSf/ZrP) composite membranes with various sulfonation degrees (20%, 35%, and 42%) and a const. concn. of ZrP (2.5%) were prepd. to mitigate the tech. challenges assocd. using conventional Nafion membranes in DMFCs. The composite membranes were studied through SEM, Electrochem. Impedance Spectroscopy (EIS), Thermogravimetric Anal. (TGA), oxidative stability and H2O uptake measurements, and single cell testing. Comparison was also made with Nafion 115. Single cell tests were performed under various MeOH concns. and cell temps. Stability characteristics of the DMFCs under charging and discharging conditions were studied via 1200 min short-term stability tests. The response characteristics of the DMFCs under dynamic conditions were detd. at the start-up and shut-down stages. Composite membranes with sulfonation degrees of 35% and 42% are highly promising due to their advanced characteristics with respect to proton cond., H2O uptake, thermal resistance, oxidative stability, and MeOH suppression. For the whole range of parameters studied, the max. power d. obtained for SPSf/ZrP-42 (119 mW cm-2) is 13% higher than that obtained for Nafion 115 (105 mW cm-2).
- 14Amoozadeh, A.; Mazdarani, H.; Beydaghi, H.; Tabrizian, E.; Javanbakht, M. Novel nanocomposite membrane based on Fe3O4@[email protected]2–SO3H: hydration, mechanical and DMFC study. New J. Chem. 2018, 42, 16855– 16862, DOI: 10.1039/c8nj03646b[Crossref], [CAS], Google Scholar14https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC1cXhs1Cgtb%252FN&md5=bdb6c823e57294a09afbb29424d9c385Novel nanocomposite membrane based on [email protected]@TiO2-SO3H: hydration, mechanical and DMFC studyAmoozadeh, Ali; Mazdarani, Hourieh; Beydaghi, Hossein; Tabrizian, Elham; Javanbakht, MehranNew Journal of Chemistry (2018), 42 (20), 16855-16862CODEN: NJCHE5; ISSN:1144-0546. (Royal Society of Chemistry)In this paper, a sulfonated poly(ether ether ketone)/SO3H-functionalized magnetic-titania (SPEEK/[email protected]@TiO2-SO3H) nanocomposite membrane is synthesized with the aim of reducing methanol permeability as well as improving the proton cond. and selectivity of pristine polymer to be used instead of Nafion in a direct methanol fuel cell (DMFC). The introduced nanocomposite membrane is prepd. by soln. casting of SPEEK in di-Me acetamide (DMAc) solvent and dispersing various percentages of [email protected]@TiO2-SO3H in the polymer matrix. The different properties of the membranes were investigated by ion exchange capacity, water uptake, mech. stability, proton cond., methanol permeability, selectivity and a DMFC test. The catalytic properties of [email protected]@TiO2-SO3H nanoparticles improve the power d. of DMFC with increasing reaction kinetics in the membrane electrode assembly (MEA). According to the obtained results, a nanocomposite membrane (with optimum 5 wt% nanoparticles) has low methanol permeability (3.35 × 10-7 cm2 s-1), high proton cond. (0.081 S cm-1), high mech. stability (34.87 MPa) and high power d. (51.27 mW cm-2), which makes it a suitable membrane for DMFCs.
- 15Selvakumar, K.; Rajendran, S.; Ramesh Prabhu, M. Influence of barium zirconate on SPEEK-based polymer electrolytes for PEM fuel cell applications. Ionics 2019, 25, 2243– 2253, DOI: 10.1007/s11581-018-2613-4[Crossref], [CAS], Google Scholar15https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC1cXhtFWiu7bF&md5=2135540e1b979a84f4957e363ca6e754Influence of barium zirconate on SPEEK-based polymer electrolytes for PEM fuel cell applicationsSelvakumar, K.; Rajendran, S.; Ramesh Prabhu, M.Ionics (2019), 25 (5), 2243-2253CODEN: IONIFA; ISSN:0947-7047. (Springer)The sulfonated poly(ether ether ketone) (SPEEK)-barium zirconate (BaZrO3)-based polymer nanocomposite membranes are prepd. by solvent casting technique. The composite membranes have been characterized by X-ray diffraction (XRD), Fourier transform IR spectroscopy (FTIR), NMR (NMR), water uptake, swelling, and ion exchange capacity (IEC). The NMR, IEC, and CHNSO analyses confirmed the degree of sulfonation level of SPEEK as 65%. Addn. of 6 wt% BaZrO3 filler improved the proton cond. of the polymer electrolyte considerably with 3.12 × 10-1 S/cm at 90 °C. SEM and AFM studies indicated that the BaZrO3 nanofillers are well distributed in the polymer up to 8 wt%. The max. power and c.d. are 183 mW cm-2 and 280 mA cm-2 for 94 wt% SPEEK and 06 wt% BaZrO3. It is concluded that the above composite membrane is a potential candidate for PEM fuel cell applications.
- 16Raja, K.; Raja Pugalenthi, M.; Ramesh Prabhu, M. Investigation on SPEEK/PAI/SrTiO3-based nanocomposite membrane for high-temperature proton exchange membrane fuel cells. Ionics 2019, 25, 5177– 5188, DOI: 10.1007/s11581-019-03100-7[Crossref], [CAS], Google Scholar16https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC1MXht1WqsbjN&md5=704a118e96aeb3b2f72e2e00b9c31c9aInvestigation on SPEEK/PAI/SrTiO3-based nanocomposite membrane for high-temperature proton exchange membrane fuel cellsRaja K; Raja Pugalenthi M; Ramesh Prabhu MIonics (2019), 25 (11), 5177-5188CODEN: IONIFA; ISSN:0947-7047. (Springer)Optimization of an alternative proton exchange membrane fuel cell (PEMFC) instead of Nafion membrane electrolyte with sulfonated poly(ether ether ketone) (SPEEK) is regarded as the most promising alternative to com. membranes. In this work, facile composite membranes consisting of SPEEK/poly (amide imide) (PAI) and SrTiO3-based nanocomposite electrolyte are prepd. by solvent casting technique. The prepd. samples are characterized by FT-IR, thermo-mech. stability, electrochem. impedance spectroscopy (EIS), water uptake capacity, swelling ratio, and ion transport capacity tests. The incorporation of PAI in the membrane structure has increased the mech. strength, increased water uptake, and restricted swelling ratio. Incorporation of SrTiO3 nanoparticle fillers are easily bounded into the polymer membrane matrix via ionic interaction due to presence of sulfonic acid groups moieties in SPEEK. The addn. of SrTiO3 filler in the blend membranes provided enhanced protonic cond., ion exchange capacity with restricted swelling capacity, and inhibit water loss at high temps. The highest proton cond. of 10.78 × 10-3 S cm-1 at 150°C is obtained by the SPEEK (90 wt%)/PAI (10 wt%)/SrTiO3 (06 wt%) coded membrane in electrochem. impedance spectroscopy. This study shows that nanocomposite blend membrane seems to be a promising alternative membrane for PEMFC application.
- 17Raja, K.; Raja Pugalenthi, M.; Ramesh Prabhu, M. The effect of incorporation of ferrous titanate nanoparticles in sulfonated poly(ether ether ketone)/poly (amide imide) acid-base polymer for cations exchange membrane fuel cells. J. Solid State Electrochem. 2019, 24, 35, DOI: 10.1007/s10008-019-04453-9
- 18Bagheri, A.; Salarizadeh, P.; Sabooni Asre Hazer, M.; Hosseinabadi, P.; Kashefi, S.; Beydaghi, H. The effect of adding sulfonated SiO2 nanoparticles and polymer blending on properties and performance of sulfonated poly ether sulfone membrane: Fabrication and optimization. Electrochim. Acta 2019, 295, 875– 890, DOI: 10.1016/j.electacta.2018.10.197[Crossref], [CAS], Google Scholar18https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC1cXit1aqt7jM&md5=b829957c1a25b643d7d0f40ea5b09147The effect of adding sulfonated SiO2 nanoparticles and polymer blending on properties and performance of sulfonated poly ether sulfone membrane: Fabrication and optimizationBagheri, Ahmad; Salarizadeh, Parisa; Sabooni Asre Hazer, Maryam; Hosseinabadi, Parisa; Kashefi, Sepideh; Beydaghi, HosseinElectrochimica Acta (2019), 295 (), 875-890CODEN: ELCAAV; ISSN:0013-4686. (Elsevier Ltd.)Sulfonated poly(phthalazinone ether ketone) and modified silica nanoparticles by poly (2-acrylamido-2-methyl-1-propanesulfonic acid) were prepd. and their impact investigated on the physicochem. and transport properties of sulfonated poly ether sulfone. To optimize the wt. percentage of incorporated components in sulfonated poly ether sulfone nanocomposite membranes and predict their performance, the central composite design (CCD) of the response surface method (RSM) was utilized. The independent parameters (wt. percentage of added sulfonated poly (phthalazinone ether ketone) (SPPEK) and nanoparticles) and the responses (water uptake (WU), swelling ratio (SR), δ value, proton cond., methanol permeability and selectivity) were developed and verified with exptl. data. The optimum parameters for achieving the highest performance represented by proton cond. of 57.9 mS cm-1, methanol permeability of 3.21 × 10-7 cm2 s-1, and membrane selectivity of 18.03 × 104 s S cm-3 obtained at contents of SPPEK and nanoparticles of 23.07 and 3.9 wt%, resp. The membrane with optimum additives demonstrated favorable direct methanol fuel cell (DMFC) characteristics such as reduced methanol permeability, high selectivity, and improved mech. integrity as well as power d.
- 19Kalaiselvimary, J.; Prabhu, M. R. Influence of sulfonated GO/sulfonated biopolymer as polymer electrolyte membrane for fuel cell application. J. Mater. Sci.: Mater. Electron. 2018, 29, 5525– 5535, DOI: 10.1007/s10854-018-8521-6[Crossref], [CAS], Google Scholar19https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC1cXhtl2qtr0%253D&md5=9d44c3c081f36f3cd6c1d81eba1ab6a8Influence of sulfonated GO/sulfonated biopolymer as polymer electrolyte membrane for fuel cell applicationKalaiselvimary, J.; Prabhu, M. RameshJournal of Materials Science: Materials in Electronics (2018), 29 (7), 5525-5535CODEN: JSMEEV; ISSN:0957-4522. (Springer)Graphene oxide is well known as a advanced functional material because of its super high sp. surface area, as well as excellent amphipathicity. Sulfonated graphene oxide bio nanocomposite membranes are presented as a potential proton exchange membrane for fuel cell applications. The GO nanopowder was produced from graphite powder by the modified Hummers method and then sulfonated by chlorosulfonic acid as a sulfonic reagent. The s-GO-based s-CS/PEO composite membranes were prepd. by soln. casting technique. The synthesized electrolytes are studied by different characterization to check the elec. and thermal properties of the membrane. FTIR and Raman showed the formation of GO, s-GO and prepd. electrolytes interaction between the functional groups resp. The max. ionic cond. of s-Chitosan (s-CS)/PEO/s-GO nanocomposite membranes at 6 wt% of s-GO in the order of 10-2 S/cm. Moreover, the existence of the intermol. interactions between sulfonated-CS/PEO and s-GO can improve the thermal stability and interfacial compatibility between nanofiller and polymer matrixes.
- 20Beydaghi, H.; Javanbakht, M.; Salarizadeh, P.; Bagheri, A.; Amoozadeh, A. Novel proton exchange membrane nanocomposites based on sulfonated tungsten trioxide for application in direct methanol fuel cells. Polymer 2017, 119, 253– 262, DOI: 10.1016/j.polymer.2017.05.026[Crossref], [CAS], Google Scholar20https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC2sXos1Sls78%253D&md5=9a0fad9a4df0518575e7e79ba5fe7ec8Novel proton exchange membrane nanocomposites based on sulfonated tungsten trioxide for application in direct methanol fuel cellsBeydaghi, Hossein; Javanbakht, Mehran; Salarizadeh, Parisa; Bagheri, Ahmad; Amoozadeh, AliPolymer (2017), 119 (), 253-262CODEN: POLMAG; ISSN:0032-3861. (Elsevier Ltd.)Novel sulfonated poly (phthalazinone ether ketone) (SPPEK)/sulfonated poly (vinylidene fluoride-co-hexafluoropropylene) (SPVdF-co-HFP)/sulfonated tungsten trioxide (SWO3) nanocomposite blend membranes were fabricated as alternative proton exchange membranes (PEM) for application in direct methanol fuel cell (DMFC). PPEK and PVdF-co-HFP were sulfonated using sulfuric acid and chlorosulfonic acid, resp. The degree of sulfonation (DS) of produced SPPEK and SPVdF-co-HFP were detd. by titrn. method and found to be 68% and 30%, resp. The dominant characteristics of the prepd. membranes, such as water uptake, membrane swelling, proton cond., methanol permeability, selectivity and DMFC performance were investigated. The membranes contg. SWO3 nanoparticles indicated higher proton cond. and lower methanol permeability compared with pristine SPPEK and blend membranes. This improvement is attributed to presence of the sulfonated groups of nanoparticles that increases proton cond. with Grotthus and vehicle mechanisms. The catalytic properties of SWO3 nanoparticles increase kinetic of reaction in interface surface of membrane and electrode and improve performance of DMFCs. Well optimized nanocomposite blend membrane (MSSW5) showed proton cond. of 0.071 S cm-1, methanol permeability of 9.5 × 10-8 cm2 S-1 and power d. of 63.60 mW cm-2 at room temp., thus it can be a suitable candidate for DMFC application.
- 21Hooshyari, K.; Heydari, S.; Javanbakht, M.; Beydaghi, H.; Enhessari, M. Fabrication and performance evaluation of new nanocomposite membranes based on sulfonated poly(phthalazinone ether ketone) for PEM fuel cells. RSC Adv. 2020, 10, 2709– 2721, DOI: 10.1039/c9ra08893h[Crossref], [CAS], Google Scholar21https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BB3cXptlahtQ%253D%253D&md5=08d8c2c38e1999e1d15d12c1d4779f2fFabrication and performance evaluation of new nanocomposite membranes based on sulfonated poly(phthalazinone ether ketone) for PEM fuel cellsHooshyari, Khadijeh; Heydari, Samira; Javanbakht, Mehran; Beydaghi, Hossein; Enhessari, MortezaRSC Advances (2020), 10 (5), 2709-2721CODEN: RSCACL; ISSN:2046-2069. (Royal Society of Chemistry)The purpose of this work is to enhance the proton cond. and fuel cell performance of sulfonated poly(phthalazinone ether ketone) (SPPEK) as a proton exchange membrane through the application of SrTiO3 perovskite nanoparticles. Nanocomposite membranes based on SPPEK and SrTiO3 perovskite nanoparticles were prepd. via a casting method. The highest proton cond. of nanocomposite membranes obtained was 120 mS cm-1 at 90°C and 95% RH. These enhancements could be related to the hygroscopic structure of SrTiO3 perovskite nanoparticles and the formation of hydrogen bonds between nanoparticles and water mols. The satisfactory power d., 0.41 W cm-2 at 0.5 V and 85°C, of the nanocomposite membrane (5 wt% content of nanoparticles) confirms their potential for application in the PEM fuel cells.
- 22Luo, T.; Zhang, Y.; Xu, H.; Zhang, Z.; Fu, F.; Gao, S.; Ouadah, A.; Dong, Y.; Wang, S.; Zhu, C. Highly conductive proton exchange membranes from sulfonated polyphosphazene-graft-copolystyrenes doped with sulfonated single-walled carbon nanotubes. J. Membr. Sci. 2016, 514, 527– 536, DOI: 10.1016/j.memsci.2016.04.071[Crossref], [CAS], Google Scholar22https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC28XovVaitrc%253D&md5=d1112a8fb67d1044fe563082ea480935Highly conductive proton exchange membranes from sulfonated polyphosphazene-graft-copolystyrenes doped with sulfonated single-walled carbon nanotubesLuo, Tianwei; Zhang, Yanxia; Xu, Hulin; Zhang, Zeyu; Fu, Fengyan; Gao, Shuitao; Ouadah, Amina; Dong, Yan; Wang, Shan; Zhu, ChangjinJournal of Membrane Science (2016), 514 (), 527-536CODEN: JMESDO; ISSN:0376-7388. (Elsevier B.V.)As polymer electrolyte candidates, a series of composite membranes CF3-PSx-PSBOSy-SCNT of copolymer poly[(4-trifluoromethylphenoxy)(4-methylphenoxy)phosphazene]-g-poly{(styrene)x-r-[4-(4-sulfobutyloxy)styrene]y} (CF3-PSx-PSBOSy) doped with sulfonated single-walled carbon nanotubes (S-SWCNTs) were prepd. Most of them showed higher proton cond. than that of Nafion 117. Compared with native membranes, the composite membranes exhibited higher proton cond. but also a significantly reduced methanol permeability, suggesting a great enhancement effect of S-SWCNTs on the proton conduction and methanol resistance. Specifically, membranes CF3-PS11-PSBOS33-SCNT and CF3-PSBOS45-SCNT showed proton cond. at 0.46 S/cm and 0.55 S/cm under fully hydrated conditions at 100 °C, resp., which were 2.2-2.6 times as much as that of Nafion 117. Excellent selectivity much more than that of Nafion 117 were also obtained for the composite membranes.
- 23Beydaghi, H.; Javanbakht, M.; Kowsari, E. Synthesis and characterization of poly(vinyl alcohol)/sulfonated graphene oxide nanocomposite membranes for use in PEMFCs. Ind. Eng. Chem. Res. 2014, 53, 16621– 16632, DOI: 10.1021/ie502491d[ACS Full Text], [CAS], Google Scholar23https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC2cXhslahsrjN&md5=ff56c8d36efcca914494c48dbf895974Synthesis and Characterization of Poly(vinyl alcohol)/Sulfonated Graphene Oxide Nanocomposite Membranes for Use in Proton Exchange Membrane Fuel Cells (PEMFCs)Beydaghi, Hossein; Javanbakht, Mehran; Kowsari, ElahehIndustrial & Engineering Chemistry Research (2014), 53 (43), 16621-16632CODEN: IECRED; ISSN:0888-5885. (American Chemical Society)In this study, novel cross-linked nanocomposite membranes have been prepd. from poly(vinyl alc.) (PVA) and aryl sulfonated graphene oxide (SGO) and a way of crosslinking to improve the chem., thermal, and mech. stabilities of the nanocomposite was adopted. The surface of the graphene oxide nanoparticles was modified by aryl diazonium salt of sulfanilic acid. It was revealed that addn. of SGO (5 wt %) into the PVA matrix improves the thermal stability (melting temp., Tm = 223 °C), mech. stability (tensile strength, TS = 67.8 MPa) and proton cond. (σ = 0.050 S cm-1) of the nanocomposite proton exchange membranes. A proton exchange membrane fuel cell (PEMFC) fabricated with the PVA/SGO membrane showed a max. power d. of 16.15 mW cm-2 at 30 °C. As a result, the investigated PVA/SGO nanocomposite membranes have good potential for further studies and applications in PEMFCs.
- 24Beydaghi, H.; Javanbakht, M. Aligned nanocomposite membranes containing sulfonated graphene oxide with superior ionic conductivity for direct methanol fuel cell application. Ind. Eng. Chem. Res. 2015, 54, 7028– 7037, DOI: 10.1021/acs.iecr.5b01450[ACS Full Text], [CAS], Google Scholar24https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC2MXhtVOktr7K&md5=2fa4bb4809d51c6f672cb78b6b2f62c8Aligned Nanocomposite Membranes Containing Sulfonated Graphene Oxide with Superior Ionic Conductivity for Direct Methanol Fuel Cell ApplicationBeydaghi, Hossein; Javanbakht, MehranIndustrial & Engineering Chemistry Research (2015), 54 (28), 7028-7037CODEN: IECRED; ISSN:0888-5885. (American Chemical Society)In this work, iron oxide (Fe3O4) nanoparticles are deposited onto sulfonated graphene oxide (SGO) nanosheets using a solvothermal method. By applying a magnetic field on the soln. during casting, the SGO/Fe3O4 nanosheets are drawn to the through-plane direction of the membrane. The structures of the nanosheets and membranes are characterized. The aligned poly(vinyl alc.) (PVA)/SGO/Fe3O4 membrane shows higher proton cond., water uptake, thermal stability, methanol permeability, and selectivity compared to a nonaligned membrane. By orientation of nanosheets, 5.7% improvement in the tensile stress of the membranes is obsd. The aligned PVA/SGO/Fe3O4 nanocomposite membrane generates the highest power d. of 25.57 mW cm-1 at 30 °C. As a result, the aligned PVA/SGO/Fe3O4 nanocomposite membrane appears to be a good candidate for direct methanol fuel cell application.
- 25Javanbakht, M.; Hooshyari, K.; Enhessari, M.; Beydaghi, H. Novel PVA/La2Ce2O7 hybrid nanocomposite membranes for application in proton exchange membrane fuel cells. Iran. J. Hydrogen Fuel Cell 2014, 1, 105– 112Google ScholarThere is no corresponding record for this reference.
- 26Hooshyari, K.; Khanamiri, S. N.; Salarizadeh, P.; Beydaghi, H. Nanocomposite membranes with high fuel cell performance based on sulfonated poly (1, 4-phenylene ether ether sulfone) and ytterbium/yttrium doped-perovskite nanoparticles. J. Electrochem. Soc. 2019, 166, F976– F989, DOI: 10.1149/2.1521912jes[Crossref], [CAS], Google Scholar26https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BB3cXhs1ymsr4%253D&md5=c4ec937436d4455978b03993d76afd11Nanocomposite membranes with high fuel cell performance based on sulfonated poly (1,4-phenylene ether ether sulfone) and ytterbium/yttrium doped-perovskite nanoparticlesHooshyari, Khadijeh; Khanamiri, Sima Nazari; Salarizadeh, Parisa; Beydaghi, HosseinJournal of the Electrochemical Society (2019), 166 (13), F976-F989CODEN: JESOAN; ISSN:0013-4651. (Electrochemical Society)In the present study, new nanocomposite membranes based on sulfonated poly(1,4-phenylene ether-ether sulfone), BaZr0.9Y0.1O3-δ and SrCe0.9Yb0.1O3-δ doped-perovskite nanoparticles were prepd. The BaZr0.9Y0.1O3-δ and SrCe0.9Yb0.1O3-δ doped-perovskite nanoparticles enhance the thermal and mech. stability of the nanocomposite membranes. Besides, the water up-take of the nanocomposite membranes increases and so, the proton cond. increase. Substitution of Ce4+ by Yb3+ in the SrCe0.9Yb0.1O3-δ doped-perovskite nanoparticles and the substitution of Zr4+ by Y3+ in the BaZr0.9Y0.1O3-δ doped-perovskite nanoparticles produce oxygen vacancies and decrease the coulombic repulsion between protons and pos. ions. The oxygen vacancies in BaZr0.9Y0.1O3-δ and SrCe0.9Yb0.1O3-δ doped-perovskite nanoparticles act as water and protons trap, and so increase the rotational motion of the proton and the proton cond. in the nanocomposite membranes. The highest proton cond. for the nanocomposite membranes contg. the BaZr0.9Y0.1O3-δ and SrCe0.9Yb0.1O3-δ doped-perovskite nanoparticles are 126 mS cm-1 and 117 mS cm-1, resp., at 80° and 95% RH. The long lifetime of the proton cond. and considerable fuel cell performance, 0.61 W cm-2 power d. at 0.5 V, of the nanocomposite membranes confirm their high potential for application in the PEM fuel cells.
- 27Beydaghi, H.; Javanbakht, M.; Badiei, A. Cross–linked poly(vinyl alcohol)/sulfonated nanoporous silica hybrid membranes for proton exchange membrane fuel cell. J. Nanostruct. Chem. 2014, 4, 97, DOI: 10.1007/s40097-014-0097-y
- 28Ru, C.; Gu, Y.; Na, H.; Li, H.; Zhao, C. Preparation of a cross-linked sulfonated poly(arylene ether ketone) proton exchange membrane with enhanced proton conductivity and methanol resistance by introducing an ionic liquid-impregnated metal organic framework. ACS Appl. Mater. Interfaces 2019, 11, 31899– 31908, DOI: 10.1021/acsami.9b09183[ACS Full Text], [CAS], Google Scholar28https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC1MXhsFKlurvI&md5=178f40a0f7fbdc2eb81efe27a174e99cPreparation of a Cross-Linked Sulfonated Poly(arylene ether ketone) Proton Exchange Membrane with Enhanced Proton Conductivity and Methanol Resistance by Introducing an Ionic Liquid-Impregnated Metal Organic FrameworkRu, Chunyu; Gu, Yiyang; Na, Hui; Li, Haolong; Zhao, ChengjiACS Applied Materials & Interfaces (2019), 11 (35), 31899-31908CODEN: AAMICK; ISSN:1944-8244. (American Chemical Society)A novel ionic liq.-impregnated metal-org.-framework ([email protected]) was prepd. and introduced into sulfonated poly(arylene ether ketone) with pendent carboxyl groups (SPAEK) as the nanofiller for achieving hybrid proton exchange membranes. The nanofiller was anchored in the polymeric matrix by the formation of amido linkage between the pendent carboxyl group attached to the mol. chain of SPAEK and amino group belonging to the inorg. framework, thus leading to the enhancement in mech. properties and dimensional stability. Besides, the hybrid membrane ([email protected]) exhibits an enhanced proton cond. up to 0.184 S·cm-1 because of the incorporation of ionic liq. in the nanocages of NH2-MIL-101. Moreover, the special structure of NH2-MIL-101 contributes to a low leakage of ionic liq. so as to retain the stable proton cond. of hybrid membranes under fully hydrated conditions. Furthermore, as a result of a crosslinked structure formed by inorg. nanofiller, the [email protected] hybrid membrane shows a lower methanol permeability (7.53 × 10-7 cm2 s-1) and superior selectivity (2.44 × 105 S s cm-3) than the pristine SPAEK membrane. Esp., [email protected] performs high single-cell efficiency with a peak power d. of 37.5 mW cm-2, almost 2.3-fold to SPAEK. Electrochem. impedance spectroscopy and SEM indicated that the nanofiller not only contributed to faster proton transfer but also resulted in a tighter bond between the membrane and catalyst. Therefore, the incorporation of [email protected] to prep. the hybrid membrane is proven to be suitable for application in direct methanol fuel cells.
- 29Wang, N.; Yu, J.; Zhou, Z.; Fang, D.; Liu, S.; Liu, Y. SPPEK/TPA composite membrane as a separator of vanadium redox flow battery. J. Membr. Sci. 2013, 437, 114– 121, DOI: 10.1016/j.memsci.2013.02.053[Crossref], [CAS], Google Scholar29https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC3sXnslait7Y%253D&md5=48a57f9add5d931ad8222e9999827d46SPPEK/TPA composite membrane as a separator of vanadium redox flow batteryWang, Nanfang; Yu, Jingang; Zhou, Zhi; Fang, Dong; Liu, Suqin; Liu, YounianJournal of Membrane Science (2013), 437 (), 114-121CODEN: JMESDO; ISSN:0376-7388. (Elsevier B.V.)To improve the performance of a low cost sulfonated poly(phthalazinone ether ketone) (SPPEK) membrane in V redox flow battery (VRFB), composite membranes composed of SPPEK and tungstophosphoric acid (TPA) with 8-25% concn. were prepd. by soln. casting. The results of SEM, energy dispersive x-ray spectroscopy (EDS), and XRD of the SPPEK/TPA composite membrane revealed that TPA had excellent compatibility with SPPEK in the bulk of the membrane. The effect of the TPA concn. on the primary properties, permeability of V ions and ionic selectivity, and chem. stability of the composite membrane was studied. The single cell tests showed that the VRFB employing the SPPEK-TPA-17 membrane with 17% TPA exhibited a higher coulombic efficiency (98.75% vs. 92.81%) and energy efficiency (74.58% vs. 73.83%) than those of the Nafion system. Cycling and chem. stability tests indicated that the SPPEK/TPA composite membrane had high stability in the VRFB system.
- 30Liu, Z.; Zhu, X.; Wang, G.; Hou, X.; Liu, D. Novel crosslinked alkaline exchange membranes based on poly(phthalazinone ether ketone) for anion exchange membrane fuel cell applications. J. Polym. Sci., Part B: Polym. Phys. 2013, 51, 1632– 1638, DOI: 10.1002/polb.23377[Crossref], [CAS], Google Scholar30https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC3sXhsVeisr3O&md5=9783a1aefa5412e9c384c1aa341d09c6Novel crosslinked alkaline exchange membranes based on poly(phthalazinone ether ketone) for anion exchange membrane fuel cell applicationsLiu, Zhi; Zhu, Xiuling; Wang, Guangfu; Hou, Xixin; Liu, DezhiJournal of Polymer Science, Part B: Polymer Physics (2013), 51 (22), 1632-1639CODEN: JPBPEM; ISSN:0887-6266. (John Wiley & Sons, Inc.)Novel crosslinked anion exchange membranes based on poly(phthalazinone ether ketone) (PPEK) were successfully prepd. through chloromethylation, quaternization, membrane casting and OH- ionic exchange reaction from the quaternized PPEK (QPPEK) membrane. The quaternization was performed with N-methylimidazolium (MIm) as ammonium agent and tetramethylethylenediamine (TMEDA) as crosslinking agent. The ion-exchange capacity, swelling ratio (SR), water uptake (WU), and ionic cond. of the QPPEK alk. membranes have been systematically investigated. The results showed that QPPEK membranes have a high hydroxide cond. and very low SR. For the QPPEK-4 alk. membrane with ion-exchange capacity (IEC) 2.63 mmol/g, the WU was 35.8%, and the hydroxide cond. was 0.028 S/cm at 30 °C and 0.032 S/cm at 70 °C, while its SR was only 7.6%. The thermal properties of the QPPEK alk. membrane and CMPPEK were characterized using thermo-gravimetric anal. measurements in a nitrogen atm. The alk. resistance of membrane QPPEK -4 was also briefly investigated in 6 M KOH at 60 °C. © 2013 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys, 2013.
- 31Hongwei, Z.; Fei, Y.; Danying, Z. Fabrication and characterization of electrospun sulfonated poly(phthalazinone ether ketone) mats as potential matrix of reinforced proton exchange membranes. J. Appl. Polym. Sci. 2013, 130, 4581– 4586, DOI: 10.1002/app.39718
- 32Rambabu, G.; Sasikala, S.; Bhat, S. D. Nanocomposite membranes of sulfonated poly(phthalalizinone ether ketone)–sulfonated graphite nanofibers as electrolytes for direct methanol fuel cells. RSC Adv. 2016, 6, 107507– 107518, DOI: 10.1039/c6ra23510g[Crossref], [CAS], Google Scholar32https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC28XhslelsbrM&md5=9ad740dc4661a806af01c7098ec341a5Nanocomposite membranes of sulfonated poly(phthalalizinone ether ketone)-sulfonated graphite nanofibers as electrolytes for direct methanol fuel cellsRambabu, Gutru; Sasikala, S.; Bhat, Santoshkumar D.RSC Advances (2016), 6 (109), 107507-107518CODEN: RSCACL; ISSN:2046-2069. (Royal Society of Chemistry)Polymer nanocomposite membranes are prepd. by the dispersion of sulfonated graphite nanofibers (SGNF) in the sulfonated poly(phthalazinone ether ketone) (SPPEK) matrix. GNF are first functionalized with 4-benzene sulfonic acid, and the presence of sulfonic acid groups in GNF is confirmed by FT-IR and elemental anal. The GNF morphol. after functionalization is analyzed via SEM and TEM. Nanocomposite membranes are then prepd. by varying the content of SGNF in SPPEK using the solvent cast technique and characterized for their physico-chem. properties in terms of mech., thermal and dimensional stability, water sorption, proton and elec. cond. along with methanol permeability. Improved mech. stability for the nanocomposite membranes is obsd. due to interfacial interactions and good compatibility between SGNF and SPPEK. The nanocomposite membranes exhibit improved electrochem. selectivity, which in turn enhances the overall DMFC power output. The DMFC performance of the nanocomposite membrane is higher than pristine SPPEK and is on par with the Nafion-117 membrane. The stability of the nanocomposite membranes is examd. by operating membrane electrode assemblies (MEAs) in the open circuit voltage (OCV) condition for 50 h. In addn., the stability of the composite membranes is also confirmed by measuring the methanol crossover c.d. using linear sweep voltammetry (LSV) for MEAs comprising these membranes before and after an OCV test.
- 33Elakkiya, S.; Arthanareeswaran, G.; Ismail, A. F.; Das, D. B.; Suganya, R. Polyaniline coated sulfonated TiO2 nanoparticles for effective application in proton conductive polymer membrane fuel cell. Eur. Polym. J. 2019, 112, 696– 703, DOI: 10.1016/j.eurpolymj.2018.10.036[Crossref], [CAS], Google Scholar33https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC1cXitVyitbrJ&md5=b290e4c6ad9e8778f3e1e917afa3599ePolyaniline coated sulfonated TiO2 nanoparticles for effective application in proton conductive polymer membrane fuel cellElakkiya, S.; Arthanareeswaran, G.; Ismail, A. F.; Das, Diganta B.; Suganya, R.European Polymer Journal (2019), 112 (), 696-703CODEN: EUPJAG; ISSN:0014-3057. (Elsevier Ltd.)The sulfonated polyethersulfone (SPES) with modified TiO2 proton exchange membrane performance for the fuel cell application was reported. TiO2 nanoparticles investigated for the fuel cell performance were modified by sulfonation and surface coated using polyaniline (PANI). Fabricated membranes were analyzed in terms of water uptake, swelling ratio, methanol uptake, ion exchange capacity, chem. stability and thermal properties. Surface and structural properties of the membranes were characterized by Field Emission Scanning electron microscope (FESEM). To understand the interaction between polymer and nanoparticle, Fourier transform IR (FTIR) and X-ray diffraction (XRD) characterization for the membranes were performed. Highest proton cond. is 2.30 × 10-4 S/cm with SPES/STiO2-PANI (0.5%) composite membrane. The presence of modified TiO2 with amine group of PANI and sulfonic acid group were the main factors for the highest cond. value. The composite membrane with modified TiO2 shows excellent chem. stability and thermal properties. Thus, the composite membrane incorporated with STiO2-PANI is a promising proton conducting material for fuel cell application.
- 34Kumar, K. S.; Rajendran, S.; Prabhu, M. R. A Study of influence on sulfonated TiO2-Poly (Vinylidene fluoride-co-hexafluoropropylene) nano composite membranes for PEM Fuel cell application. Appl. Surf. Sci. 2017, 418, 64– 71, DOI: 10.1016/j.apsusc.2016.11.139[Crossref], [CAS], Google Scholar34https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC28XhvFOgs7fN&md5=a4320291cb3bb8c2ed50fdcd46027b3eA Study of influence on sulfonated TiO2-Poly (Vinylidene fluoride-co-hexafluoropropylene) nano composite membranes for PEM Fuel cell applicationkumar, K. Selva; Rajendran, S.; Prabhu, M. RameshApplied Surface Science (2017), 418 (Part_A), 64-71CODEN: ASUSEE; ISSN:0169-4332. (Elsevier B.V.)The present work describes the sulfonated Titania directly blended with Poly (Vinylidene fluoride-co-hexafluoropropylene) as a host polymer by solvent casting technique for PEM fuel cell application. Characterization studies such as FT-IR, SEM, EDX, AFM, Proton cond., contact angle measurement, IEC, TG, water uptake, tensile strength were performed by for synthesized proton conducting polymer electrolytes. The max. proton cond. value was found to be 3.6 × 10-3S/cm for 25 wt% sulfonated Titania based system at 80 °C. The temp. dependent proton cond. of the polymer electrolyte follows an Arrhenius relationship. Surface morphol. of the composite membranes was investigated by tapping mode. Thermal stability of the system was studied by TG anal. The fabricated composite membranes with high proton cond., good water uptake and IEC parameters exhibited a max. fuel cell power d. of 85 Mw/cm2for PEM fuel cell application.
- 35Ayyaru, S.; Dharmalingam, S. A study of influence on nanocomposite membrane of sulfonated TiO2 and sulfonated polystyrene-ethylene-butylene-polystyrene for microbial fuel cell application. Energy 2015, 88, 202– 208, DOI: 10.1016/j.energy.2015.05.015[Crossref], [CAS], Google Scholar35https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC2MXovVersrw%253D&md5=d754342e8a1885cd68ad452e1f2cb8e9A study of influence on nanocomposite membrane of sulfonated TiO2 and sulfonated polystyrene-ethylene-butylene-polystyrene for microbial fuel cell applicationAyyaru, Sivasankaran; Dharmalingam, SangeethaEnergy (Oxford, United Kingdom) (2015), 88 (), 202-208CODEN: ENEYDS; ISSN:0360-5442. (Elsevier Ltd.)Microbial fuel cell (MFC) is a device that uses bacteria as a catalyst to oxidize various substrates for simultaneous electricity generation and wastewater treatment. In the present work, (sulfonated TiO2 (S-TiO2)/polystyrene ethylene butylene polystyrene) SPSEBS nanocomposite membranes were prepd. by soln. casting. The IEC (ion exchange capacity), water uptake, proton cond. and MFC performance of the composite membranes were explored. SPSEBS-S-TiO2 membrane (7.5%) exhibited the highest IEC value, water uptake and proton cond. capacity. The results revealed that the incorporation of sulfonated TiO2 improved the proton cond. of the SPSEBS membrane effectively and exhibited the highest peak power d. of 1345 ± 17 mWm-2 for SPSEBS-S-TiO2 7.5%, when compared to 695 ± 7 mWm-2 and 835 ± 8 mWm-2 obtained for SPSEBS and SPSEBS-TiO2 membranes resp. in a (single chambered microbial fuel cell) SCMFC. In comparison to previously reported work with Nafion (300 ± 10 mWm-2) in MFCs, the composite membrane delivered more than 4-fold higher power d. The oxygen mass transfer coeff. (KO) of nanocomposite membranes decreased with incorporation of the sulfonated TiO2 which in turn increased the (columbic efficiency) CE.
- 36Cotton, F. A.; Stokely, P. F. Structural basis for the acidity of sulfonamides. Crystal structures of dibenzenesulfonamide and its sodium salt. J. Am. Chem. Soc. 1970, 92, 294– 302, DOI: 10.1021/ja00705a012[ACS Full Text], [CAS], Google Scholar36https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADyaE3cXmtVWktQ%253D%253D&md5=f73dc6d5d243606293dd633fd7174fd9Structural basis for the acidity of sulfonamides. Crystal structures of dibenzenesulfonamide and its sodium saltCotton, F. Albert; Stokely, P. F.Journal of the American Chemical Society (1970), 92 (2), 294-302CODEN: JACSAT; ISSN:0002-7863.To ascertain what role structural factors-and, hence, by implication , bonding factors-play in the pronounced acidity of dibenzenesulfonami de (pKa = 1.45), the structures of the acid itself, (PhSO2)2NH, and the Na salt, Na+-(C5H5SO2)2N-, have been detd. For (PhSO2)2NH: space group, P21/c; Z = 4; d0 = 1.470; dc = 1.468; a = 8.625 ± 0.004, b = 10.164 ± 0.004, c = 15.627 ± 0.004 Å; β = 101.09 ± 0.05°. Intensities of 2364 independent reflections were measured using Mo Kα radiation and employing an automated diffractometer. The 1276 reflections accepted as statistically reliable and nonzero were used to solve (by application of the Karle-Hauptman sigma-2 relation) and refine the structure. For Na+ (PhSO2)2N-: space group, Pbcn; Z = 8; d0 = 1.585; dc = 1.580; a = 15.218 ± 0.004, b = 17.210 ± 0.004, c = 10.252 ± 0.004 Å. Intensities of 1639 independent reflections were measured by using Cu Kα radiation and employing an automated diffractometer. Of these, 1251 reflections were used to solve the structure by the symbolic addn. procedure and to refine it. In (PhSO2)2NH, the Ph groups lie above and below the S-N-S plane, giving approx. mol. symmetry C2; in [PhSO2)2N]-, they lie on the same side of the S-N-S plane giving approx. Cs symmetry. This difference seems to be caused primarily by steric, electrostatic, and packing forces. The SNS angle, mean S-N distances, and mean S-O distance in (Ph-sO2)2NH and [(PhSO2)2N]- are, resp.: 127.7(3)°, 1.650(7) Å, an d 1.415 (18) Å; and 127.5(3)°, 1.580(9) Å, 1.446 (8) Å. Thus, the only major change attributable directly to deprotonation of (PhSO2)2NH is the decrease of 0.070(16) Å in the mean S-N bond length.
- 37Tabrizian, E.; Amoozadeh, A.; Shamsi, T. A novel class of heterogeneous catalysts based on toluene diisocyanate: the first amine-functionalized nano-titanium dioxide as a mild and highly recyclable solid nanocatalyst for the Biginelli reaction. React. Kinet., Mech. Catal. 2016, 119, 245– 258, DOI: 10.1007/s11144-016-1047-0[Crossref], [CAS], Google Scholar37https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC28XhtVyrtrnO&md5=6c9ff13ee9336f8c4bcf3fa83929d0c0A novel class of heterogeneous catalysts based on toluene diisocyanate: the first amine-functionalized nano-titanium dioxide as a mild and highly recyclable solid nanocatalyst for the Biginelli reactionTabrizian, Elham; Amoozadeh, Ali; Shamsi, TaiebehReaction Kinetics, Mechanisms and Catalysis (2016), 119 (1), 245-258CODEN: RKMCAJ; ISSN:1878-5190. (Springer)Amine-functionalized titania as a novel inorg.-org. hybrid heterogeneous basic nanocatalyst has been synthesized by the covalent grafting of toluene diisocyanate as a precursor of amine on the surface of titania. The prepd. nanocatalyst was characterized by Fourier transform IR spectroscopy, field emission SEM, X-ray diffraction and thermogravimetric anal. The catalytic activity of resultant nanocatalyst was effectively evaluated for the synthesis of 3,4-dihydopyrimidin-2(1H)-ones through a one-pot three components condensation reaction of various aldehydes, β-dicarbonyl compds. and urea (or thiourea) at 100°C under solvent-free conditions with good to excellent yields. Optimization of the reaction condition was investigated by central composite design under response surface methodol. The catalyst can be recovered easily by simple filtration and reused for eight consecutive runs without significant decrease of its catalytic efficiency.
- 38Xu, T.; Hou, W.; Shen, X.; Wu, H.; Li, X.; Wang, J.; Jiang, Z. Sulfonated titania submicrospheres-doped sulfonated poly(ether ether ketone) hybrid membranes with enhanced proton conductivity and reduced methanol permeability. J. Power Sources 2011, 196, 4934– 4942, DOI: 10.1016/j.jpowsour.2011.02.017[Crossref], [CAS], Google Scholar38https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC3MXjvVSgt78%253D&md5=6f6c26cc12f29f43bfba132f236ba7d9Sulfonated titania submicrospheres-doped sulfonated poly(ether ether ketone) hybrid membranes with enhanced proton conductivity and reduced methanol permeabilityXu, Tao; Hou, Weiqiang; Shen, Xiaohui; Wu, Hong; Li, Xicheng; Wang, Jingtao; Jiang, ZhongyiJournal of Power Sources (2011), 196 (11), 4934-4942CODEN: JPSODZ; ISSN:0378-7753. (Elsevier B.V.)Sulfonated titania submicrospheres (TiO2-SO3H) prepd. through a facile chelation method are incorporated into sulfonated poly(ether ether ketone) (SPEEK) to fabricate org.-inorg. hybrid membranes with enhanced proton cond. and reduced methanol permeability for potential use in direct methanol fuel cells (DMFCs). The pristine titania submicrospheres (TiO2) with a uniform particle size are synthesized through a modified sol-gel method and sulfonated using 4,5-dihydroxy-1,3-benzenedisulfonic acid disodium salt as the sulfonation reagent. The sulfonation process is confirmed by Fourier transform IR spectroscopy (FTIR) and X-ray photoelectron spectra (XPS). The hybrid membranes are systematically characterized in terms of thermal property, mech. property, ionic exchange capacity (IEC), swelling behavior, and microstructural features. The methanol barrier property and the proton cond. of the SPEEK/TiO2-SO3H hybrid membranes are evaluated. The presence of the fillers reduces methanol crossover through the membrane. Compared with the unsulfonated TiO2-doped membranes, the TiO2-SO3H-doped ones exhibit higher proton cond. due to the addnl. sulfonic acid groups on the surface of TiO2. The hybrid membrane doped with 15 wt. % TiO2-SO3H submicrospheres exhibits an acceptable proton cond. of 0.053 S cm-1 and a reduced methanol permeability of 4.19 × 10-7 cm2 s-1.
- 39Venkatachalam, N.; Palanichamy, M.; Murugesan, V. Sol–gel preparation and characterization of alkaline earth metal doped nano TiO2: Efficient photocatalytic degradation of 4-chlorophenol. J. Mol. Catal. A: Chem. 2007, 273, 177– 185, DOI: 10.1016/j.molcata.2007.03.077[Crossref], [CAS], Google Scholar39https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BD2sXntF2qsLw%253D&md5=45604d20cd5e19eb1929621fa6eaa9a9Sol-gel preparation and characterization of alkaline earth metal doped nano TiO2: Efficient photocatalytic degradation of 4-chlorophenolVenkatachalam, N.; Palanichamy, M.; Murugesan, V.Journal of Molecular Catalysis A: Chemical (2007), 273 (1-2), 177-185CODEN: JMCCF2; ISSN:1381-1169. (Elsevier B.V.)Magnesium- and barium doped TiO2 nanoparticles were synthesized by sol-gel method. The materials were characterized by XRD, BET, FT-IR, TGA, UV-vis, SEM and TEM techniques. The pure TiO2 nanoparticles contained both anatase and rutile phases together, but Mg2+ or Ba2+ metal ion doped nanosize TiO2 gave only anatase phase. The framework substitution of Mg2+ in TiO2 was established by XRD and FT-IR techniques. However, Ba2+ was retained only on the surface of TiO2 as BaCO3 and the absence of framework substitution of Ba2+ in TiO2 was evident from XRD and FT-IR anal. The band gap values of Mg2+ and Ba2+ doped TiO2 were higher than the pure TiO2. The presence of anatase type structure in TiO2 with high crystallinity and high phase stability even after annealing at 800° C substantially indicates that the dopants might inhibit densification and crystallite growth in nanosized TiO2 by providing dissimilar boundaries. The photocatalytic activity in the degrdn. of 4-chlorophenol was found to be higher for Mg2+ and Ba2+ doped TiO2 than both pure TiO2 and com. TiO2 (Degussa P-25). The influence of various parameters such as initial concn. of 4-chlorophenol, catalyst loading, pH and light intensity were optimized to obtain max. degrdn.
- 40Solymosi, F.; Raskó, J. An infrared study on the formation of isocyanate in the NO + CO reaction on supported Ir catalyst. J. Catal. 1980, 63, 217– 225, DOI: 10.1016/0021-9517(80)90074-3[Crossref], [CAS], Google Scholar40https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADyaL3cXktlagtrg%253D&md5=404284ca47b458bd5488017925c15040An infrared study on the formation of isocyanate in the nitric oxide + carbon monoxide reaction on supported iridium catalystSolymosi, F.; Rasko, J.Journal of Catalysis (1980), 63 (1), 217-25CODEN: JCTLA5; ISSN:0021-9517.The formation of isocyanate surface species in the NO + CO reaction was studied on supported Ir catalyst as a function of temp. and compn. of the reacting gas mixt. On reduced Ir/Al2O3 samples absorption bands due to isocyanate were obsd. at 2260-2240 cm-1. The isocyanate band was first detected at 200°, and its max. intensity was registered at 280-300°. It is stable at <200° but decomps. rapidly at >300° in vacuo to give CO2, CO, and N2. Isocyanate was also formed on oxidized surfaces but with considerably lower intensities. The reaction between preadsorbed NO and gaseous CO also resulted in the formation of isocyanate, but it was not identified when NO was admitted onto preadsorbed CO. During the surface interaction of NO and CO a large downscale shift of the NO band occurred which was explained by the perturbing effect of adsorbed CO. The primary step in the formation of isocyanate is the dissocn. of NO on the reduced centers. Isocyanate formed on the IR migrates to the acceptor sites of the support. This explanation is supported by the observations that the different supports markedly affect the location, formation, and stability of the isocyanate band.
- 41Ou, B.; Li, D.; Liu, Q.; Zhou, Z.; Liao, B. Functionalized TiO2 nanoparticle containing isocyanate groups. Mater. Chem. Phys. 2012, 135, 1104– 1107, DOI: 10.1016/j.matchemphys.2012.06.027[Crossref], [CAS], Google Scholar41https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC38XpvVSks7s%253D&md5=fcea8921d01642f68835c784cf89bd48Functionalized TiO2 nanoparticle containing isocyanate groupsOu, Baoli; Li, Duxin; Liu, Qingquan; Zhou, Zhihua; Liao, BoMaterials Chemistry and Physics (2012), 135 (2-3), 1104-1107CODEN: MCHPDR; ISSN:0254-0584. (Elsevier B.V.)Functionalized TiO2 nanoparticle contg. isocyanate groups can extend the TiO2 nanoparticle chem., and may promote their many potential applications such as in polymer composites and coatings. This paper describes a facile method to prep. functionalized TiO2 nanoparticle with highly reactive isocyanate groups on its surface, via the reaction between toluene-2,4-diisocyanate (TDI) and hydroxyl on TiO2 nanoparticle surface. The main effect factors on the reaction of TiO2 with TDI were studied by detg. the reaction extent of hydroxyl groups on TiO2 surface. Fourier-transformed IR spectroscopy (FTIR) and TGA confirmed that reactive isocyanate groups were covalently attached to the TiO2 nanoparticle surface. The dispersion of the TDI-functionalized TiO2 nanoparticle was studied by TEM. Owing to the TDI mols. covalently bonded on TiO2 nanoparticle surface, the TiO2 nanoparticle can be uniformly dispersed in toluene, thus indicating that this functionalization method can prevent TiO2 nanoparticle from agglomerating.
- 42Shaterian, H. R.; Ghashang, M.; Feyzi, M. Silica sulfuric acid as an efficient catalyst for the preparation of 2 H-indazolo[2,1- b]phthalazine-triones. Appl. Catal., A 2008, 345, 128– 133, DOI: 10.1016/j.apcata.2008.04.032[Crossref], [CAS], Google Scholar42https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BD1cXotFCksb0%253D&md5=285d10fc342a0917710773b13d4ea284Silica sulfuric acid as an efficient catalyst for the preparation of 2H-indazolo[2,1-b]phthalazinetrionesShaterian, Hamid Reza; Ghashang, Majid; Feyzi, MostafaApplied Catalysis, A: General (2008), 345 (2), 128-133CODEN: ACAGE4; ISSN:0926-860X. (Elsevier B.V.)Silica sulfuric acid as an efficient and reusable heterogeneous catalyst was used for the prepn. of the title compds. [I; Ar = (un)substituted phenyl] from the three-component condensation reaction of phthalhydrazide, dimedone, and arom. aldehydes under solvent-free conditions in good to excellent yields and short reaction times.
- 43Inan, T. Y.; Doğan, H.; Unveren, E. E.; Eker, E. Sulfonated PEEK and fluorinated polymer based blends for fuel cell applications: Investigation of the effect of type and molecular weight of the fluorinated polymers on the membrane’s properties. Int. J. Hydrogen Energy 2010, 35, 12038– 12053, DOI: 10.1016/j.ijhydene.2010.07.084[Crossref], [CAS], Google Scholar43https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC3cXht1emsrfM&md5=2631a913b7e9aef6d34fa2be142423c0Sulfonated PEEK and fluorinated polymer based blends for fuel cell applications: Investigation of the effect of type and molecular weight of the fluorinated polymers on the membrane's propertiesInan, Tuelay Y.; Dogan, Hacer; Unveren, Elif E.; Eker, ErsoyInternational Journal of Hydrogen Energy (2010), 35 (21), 12038-12053CODEN: IJHEDX; ISSN:0360-3199. (Elsevier Ltd.)This work clearly demonstrates the effect and mol. wt. of the fluorinated polymer of SPEEK/Fluorinated polymer blends for low temp. ( < 80°) Fuel Cell Applications. Comparisons with trademarks (e.g., Nafion) suggests that the membranes the authors prepd. in this study have good compatibility in all application respects. Membranes were prepd. by soln. casting method from four different fluorinated polymers; poly(vinylidene fluoride) with three different mol. wts. (PVDF, Mw: 180.000, Mw: 275.000, Mw: 530.000); Poly(vinylidene fluoride-co-Hexafluoro propylene) (PVDF-HFP Mn:130.000) and sulfonated poly(ether ether ketone) (SPEEK) with sulfonation degree (SD) of 70. The sulfonation degree (SD) of SPEEK was detd. by FTIR, 1H NMR and ion exchange capacity (IEC) measurements. Thermo-oxidative stability and proton cond. of the membranes were detd. by using TGA and BT-512 BekkTech membrane test systems, resp. Chem. degrdn. of SPEEK membranes was studied via Fenton test. The morphol. of the membranes were examd. by SEM and TEM. Water uptake and proton cond. values decreased with the addn. of fluorinated polymers (PVDF, PVDF-HFP) as expected, but proton cond. values were still comparable to that of Nafion 117 membrane. Addn. of fluorinated polymers improved chem. degrdn. of the blend membranes in all ratios while addn. of PVDF-HFP to the SPEEK70 caused phase sepns. in all ratios. Methanol permeability value of SPEEK70/PVDF(Mw = 275.000) blend membrane (3.13E-07 (cm2/s)) was much lower than Nafion 117 (1.21E-06 (cm2/s)). PVDF addn. to the SPEEK polymers caused increase in elongation of the membranes. Increase in the mol. wt. of the PVDF did not show any effect on the Young modulus, but resulted in high elongation values. However, increasing PVDF content of the blend membranes caused lower elongation values at break and didn't have any effect on the Young modulus. The gas permeability values of SPEEK70/PVDF type blend membranes were lower than that of the Nafion. Hydrogen and oxygen permeability values were 1-tenth and 1/5 of the Nafion, resp.
- 44Chi, L.; Qian, Y.; Guo, J.; Wang, X.; Arandiyan, H.; Jiang, Z. Novel g-C3N4/TiO2/PAA/PTFE ultrafiltration membrane enabling enhanced antifouling and exceptional visible-light photocatalytic self-cleaning. Catal. Today 2019, 335, 527– 537, DOI: 10.1016/j.cattod.2019.02.027[Crossref], [CAS], Google Scholar44https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC1MXks1yqu7w%253D&md5=2a435ff299acea4499bd7d5888cfc828Novel g-C3N4/TiO2/PAA/PTFE ultrafiltration membrane enabling enhanced antifouling and exceptional visible-light photocatalytic self-cleaningChi, Lina; Qian, Yingjia; Guo, Junqiu; Wang, Xinze; Arandiyan, Hamidreza; Jiang, ZhengCatalysis Today (2019), 335 (), 527-537CODEN: CATTEA; ISSN:0920-5861. (Elsevier B.V.)Membrane fouling due to superhydropobicity of polytetrafluoroethylene ultrafiltration membranes (PTFE UFMs) represents a grand challenge for their practical applications in diverse water treatment industries. Surface immobilization of hydrophilic and chem. stable inorg. metal oxides (TiO2, ZrO2, etc) has been developed to improve hydrophilicity of the PTFE UFMs, though they still suffer from expensive and repeating regenerations once fouled. To address such issues, we strive to firmly immobilize g-C3N4 modified TiO2 (g-C3N4/TiO2, hereafter CNTO) onto PTFE UFM via a facile plasma-enhanced surface graft technique using polyacrylic acid (PAA) as a bridging agent. As reported here, the obtained CNTO/PAA/PTFE UFM shows much smaller surface water contact angle (WCA) of 62.3° than that of bare PTFE UFM(115.8°), leading to enhanced water flux of 830 L m-2 h-1 in the initial ultrafiltration of modelled waste-water contg. methylene blue (MB). The CNTO/PAA/PTFE UFM is highly resistant to fouling in the prolonged filtration of 1000 mg/L bovine serum albumin (BSA) soln., while the fouled CNTO/PAA/PTFE UFM is able to regenerate rapidly under either UV or visible-light irradn. The enhanced performance of the novel CNTO/PAA/PTFE UFM is reasonably attributed to its high wettability and robust photocatalytic activity of the g-C3N4/TiO2 coating that follows different self-cleaning mechanisms under UV and visible light irradiations.
- 45Kermani, H.; Rohrbach, A. Orientation-control of two plasmonically coupled nanoparticles in an optical trap. ACS Photonics 2018, 5, 4660– 4667, DOI: 10.1021/acsphotonics.8b01145[ACS Full Text], [CAS], Google Scholar45https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC1cXhslGgu7bK&md5=a6571081b4669ed85cbd883f90cec8e2Orientation-Control of Two Plasmonically Coupled Nanoparticles in an Optical TrapKermani, Hamideh; Rohrbach, AlexanderACS Photonics (2018), 5 (11), 4660-4667CODEN: APCHD5; ISSN:2330-4022. (American Chemical Society)Optical monitoring of nanoparticle (NP) dynamics is typically beyond the spatial and temporal resoln. limit of light microscopy. However, the orientation and assembly of NPs can be controlled by various light scattering methods. Here we demonstrate how two 80 nm silver NPs form a dimer inside an optical trap and orient along the elec. field of the trapping laser, therefore allowing to rotate them stably in the horizontal plane. We built a dual-path spectrometer for two orthogonal polarization directions to det. the azimuthal dimer angle for different plasmonic coupling strengths by the difference in the measured spectral intensity maxima. The azimuthal angle of the dimer could be retrieved with an accuracy of a few degrees independent of the spectral frequency or the distance between the NPs. Our results coincide well with a developed theor. model predicting polarization-dependent scattering spectra for dimers with different orientations and NP distances. Our study points out another strategy for a highly controlled assembly of single NPs using optical tweezers and multimodal scattered light.
- 46Wang, L.; Deng, N.; Wang, G.; Ju, J.; Cheng, B.; Kang, W. Constructing amino-functionalized flower-like metal–organic framework nanofibers in sulfonated poly(ether sulfone) proton exchange membrane for simultaneously enhancing interface compatibility and proton conduction. ACS Appl. Mater. Interfaces 2019, 11, 39979– 39990, DOI: 10.1021/acsami.9b13496[ACS Full Text], [CAS], Google Scholar46https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC1MXhvFektLbE&md5=884cabdef9c72e24f3c29e61b2df4d7eConstructing Amino-Functionalized Flower-like Metal-Organic Framework Nanofibers in Sulfonated Poly(ether sulfone) Proton Exchange Membrane for Simultaneously Enhancing Interface Compatibility and Proton ConductionWang, Liyuan; Deng, Nanping; Wang, Gang; Ju, Jingge; Cheng, Bowen; Kang, WeiminACS Applied Materials & Interfaces (2019), 11 (43), 39979-39990CODEN: AAMICK; ISSN:1944-8244. (American Chemical Society)A novel flower-like MIL-53(Al)-NH2 nanofiber (MNF) was constructed, in which the electro-blown spinning Al2O3 nanofibers were introduced as Al precursors to coordinate with ligand in hydrothermal reaction for the formation of MOFs nanofibers. By incorporating the functional and consecutive MNFs fillers in sulfonated poly(ether sulfone) (SPES) matrix, high-performance [email protected] hybrid membranes were obtained. Specifically, the peak stress strength could be strengthened to 33.42 MPa and the proton cond. was remarkably improved to 0.201 S/cm as MNFs content increased to 5 wt.%, achieving a simultaneous improvement on proton conduction and membrane stability. The highly promoted performance could be ascribed to the synergy advantages of unique structure and amino modification of MNFs: (1) the flower-like nanofiber structure of MNFs with high surface area could be beneficial to construct long-range and compatible interfaces between MNFs and SPES matrix, leading to sufficient continuous proton pathways as well as strengthened stability for the hybrid membrane. (2) the hydrophilic MNFs rendered the hybrid membrane with sufficient water retention for proton transfer via Vehicle mechanism. (3) functional -NH2 groups of MNFs and -SO3H groups of SPES were consecutively and tightly bonded via acid-base electrostatic interactions, which further accelerated the proton conduction via Grotthuss hopping mechanism and effectively suppressed the MeOH penetration in the meanwhile for the [email protected] hybrid membranes.
- 47Muthumeenal, A.; Neelakandan, S.; Rana, D.; Matsuura, T.; Kanagaraj, P.; Nagendran, A. Sulfonated polyethersulfone (SPES)–charged surface modifying macromolecules (cSMMs) blends as a cation selective membrane for fuel cells. Fuel Cells 2014, 14, 853– 861, DOI: 10.1002/fuce.201400044[Crossref], [CAS], Google Scholar47https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC2cXitVamurbN&md5=ae90a5f3411720a0cc12f87727ff3781Sulfonated Polyethersulfone (SPES) - Charged Surface Modifying Macromolecules (cSMMs) Blends as a Cation Selective Membrane for Fuel CellsMuthumeenal, A.; Neelakandan, S.; Rana, D.; Matsuura, T.; Kanagaraj, P.; Nagendran, A.Fuel Cells (Weinheim, Germany) (2014), 14 (6), 853-861CODEN: FUCEFK; ISSN:1615-6846. (Wiley-Blackwell)Polyethersulfone (PES) was sulfonated by chlorosulfonic acid and concd. sulfuric acid. The pure sulfonated PES (SPES) and modified SPES membranes were prepd. by blending with different charged surface modifying macromols. (cSMMs) namely, SPES/DEG-HBS, SPES/PEG-HBS, and SPES/PPG-HBS. Membranes were characterized for their morphol., phys. properties, and electrochem. properties in order to evaluate these membranes as cation exchange membranes. The blended membranes showed an increase in hydrophilicity, water uptake, and proton cond. compared to the pure SPES membranes. The highest values of water uptake and proton cond. were obtained for the SPES/PPG-HBS blended membrane. Morphol. studies revealed that the nodule size and surface roughness also influenced the water uptake, apart from the addnl. -SO3H group. Among the modified membranes, the SPES/DEG-HBS blended membrane exhibited a lower methanol permeability value of 8.895 × 10-8 cm2 s-1 than the corresponding SPES membrane. The other two cSMM blended membranes showed higher methanol permeability values than SPES but still a smaller value than Nafion 117. The highest selectivity ratio (i.e., ratio of proton cond. to methanol permeability) was obtained with the SPES/DEG-HBS cSMM blended membrane. These results showed that the SPES/cSMM blended membranes have promise for possible use as a cation exchange membrane in fuel cells and electrolyzer applications.
- 48Rao, Z.; Feng, K.; Tang, B.; Wu, P. Construction of well interconnected metal-organic framework structure for effectively promoting proton conductivity of proton exchange membrane. J. Membr. Sci. 2017, 533, 160– 170, DOI: 10.1016/j.memsci.2017.03.031[Crossref], [CAS], Google Scholar48https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC2sXls1Kitb8%253D&md5=9ff48a75cde885eae9286970fff2c582Construction of well interconnected metal-organic framework structure for effectively promoting proton conductivity of proton exchange membraneRao, Zhuang; Feng, Kai; Tang, Beibei; Wu, PeiyiJournal of Membrane Science (2017), 533 (), 160-170CODEN: JMESDO; ISSN:0376-7388. (Elsevier B.V.)To obtain proton exchange membrane (PEM) with high proton conductivities under both high humidity and anhyd. condition, interconnected UiO-66-NH2 was tethered onto graphene oxide (GO) surfaces, and then incorporated into Nafion matrix. Thanks to tethering effect of GO surfaces and interconnection among MOF grains, well interconnected metal-org. framework (MOF) structures ([email protected]) were constructed. The structural advantage and mechanism of [email protected] in proton conduction were explored. It was found the synergistic effect between GO and UiO-66-NH2 with suitable particle size was esp. important for promoting proton transfer. Such interconnected structure of MOF on GO also made acid/base pair pathways between -SO3H of Nafion and -NH2 of [email protected] more consecutive. This was favorable to proton conduction via both vehicle mechanism and Grotthuss mechanism. The proton cond. of the as-prepd. composite membrane reached up to 0.303 S/cm under 90°, 95% RH, and 3.403 × 10-3 S/cm under anhyd. condition, which was about 1.57 and 1.88 times higher than that of the recast Nafion (0.118 S/cm and 1.182 × 10-3 S/cm), resp. Furthermore, the composite membrane showed a reduced methanol permeability, which was attributed to the barrier effect of the two-dimensional GO and the trapping of methanol by UiO-66-NH2 pores.
- 49Cele, N.; Ray, S. S. Recent progress on Nafion-based nanocomposite membranes for fuel cell applications. Macromol. Mater. Eng. 2009, 294, 719– 738, DOI: 10.1002/mame.200900143[Crossref], [CAS], Google Scholar49https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BD1MXhsVaju7bI&md5=eecc9bc56befa2efd0dbb6a5e560d474Recent Progress on Nafion-Based Nanocomposite Membranes for Fuel Cell ApplicationsCele, Nonhlanhla; Ray, Suprakas SinhaMacromolecular Materials and Engineering (2009), 294 (11), 719-738CODEN: MMENFA; ISSN:1438-7492. (Wiley-VCH Verlag GmbH & Co. KGaA)A review of recent progress in the field of Nafion-based nanocomposite membranes for proton exchange membrane fuel cells. The membranes exhibit a significant improvement in thermomech. and thermal stability as well as proton cond. at very low filler contents. Prepn., characterization, and properties of various types of Nafion-based nanocomposite membranes are critically discussed, and detailed examples are summarized. A large variety of nanoparticles of different natures and sizes can be blended with a Nafion matrix, generating a new class of nanostructured electrolyte membrane with interesting phys. properties.
- 50Shaari, N.; Kamarudin, S. K.; Zakaria, Z. Potential of sodium alginate/titanium oxide biomembrane nanocomposite in DMFC application. Int. J. Energy Res. 2019, 43, 8057– 8069, DOI: 10.1002/er.4801[Crossref], [CAS], Google Scholar50https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC1MXitVKgsbzI&md5=13b99032d8c65a6493a8b537e701cbcaPotential of sodium alginate/titanium oxide biomembrane nanocomposite in DMFC applicationShaari, Norazuwana; Kamarudin, Siti Kartom; Zakaria, ZulfirdausInternational Journal of Energy Research (2019), 43 (14), 8057-8069CODEN: IJERDN; ISSN:0363-907X. (John Wiley & Sons Ltd.)Summary : A proton exchange membrane was synthesized consuming a sodium alginate biopolymer as the matrix and titanium oxide as the nanofiller. The titanium oxide content varied from 5 to 25 wt%. The biomembrane nanocomposite performs better than the pristine sodium alginate membrane based on liq. uptake, methanol permeability, proton cond., ion exchange capacity, and oxidative stability outcomes. The unique properties of sodium alginate and titanium oxide lead to outstanding interconnections, thus producing new materials with great characteristics and enhanced performance. The highest proton cond. achieved in this study is 17.3 × 10-3 S cm-1, which performed by SAT5 (25 wt%) membranes at 70°C. An optimal content of titanium oxide enhances the cond. and methanol permeability of the membrane. Addnl., the hydrophilicity of pure sodium alginate is greatly reduced and achieves a good liq. uptake capacity and swelling ratio. The characteristics of the SA/TiO2 biomembrane nanocomposite were detd. with field emission scanning electron microscope, Fourier transform IR, X-ray diffraction, thermal gravimetric anal./differential scanning calorimetry, and mech. strength anal.
- 51Kim, D. S.; Liu, B.; Guiver, M. D. Influence of silica content in sulfonated poly(arylene ether ether ketone ketone) (SPAEEKK) hybrid membranes on properties for fuel cell application. Polymer 2006, 47, 7871– 7880, DOI: 10.1016/j.polymer.2006.09.001[Crossref], [CAS], Google Scholar51https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BD28XhtFSnurzO&md5=0bb091795fbdacd7a007dc5707cb61adInfluence of silica content in sulfonated poly(arylene ether ether ketone ketone) (SPAEEKK) hybrid membranes on properties for fuel cell applicationKim, Dae Sik; Liu, Baijun; Guiver, Michael D.Polymer (2006), 47 (23), 7871-7880CODEN: POLMAG; ISSN:0032-3861. (Elsevier Ltd.)Sulfonated poly(arylene ether ether ketone ketone) (SPAEEKK) copolymer with a pendant sulfonic acid group (sulfonic acid content (SC) = 0.67) was synthesized from the com. available monomers Na 6,7-dihydroxy-2-naphthalenesulfonate (DHNS), 1,3-bis(4-fluorobenzoyl)-benzene (BFBB), and hexafluorobisphenol A (6F-BPA). SPAEEKK/SiO2 hybrid membranes were prepd. using a sol-gel process under acidic conditions. SPAEEKK/SiO2 hybrid membranes were fabricated with different SiO2 contents and the membranes were modified to achieve improved p cond. incorporating P-OH groups through H3PO4 treatment. The SiO2 particles within the membranes blocked excessive MeOH cross-over and form a pathway for p transport due to H2O absorption onto the hydrophilic ≡SiOH surface. The p conductivities of H3PO4-doped membranes were somewhat higher than the un-doped membranes due to increasing hydrophilicity of the membranes. The presence of SiO2 particles within the org. polymer matrix, which decreases the ratio of free H2O to bound H2O due to the ≡SiOH on the surface of SiO2 derived from sol-gel reaction, results in hybrid membranes with reduced MeOH permeability and improved p cond.
- 52Liu, X.; Zhang, Y.; Chen, Y.; Li, C.; Dong, J.; Wang, J.; Yang, Z.; Cheng, H. Investigation of diamine cross-linker on semi-IPNs of BPPO/SPEEK membranes for direct methanol fuel cell. Energy Technol. 2018, 6, 2264– 2272, DOI: 10.1002/ente.201800274[Crossref], [CAS], Google Scholar52https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC1cXitlShsrfK&md5=b16d2f6f7737e108a4f7099d33610663Investigation of Diamine Cross-Linker on Semi-IPNs of BPPO/SPEEK Membranes for Direct Methanol Fuel CellLiu, Xupo; Zhang, Yunfeng; Chen, Yazhou; Li, Cuicui; Dong, Jiaming; Wang, Jiaying; Yang, Zehui; Cheng, HansongEnergy Technology (Weinheim, Germany) (2018), 6 (11), 2264-2272CODEN: ETNEFN; ISSN:2194-4296. (Wiley-VCH Verlag GmbH & Co. KGaA)Low methanol permeability is one of the most crit. factors for proton exchange membranes utilized in direct methanol fuel cells (DMFCs). Here, sulfonated poly(ether ether ketone) (SPEEK) polymer chains are interpenetrated into the semi-interpenetrating polymer networks (semi-IPNs) constructed by the alkylation reaction between bromobenzyl groups of bromomethylated poly(phenylene oxide) and amine groups of 2,2'-(ethylenedioxy)bis(ethylamine) cross-linker. The influences of crosslinking network contents on the key properties of SPEEK membranes are systematically investigated. Dimensional stability and methanol-permeability resistance are enhanced as the increase of the crosslinking network contents. The relative selectivity is significantly improved due to the largely reduced methanol permeability. The DMFC assembled by the membrane with 20 wt.% crosslinking networks demonstrates four times higher power output than the Nafion 117 DMFC in 5 M methanol soln.
- 53Salarizadeh, P.; Bagheri, A.; Beydaghi, H.; Hooshyari, K. Enhanced properties of SPEEK with incorporating of PFSA and barium strontium titanate nanoparticles for application in DMFCs. Int. J. Energy Res. 2019, 43, 4840– 4853, DOI: 10.1002/er.4635[Crossref], [CAS], Google Scholar53https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC1MXhsVamtLnO&md5=a2f4c5ec90e27e41d4ead0d478b06745Enhanced properties of SPEEK with incorporating of PFSA and barium strontium titanate nanoparticles for application in DMFCsSalarizadeh, Parisa; Bagheri, Ahmad; Beydaghi, Hossein; Hooshyari, KhadijehInternational Journal of Energy Research (2019), 43 (9), 4840-4853CODEN: IJERDN; ISSN:0363-907X. (John Wiley & Sons Ltd.)Summary : Novel blend nanocomposite proton-exchange membranes were prepd. using sulfonated poly (ether ether ketone) (SPEEK), perfluorosulfonic acid (PFSA), and Ba0.9Sr0.1TiO3 (BST) doped-perovskite nanoparticles. The membranes were evaluated by attenuated total reflection, X-ray diffraction spectroscopy, water uptake, proton cond., methanol permeability, and direct methanol fuel cell test. The effect of two additives, PFSA and BST, were investigated. Results indicated that both proton cond. and methanol barrier of the blend nanocomposite membranes improved compared with pristine SPEEK and the as-prepd. blend membranes. The methanol permeability and the proton cond. of the blend membrane contg. 6 wt% BST obtained 3.56 × 10-7 cm2 s-1 (at 25 °C) and 0.110 S cm-1 (at 80 °C), resp. The power d. value for the optimum blend nanocomposite membrane (15 wt% PFSA and 6 wt% BST) (54.89 mW cm-2) was higher than that of pristine SPEEK (31.34 mW cm-2) and SPF15 blend membrane (36.12 mW cm-2).
- 54Jiang, Z.; Zhao, X.; Manthiram, A. Sulfonated poly(ether ether ketone) membranes with sulfonated graphene oxide fillers for direct methanol fuel cells. Int. J. Hydrogen Energy 2013, 38, 5875– 5884, DOI: 10.1016/j.ijhydene.2013.02.129[Crossref], [CAS], Google Scholar54https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC3sXlt1aqt7g%253D&md5=2c8d299f7c23283383181fcef2c46b61Sulfonated poly(ether ether ketone) membranes with sulfonated graphene oxide fillers for direct methanol fuel cellsJiang, Zhongqing; Zhao, Xinsheng; Manthiram, ArumugamInternational Journal of Hydrogen Energy (2013), 38 (14), 5875-5884CODEN: IJHEDX; ISSN:0360-3199. (Elsevier Ltd.)Sulfonated organosilane functionalized graphene oxides (SSi-GO) synthesized through the grafting of graphene oxide (GO) with 3-mercaptopropyl trimethoxysilane and subsequent oxidn. have been used as a filler in sulfonated poly(ether ether ketone) (SPEEK) membranes. The incorporation of SSi-GOs greatly increases the ion-exchange capacity (IEC), water uptake, and proton cond. of the membrane. With well-controlled contents of SSi-GOs, the composite membranes exhibit higher proton cond. and lower methanol permeability than Nafion 112 and Nafion 115, making them particularly attractive as proton exchange membranes (PEMs) for direct methanol fuel cells (DMFC). The composite membrane with optimal SSi-GOs content exhibit over 38 and 17% higher power densities, resp., than Nafion 112 and Nafion 115 membranes in DMFCs, offering the possibilities to reduce the DMFC membrane cost significantly while keeping high-performance.
- 55Sun, H.; Tang, B.; Wu, P. Two-Dimensional zeolitic imidazolate framework/carbon nanotube hybrid networks modified proton exchange membranes for improving transport properties. ACS Appl. Mater. Interfaces 2017, 9, 35075– 35085, DOI: 10.1021/acsami.7b13013[ACS Full Text], [CAS], Google Scholar55https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC2sXhsFOjt7nE&md5=7ffb1094a39afb9c747648de7090c44aTwo-Dimensional Zeolitic Imidazolate Framework/Carbon Nanotube Hybrid Networks Modified Proton Exchange Membranes for Improving Transport PropertiesSun, Huazhen; Tang, Beibei; Wu, PeiyiACS Applied Materials & Interfaces (2017), 9 (40), 35075-35085CODEN: AAMICK; ISSN:1944-8244. (American Chemical Society)Metal-org. framework (MOF)/polymer composite proton exchange membranes (PEMs) are being intensively investigated due to their potentials for the systematic design of proton-conducting properties. However, the development of MOF/polymer composite PEMs possessing high selectivity remains exceedingly desirable and challenging for practical application. Herein, two-dimensional (2D) zeolitic imidazolate framework (ZIF-8)/carbon nanotube (CNT) hybrid cross-linked networks (ZCN) were synthesized via the rational design of the phys. form of ZIF-8, and then a series of composite PEMs were prepd. by hybridizing ZCN with sulfonated poly(ether ether ketone) (SPEEK) matrix. The effect of the incorporation of zero-dimensional (0D) raw ZIF-8 nanoparticles and 2D ZCN on the proton conduction and methanol permeability of the composite membranes was systemically studied. Benefiting from the morphol. and compositional advantages of ZCN, the SPEEK/ZCN composite membranes displayed a significant enhancement in proton cond. under various conditions. In particular, the proton cond. of SPEEK/ZCN-2.5 membrane was up to 50.24 mS cm-1 at 120 °C-30% RH, which was 11.2 times that of the recast SPEEK membrane (4.50 mS cm-1) and 2.1 times that of SPEEK/ZIF membrane (24.1 mS cm-1) under the same condition. Meanwhile, the methanol permeability of the SPEEK/ZCN composite membranes was greatly reduced. Therefore, novel MOF/polymer composite PEMs with high selectivity were obtained. Our investigation results reveal that the proton cond. and methanol permeability of the MOF/polymer composite membranes can be effectively tailored via creating more elaborate superstructures of MOFs rather than altering the chem. component. This effective strategy may provide a useful guideline to integrate with other interesting MOFs to design MOF/polymer composite membranes.
- 56Liu, D.; Xie, Y.; Li, S.; Han, X.; Zhang, H.; Chen, Z.; Pang, J.; Jiang, Z. High dimensional stability and alcohol resistance aromatic poly(aryl ether ketone) polyelectrolyte membrane synthesis and characterization. ACS Appl. Energy Mater. 2019, 2, 1646– 1656, DOI: 10.1021/acsaem.8b01557[ACS Full Text], [CAS], Google Scholar56https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC1MXjtVShtLc%253D&md5=e7ac011db44d1ceeb85640cfb9e5894cHigh Dimensional Stability and Alcohol Resistance Aromatic Poly(aryl ether ketone) Polyelectrolyte Membrane Synthesis and CharacterizationLiu, Di; Xie, Yunji; Li, Su; Han, Xiaocui; Zhang, Haibo; Chen, Zheng; Pang, Jinhui; Jiang, ZhenhuaACS Applied Energy Materials (2019), 2 (3), 1646-1656CODEN: AAEMCQ; ISSN:2574-0962. (American Chemical Society)Crystd. sulfonated poly(arylene ether ketone) (Cr-SPAEK) materials constructed from dense sulfonated hydrophilic segments and cryst. poly(ether ketone) (PEK) hydrophobic backbone were designed. The membrane exhibited considerable proton cond. and superb solvent resistance owing to its special phase morphol., the presence of a broad hydrophilic ion transport channel, and a cryst. hydrophobic matrix. The dense sulfonated hydrophilic segment provides excellent proton cond.; the Cr-SPAEK-20 membrane exhibits higher proton-conducting ability than Nafion 117 at of 20-100 °C; its proton cond. reaches about 168 mS cm-1 at 100 °C. The cryst. PEK hydrophobic segment ensures superior solvent resistance and dimensional stability, guaranteeing the durability of the membrane in practical applications. The methanol permeability of Cr-SPAEK-20 is only one-eighth that of Nafion 117 when the test conditions are the same. The direct methanol fuel cell (DMFC), which is assembled by Cr-SPAEK-20, exhibited satisfactory open circuit voltage and max. power d. during the testing process. The Cr-SPAEK membranes have shown potential for DMFCs as polymer electrolyte materials.
- 57Dong, F.; Li, Z.; Wang, S.; Xu, L.; Yu, X. Preparation and properties of sulfonated poly(phthalazinone ether sulfone ketone)/zirconium sulfophenylphosphate/PTFE composite membranes. Int. J. Hydrogen Energy 2011, 36, 3681– 3687, DOI: 10.1016/j.ijhydene.2010.12.014[Crossref], [CAS], Google Scholar57https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC3MXisFait78%253D&md5=4053924511f4dd7c3bb89f135b14d930Preparation and properties of sulfonated poly(phthalazinone ether sulfone ketone)/zirconium sulfophenylphosphate/PTFE composite membranesDong, Feilong; Li, Zhongfang; Wang, Suwen; Xu, Lijuan; Yu, XianjinInternational Journal of Hydrogen Energy (2011), 36 (5), 3681-3687CODEN: IJHEDX; ISSN:0360-3199. (Elsevier Ltd.)Porous polytetrafluoroethylene (PTFE) membranes were used as support material for sulfonated poly(phthalazinone ether sulfone ketone) (SPPESK)/zirconium sulfophenyl phosphate (ZrSPP)/PTFE composite membranes. The membranes were prepd. via a spray painting method. Membranes were characterized by thermal gravimetric anal. (TGA) and SEM. The composite membranes exhibited good thermal stabilities. SEM micrographs confirmed that the pores of the PTFE were filled entirely with SPPESK and ZrSPP. The resulting composite membranes were mech. durable, dimensionally stable in alternating wet/dry environments, and had lower methanol permeabilities compared with the unsupported SPPESK/ZrSPP composite membranes reported in our previous work. The water uptake of these membranes was also lower than previous SPPESK/ZrSPP composite membranes. The proton cond. of PTFE supported SPPESK (DS 81%)/ZrSPP(10 wt%) composite membrane was as high as 0.24 S/cm at 120 °C. Thus, the composite membranes exhibited good thermal stabilities, proton conductivities, and good methanol resistance, indicating that these composite membranes could serve as effective alternative membranes for direct methanol fuel cells (DMFCs).
- 58Zhen, D.; He, G.; Xu, X.; Yan, X.; Du, N.; Gong, X.; Li, T.; Dai, Y.; Wu, X. Simultaneous enhancement of proton conductivity and methanol resistance of sulfonated poly(phthalazinone ether sulfone ketone)/superacid sulfated zirconia composite membranes for direct methanol fuel cells. J. Appl. Polym. Sci. 2018, 135, 46758– 46769, DOI: 10.1002/app.46758
- 59Rambabu, G.; Bhat, S. D. Sulfonated fullerene in SPEEK matrix and its impact on the membrane electrolyte properties in direct methanol fuel cells. Electrochim. Acta 2015, 176, 657– 669, DOI: 10.1016/j.electacta.2015.07.045[Crossref], [CAS], Google Scholar59https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC2MXhsVajtbjE&md5=bddd2e811db2ef2199237f3f6948be2bSulfonated fullerene in SPEEK matrix and its impact on the membrane electrolyte properties in direct methanol fuel cellsRambabu, Gutru; Bhat, Santoshkumar D.Electrochimica Acta (2015), 176 (), 657-669CODEN: ELCAAV; ISSN:0013-4686. (Elsevier Ltd.)Composite membranes of sulfonated polyether ether ketone (SPEEK) are prepd. with sulfonated fullerene as an additive by soln. cast methodol. for its use as polymer electrolyte in direct methanol fuel cells (DMFCs). Fullerene is functionalized by attaching sulfonic acid groups by formed precursor (4-benzene diazonium sulfonic acid) through diazotization reaction route. Functionalized fullerene is extensively characterized by FT-IR, XPS, 1H-NMR and elemental anal. to confirm the sulfonation. Structural changes in sulfonated fullerene (Sfu) are obsd. through FE-SEM and TEM anal. The composite membranes prepd. with varying Sfu content in SPEEK are characterized in terms of their physico-chem. properties in conjunction with ionic cond. and methanol permeability. Oxidative stabilities of these composite membranes are compared with pristine SPEEK membrane. DMFC performance of these membranes is evaluated and the results are compared with pristine SPEEK and Nafion-117 membranes. Steady state polarization in DMFC for SPEEK-Sfu (0.5 wt. %) exhibits peak power d. of 103 mW/cm2 which is at par with Nafion-117 membrane. Membrane electrode assemblies comprising optimized SPEEK-Sfu (0.5 wt. %) and pristine SPEEK matrix are subjected for time evolution studies to evaluate steady state peak power densities.
- 60Liang, Y.; Gong, C.; Qi, Z.; Li, H.; Wu, Z.; Zhang, Y.; Zhang, S.; Li, Y. Intermolecular ionic cross-linked sulfonated poly(ether ether ketone) membranes containing diazafluorene for direct methanol fuel cell applications. J. Power Sources 2015, 284, 86– 94, DOI: 10.1016/j.jpowsour.2015.02.159[Crossref], [CAS], Google Scholar60https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC2MXjslClsL0%253D&md5=10dcee21b08a570597f64a46361cbe2aIntermolecular ionic cross-linked sulfonated poly(ether ether ketone) membranes containing diazafluorene for direct methanol fuel cell applicationsLiang, Yu; Gong, Chenliang; Qi, Zhigang; Li, Hui; Wu, Zhongying; Zhang, Yakui; Zhang, Shujiang; Li, YanfengJournal of Power Sources (2015), 284 (), 86-94CODEN: JPSODZ; ISSN:0378-7753. (Elsevier B.V.)A series of novel ionic crosslinking sulfonated poly(ether ether ketone) (SPEEK) membranes contg. the diazafluorene functional group are synthesized to reduce the swelling ratio and methanol permeability for direct methanol fuel cell (DMFC) applications. The ionic crosslinking is realized by the interaction between sulfonic acid groups and pyridyl in diazafluorene. The prepd. membranes exhibit good mech. properties, adequate thermal stability, good oxidative stability, appropriate water uptake, and low swelling ratio. Moreover, the ionic cross-linked membranes exhibit lower methanol permeability in the range between 0.56 × 10-7 cm2 s-1 and 1.8 × 10-7 cm2 s-1, which is lower than Nafion 117, and they exhibit higher selectivity than Nafion 117 at 30° on the basis of applicable proton cond.
- 61Bu, F.; Zhang, Y.; Hong, L.; Zhao, W.; Li, D.; Li, J.; Na, H.; Zhao, C. 1,2,4-Triazole functionalized poly(arylene ether ketone) for high temperature proton exchange membrane with enhanced oxidative stability. J. Membr. Sci. 2018, 545, 167– 175, DOI: 10.1016/j.memsci.2017.09.072[Crossref], [CAS], Google Scholar61https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC2sXhsF2gsr7L&md5=b8a3e643ba9e6e449804849093e21cac1,2,4-Triazole functionalized poly(arylene ether ketone) for high temperature proton exchange membrane with enhanced oxidative stabilityBu, Fanzhe; Zhang, Yurong; Hong, Lihua; Zhao, Wanchen; Li, Di; Li, Jialin; Na, Hui; Zhao, ChengjiJournal of Membrane Science (2018), 545 (), 167-175CODEN: JMESDO; ISSN:0376-7388. (Elsevier B.V.)A series of novel 1,2,4-triazole grafted poly(arylene ether ketone) membranes were prepd. to absorb phosphoric acid and used as high temp. proton exchange membranes. Poly(arylene ether ketone) is firstly bromomethylated, followed by nucleophilic substitution of bromomethylated poly(arylene ether ketone) with 3-mercapto-1,2,4-triazole. The structure and the degree of substitution were confirmed by their 1H NMR spectra. 1,2,4-Triazole functionalized poly(arylene ether ketone) membranes exhibited high thermal decompn. temp. (Td(5%) higher than 271 °C) and tensile strengths (higher than 78 MPa). After doping with phosphoric acid, these membranes showed enhanced abilities to phosphoric acid absorption with increasing the amt. of triazole groups on the side chains. Phosphoric acid doped MTZPAEK(2.15) showed the highest Wdoping value of 142% and the proton cond. of 51 mS cm-1 at 190 °C. Remarkably, all the membranes exhibited great oxidative stabilities and could retain their shapes for more than 50 h in Fenton's reagent (3 wt% H2O2, 4 ppm Fe2+) at 80 °C. This advantage could be ascribed to the unique sulfide groups, which were introduced by nucleophilic substitution reaction and acted as free radical scavengers. The supposed mechanism of enhancing oxidative stability by sulfide groups was confirmed via FT-IR.
- 62Zhang, Y.; Miyake, J.; Akiyama, R.; Shimizu, R.; Miyatake, K. Sulfonated phenylene/quinquephenylene/perfluoroalkylene terpolymers as proton exchange membranes for fuel cells. ACS Appl. Energy Mater. 2018, 1, 1008– 1015, DOI: 10.1021/acsaem.7b00162[ACS Full Text], [CAS], Google Scholar62https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC1cXivVCitr0%253D&md5=9840edbfb61e4dde2cbcbae8d3e5f64dSulfonated phenylene/quinquephenylene/perfluoroalkylene terpolymers as proton exchange membranes for fuel cellsZhang, Yaojian; Miyake, Junpei; Akiyama, Ryo; Shimizu, Ryo; Miyatake, KenjiACS Applied Energy Materials (2018), 1 (3), 1008-1015CODEN: AAEMCQ; ISSN:2574-0962. (American Chemical Society)A novel series of terpolymers (SQF) contg. sulfophenylene, quinquephenylene, and perfluoroalkylene groups in the polymer main chain were designed and synthesized as proton exchange membranes for fuel cells. The terpolymers with high mol. wt. (Mw = 179-207 kDa, Mn = 41-50 kDa) and different ion exchange capacity (IEC) values (1.70, 2.56, and 3.34 mequiv g-1) gave flexible self-standing membranes by soln. casting. Compared to the two-component (sulfophenylene and quinquephenylene segments) copolymer membranes, the incorporation of the third component, perfluoroalkylene groups, resulted in better water utilization for the proton conduction, while it did not alter the other properties such as gas permeability and mech. strength. The selected membrane (SQF-3 with IEC = 2.56 mequiv g-1) exhibited high fuel cell performance under high- and low-humidity conditions with max. power d. reaching 0.97 W cm-2 at 100% RH (relative humidity) and 0.82 W cm-2 at 30% RH, resp., at a c.d. of 1.51 A cm-2 with oxygen. A good interfacial compatibility between the SQF-3 membrane and catalyst layers resulted in mass activity of the cathode catalyst comparable to that obtained with the Nafion membrane NRE 211. During the open circuit voltage (OCV) hold test with air and hydrogen at 80°C and 30% RH for 1000 h, the OCV showed a slight decrease from 0.97 to 0.88 V. Post-test analyses revealed that the SQF-3 membrane retained its initial high fuel cell performance due to its high chem. stability as well as low gas permeability.
- 63Chen, L.; Zhang, S.; Jiang, Y.; Jian, X. Preparation and characterization of sulfonated poly(aryl ether ketone)s containing 3,5-diphenyl phthalazinone moieties for proton exchange membrane. RSC Adv. 2016, 6, 75328– 75335, DOI: 10.1039/c6ra14848d[Crossref], [CAS], Google Scholar63https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC28Xht1Kltb3J&md5=bfc0b3d988ec52531299bce80a8aa06dPreparation and characterization of sulfonated poly(aryl ether ketone)s containing 3,5-diphenyl phthalazinone moieties for proton exchange membraneChen, Liyun; Zhang, Shouhai; Jiang, Yiwen; Jian, XigaoRSC Advances (2016), 6 (79), 75328-75335CODEN: RSCACL; ISSN:2046-2069. (Royal Society of Chemistry)A series of sulfonated poly(phthalazinone ether ketone)s contg. 3,5-di-Ph phthalazinone moieties (SPPEK-dPs) were prepd. by the sulfonation of poly(aryl ether ketone)s contg. 3,5-di-Ph phthalazinone moieties (PPEK-dPs) which were synthesized via direct nucleophilic polycondensation from 4-(4-hydroxyphenyl)-2,3-phthalazin-1-ketone (DHPZ), 4-(3,5-diphenyl-4-hydroxyphenyl)-2,3-phthalazin-1-ketone (DHPZ-dP) and 4,4-difluorobenzophenone (DFB). The mol. structures were assessed by FTIR and 1H-NMR spectroscopy. The ion exchange capacity (IEC) of these sulfonated polymers were in the range of 0.99-1.81 mmol g-1. SPPEK-dP proton exchange membranes demonstrated good mech. properties as well as dimensional, thermal, and oxidative stability. The proton conductivities of SPPEK-dP membranes increased with DHPZ-dP content and temp. The proton cond. of SPPEK-dP-55 was 13.18 × 10-2 S cm-1 at 95 °C. Furthermore, the methanol diffusion coeffs. of SPPEK-dP membranes were 0.12 × 10-7 cm2 s-1 to 1.09 × 10-7 cm2 s-1 depending on the molar ratio of DHPZ-dP. Remarkably, the selectivity of SPPEK-dP membranes was 5-7 times higher than that of Nafion 117 membranes under the same conditions. All of the above properties indicate that SPPEK-dPs have potential applications in proton exchange membranes for direct methanol fuel cells.
- 64Zhang, H.; Zhou, Z. Modified poly(phthalazinone ether ketone) membranes for direct methanol fuel cell. Polym. Adv. Technol. 2008, 19, 425– 431, DOI: 10.1002/pat.1028[Crossref], [CAS], Google Scholar64https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BD1cXntlWku78%253D&md5=9f2d76a2ba803ccb40f2a533bdd00faaModified poly(phthalazinone ether ketone) membranes for direct methanol fuel cellZhang, Hongwei; Zhou, ZhentaoPolymers for Advanced Technologies (2008), 19 (5), 425-431CODEN: PADTE5; ISSN:1042-7147. (John Wiley & Sons Ltd.)Sulfonated poly(phthalazinone ether ketone) (SPPEK) was prepd. by modification of poly(phthalazinone ether ketone) (PPEK) with 98% concd. H2SO4 or 98% concd. H2SO4 and chlorosulfonic acid mixt. at 80-100°. The presence of sulfonic acid groups in SPPEKs was confirmed by FTIR anal. and NMR and the DSs were detd. by EDX. A blend membrane of No. 21 SPPEK and phosphotungstic acid was prepd. The MeOH permeabilities of SPPEK and blend membranes were ∼20 times lower than that of Nafion 117 at room temp. A direct MeOH fuel cell test with 2 M MeOH soln. and air breathing showed that the blend membrane had a better performance than that of the Nafion 117.