Biobutanol as Fuel for Direct Alcohol Fuel Cells-Investigation of Sn-Modified Pt Catalyst for Butanol Electro-oxidation

: Direct alcohol fuel cells (DAFCs) mostly use low molecular weight alcohols such as methanol and ethanol as fuels. However, short-chain alcohol molecules have a relative high membrane crossover rate in DAFCs and a low energy density. Long chain alcohols such as butanol have a higher energy density, as well as a lower membrane crossover rate compared to methanol and ethanol. Although a signi ﬁ cant number of studies have been dedicated to low molecular weight alcohols in DAFCs, very few studies are available for longer chain alcohols such as butanol. A signi ﬁ cant development in the production of biobutanol and its proposed application as an alternative fuel to gasoline in the past decade makes butanol an interesting candidate fuel for fuel cells. Di ﬀ erent butanol isomers were compared in this study on various Pt and PtSn bimetallic catalysts for their electro-oxidation activities in acidic media. Clear distinctive behaviors were observed for each of the di ﬀ erent butanol isomers using cyclic voltammetry (CV), indicating a di ﬀ erence in activity and the mechanism of oxidation. The voltammograms of both n -butanol and iso -butanol showed similar characteristic features, indicating a similar reaction mechanism, whereas 2-butanol showed completely di ﬀ erent features; for example, it did not show any indication of poisoning. Ter -butanol was found to be inactive for oxidation on Pt. In situ FTIR and CV analysis showed that OH ads was essential for the oxidation of primary butanol isomers which only forms at high potentials on Pt. In order to enhance the water oxidation and produce OH ads at lower potentials, Pt was modi ﬁ ed by the oxophilic metal Sn and the bimetallic PtSn was studied for the oxidation of butanol isomers. A signi ﬁ cant enhancement in the oxidation of the 1 ° butanol isomers was observed on addition of Sn to the Pt, resulting in an oxidation peak at a potential ∼ 520 mV lower than that found on pure Pt. The higher activity of PtSn was attributed to the bifunctional mechanism on PtSn catalyst. The positive in ﬂ uence of Sn was also con ﬁ rmed in the PtSn nanoparticle catalyst prepared by the modi ﬁ cation of commercial Pt/ C nanoparticle and a higher activity was observed for PtSn (3:1) composition. The temperature-dependent data showed that the activation energy for butanol oxidation reaction over PtSn/C is lower than that over Pt/C.


INTRODUCTION
Direct alcohol fuel cells (DAFCs) are promising alternative power sources and have advantages over hydrogen fuel cells for portable applications.For example, DAFCs utilize liquid fuels, which increase the ease of handling and safety of the alcohol fuel. 1,2In addition, the energy densities of low molecular weight alcohols are higher than liquid hydrogen. 1In DAFCs, the alcohol molecule is directly oxidized on the anode, releasing protons and electrons.The electrons travel through an external circuit to the cathode side whereas the proton is transported through a proton exchange membrane (e.g., Nafion) to the cathode and reacts with the oxygen and electrons to produce water.Various alcohol molecules, such as methanol, ethanol, propanol, ethylene glycol, and glycerol, have been studied as fuels for DAFCs.However, to date, there are two major obstacles facing the development of DAFCs: (i) alcohol crossover from anode to cathode through the membrane and (ii) low activity and complex reaction mechanism of alcohol oxidation.In addition to this, the intermediates formed during the alcohol oxidation reaction, such as CO ads , poison the Pt catalysts.
Methanol, being the simplest alcohol with no C−C bond, has been studied widely 2 and has been shown to be able to completely oxidize to CO 2 giving 6e − , but can also undergo multistep electron transfer reactions resulting in several reaction products and intermediates such as formaldehyde and formic acid.Higher alcohols which contain the C−C bonds are more difficult to oxidize as they form various adsorbed and intermediate species instead of completely oxidizing to CO 2 , thus reducing the efficiency of the fuel cell. 2 For example, on a Pt electrode in acidic media, within the fuel cell operating potential range, often the number of electrons obtained for CH 3 CH 2 OH (4e − ), HCHO (4e − ), HCOOH (2e − ), n-PrOH (4e − ), i-PrOH (2e − ), and ethylene glycol (4e − ) oxidation are lower than the theoretical e − yield for complete conversion to CO 2 . 3Ethanol has been found to oxidize predominantly by 2e − and 4e − pathways to give acetaldehyde (AAL) and acetic acid (AA) as the major products, respectively.The reactivity of small primary alcohols have been observed to be in the order methanol > ethanol > propanol > n-butanol over Pt electrode in acidic media. 4Adsorbed CO formed as an intermediate during the alcohol oxidation, irreversibly adsorbs on Pt and acts as a catalyst poison, hindering further alcohol adsorption.Moreover, the removal of C 2 , C 3 , and C 4 intermediates formed during alcohol oxidation from the Pt surface is also a difficult process. 5 Therefore, the complete oxidation of alcohol fuels to CO 2 is difficult to achieve, even with state-of-the-art Pt catalysts.
A general reaction of monoalcohol oxidation in acidic media can be written as in eq 1. 2 Since an alcohol molecule contains only one oxygen atom, the complete oxidation to CO 2 requires an additional O atom, which is provided by the water or water adsorbed residue (OH ads ) 2 formed by water oxidation on Pt.However, the oxidation of water on Pt is a difficult process and requires a high potential which increases the anodic overpotential in DAFCs.(1) It is clear from eq 1 that as the number of carbon atoms (n) increases, the number of e − , which can be released during oxidation also increases (e.g., 6 e − per molecule for methanol to 24 e − per molecule for butanol).This makes longer chain length alcohol molecules, such as butanol, interesting fuel candidates for DAFCs.In addition, the alcohol crossover rate is expected to decrease with the alcohol chain length. 6Thus, by achieving a complete oxidation of the alcohol molecule at a lower potential, a high fuel cell efficiency could be achieved.
Various other factors such as availability, cost and sustainability also have to be considered, while selecting a suitable fuel for DAFCs.Although methanol is relatively facile to oxidation, it is toxic, flammable with low boiling point (65  °C) and is not a primary/renewable fuel and cannot be considered as an ideal fuel for practical DAFCs.In contrast, ethanol is nontoxic and can be produced by fermentation of sugars.However, the utilization of first generation biofuels produced from food-based biomass feedstock, such as bioethanol, have been the subject of significant debate over the ethics of utilizing food stock for fuel production instead of nutrition. 7An alternate renewable source, which does not compete with the food production, is required for a sustainable energy future.Thus, second generation biofuels are proposed to be produced from nonfood based biomass feedstock such as lignocellulose biomass (LCB) (e.g., corn stover and fiber, wheat and barley straw, switchgrass, miscanthus). 7,8The advantages of cellulose and lignin based feedstock are that they are abundant and can be considered as a waste product.In this regard, butanol is considered a second generation biofuel, with better infrastructure compatibility and higher energy density than ethanol and are superior to ethanol as a fuel itself or as a gasoline additive. 7,8Also, biobutanol is nonpoisonous, noncorrosive, biodegradable and does not lead to soil and water pollution. 9maller chain alcohols, such as methanol and ethanol, have been widely studied as fuels for DAFCs and their electrooxidation mechanism well documented.However, butanol has been much less studied.Higher alcohols have also been studied due to the interest in the adsorption and oxidation of these molecules.The oxidation of butanol isomers on various electrodes (Pt, Au, Pd and Rh polycrystalline electrodes) in alkaline media was studied by Lamy et al. 10 They have observed that the two primary alcohols, n-butanol and iso-butanol, have a similar activity on Pt in alkaline media, whereas the secondary isomer behaves differently.The ter-butanol was found to be unreactive on all electrodes studied at room temperature. 10imilar behavior was also observed by the present authors over Pt in alkaline media. 11Since the activation of αC−H was generally identified as the initial step in the alcohol oxidation, 12 the different behaviors of the butanol isomers were assumed to be caused by the inductive effect. 13A study on single crystal Pt electrode has shown that Pt(111) is the most active surface with lower poisoning, whereas Pt(100) and Pt(110) surfaces showed high poisoning during n-BtOH oxidation in alkaline media, and based on the activity the single crystal planes were classified as Pt(111) ≫ Pt(110) > Pt(100) > Pt polycrystalline. 14imetallic catalysts are generally found to be more active than the monometallic catalysts for alcohol oxidation reactions.This has been generally attributed to the bifunctional mechanism and/or ligand effect. 15−21 The addition of an oxophilic metal to Pt provides OH ads at a lower potential than that on pristine Pt 15,22 which helps the removal of the poisoning species, CO ads , by oxidizing it to CO 2 .−29 It has been observed that nonalloyed Sn is more active in providing OH species at lower potential than the alloyed Sn 29,30 which assists in the CO ads poisoning removal.PtSn was highly selective toward acetic acid formation during ethanol oxidation, whereas Pt showed selectivity toward acetaldehyde at potentials lower than that for PtOH x formation. 26,30The CO adsorbate was found to form at lower potential on PtSn compared to that on Pt during ethanol oxidation, indicating that PtSn also activates the dissociative adsorption of ethanol. 26FT calculations on the PtSn system for CO oxidation showed that the CO binds only to Pt but not on Sn, whereas OH ads preferentially adsorbs on the Sn sites 31 confirming the bifunctional mechanism on PtSn.
Gonzaĺez et al. 3 reported that alcohols with H at βcarbon are readily oxidizable on PtSn electrode at lower potential than on pure Pt.They proposed that H abstraction from α and β carbon could lead to a stabilizing enol form which could then easily convert to aldehyde by the adsorbed water on Sn active sites.Zhou et al. 32  To the best of our knowledge, there are no reports on the comparison of the activity of butanol isomers on Pt in acidic media or on bimetallic catalysts.In this paper, attempt has been made to give insight into the activity of various isomers of butanol on Pt and PtSn catalysts in acidic media, building upon our previous reported data on n-BtOH over Pt and PtSn. 33oth electrodeposited PtSn and Sn-modified commercial Pt/C have been studied.
2.1.Synthesis of Carbon-Supported PtSn Catalysts.The carbon-supported PtSn catalysts were prepared by modifying the commercial catalyst HiSPEC-4000 Pt/C (40 wt %) catalyst with Sn using the ethylene glycol (Alfa aesar, 99%) reduction method.For this, about 300 mg of Pt/C (40 wt %) was dispersed in 30 cm 3 ethylene glycol (EG) by ultrasonication and to this, the required amount of SnCl 2 •2H 2 O was added to obtain the various mol % of Sn.The pH of the mixture was then adjusted to ∼11−13 by using 1 M NaOH (in EG) and the mixture was refluxed at 180−190 °C for 2 h.The mixture was then cooled to room temperature slowly.The catalyst was then filtered, washed with deionized water and dried overnight in a drying oven.The catalysts prepared are denoted as PtSn (1:2), PtSn (3:1), and PtSn (2:1) based on the mole ratios of Pt and Sn.An alloy PtSn (3:1) was also prepared by the same method for comparison.In this case, H 2 PtCl 6 was used as the Pt precursor and Vulcan XC-72 carbon black was used as a support.The H 2 PtCl 6 and SnCl 2 were dissolved together and added slowly to the EG solution containing Vulcan XC-72 followed by the heat treatment and drying as explained above.
2.2.Physical Characterization.The structure of the carbon supported PtSn catalysts was investigated by powder X-ray diffraction (XRD) utilizing a Panalytical X-Pert Pro with Cu Kα radiation (λ = 1.5406Å).The crystallite sizes of the catalyst particles were evaluated using Scherrer equation 34 from the average of the crystallite sizes of Pt(111), Pt(200), and Pt(220) planes.The surface morphology and elemental composition were studied by transmission electron microscopy (TEM) coupled with energy disperse spectroscopy (EDS) using a JEOL JEM 2100 electron microscope.The samples for TEM were prepared by adding a drop of the catalyst suspension (prepared by the ultrasonically dispersing the catalyst in ethanol) onto a Cu grid and then evaporating the ethanol.The average elemental composition was calculated from about 4−5 EDS spectra.The particle size was calculated from the TEM images (average particle size of <50−80 particles) manually using ImageJ software.
2.3.Electrochemical Analysis.The electrochemical measurements were carried out in a three electrode cell using a potentiostat (SP240, Bio-Logic).An Ag/AgCl-3 M NaCl (BaSi, USA) (0.210 V vs SHE) and a Pt mesh (Goodfellow, UK) were used as reference and counter electrodes, respectively.All potentials are referred in this article with respect to Ag/AgCl-3 M NaCl unless specified otherwise.The cyclic voltammogram (CV) analyses were carried out in 0.1 M butanol isomer +0.1 M H 2 SO 4 solution.N 2 gas was passed through the electrolyte solution for 15 min before carrying out the electrochemical analysis.All electrodes were tested in the supporting electrolyte before testing in the butanol containing solution.The current values were normalized with the active area of Pt calculated from the hydrogen desorption area in the supporting electrolyte free from butanol.
The Pt was deposited on glassy carbon (GC) electrode (Goodfellow, UK) from 5 mM H 2 PtCl 6 + 0.5 M H 2 SO 4 solution at a deposition potential of −0.22 V.The electrochemical active area of Pt, A r (in cm 2 ) was calculated from the CV of Pt in sulfuric acid (SA) supporting electrolyte using eq 2 where Q H is the charge for hydrogen desorption and Q H o is the charge required to oxidize a monolayer of hydrogen from Pt surface (0.21 mC cm −2 ).The current values in the CVs were normalized using A r of Pt to give the specific current density.
The PtSn electrode was prepared by the Sn deposition onto Pt from a freshly prepared solution of 1 mM SnCl 2 + 0.5 M H 2 SO 4 at a deposition potential of −0.21 V (the standard reduction potential of Sn(II)/Sn(0) is −0.35V). 35,36 The Sn coverage was calculated from the CV data obtained in the supporting electrolyte, that is, the difference in the hydrogen desorption charge before and after the deposition.
For each of the carbon supported catalysts, a catalyst ink was prepared by mixing 5 mg of the catalyst with 1.5 cm 3 (ethanol + water) solvent and 20 μL Nafion solution (5 wt % solution).The latter served both as adhesive and proton conductor.The mixture was then ultrasonicated for 30 min and 10 μL ink was drop casted on to a GC electrode (7 mm diameter).The electrode was then dried at ambient temperature and electrochemical tests were carried out in the supporting electrolyte as well as in butanol containing solution.

RESULTS AND DISCUSSION
The CVs of Pt electrodes between the hydrogen evolution and oxygen evolution potential limits in 0.1 M H 2 SO 4 showed characteristic features of Pt such as hydrogen adsorption/ desorption region, double layer region, and Pt oxide formation/ reduction processes (Figure 1).
3.1.Butanol Isomers in Acidic Media.In our previous study, 11 the activities of butanol isomers oxidation on Pt and Pd electrodes were studied in alkaline media and the reactivities were observed to be in the order of n-butanol > iso-butanol >2butanol > ter-butanol.Herein, the activities are compared in acidic media for butanol isomer oxidation on Pt.Since the state-of-the-art fuel cells use acidic type Nafion membranes, activities in acidic media are more important from a technological perspective.The CVs of the oxidation of four butanol isomers on Pt in acidic media at room temperature are shown in Figure 1 (red in color).
Both n-BtOH and iso-BtOH (1°alcohols) showed similar oxidation profiles in the CV (Figure 1a and b), whereas 2butanol (2°alcohol) showed significantly different oxidation features (Figure 1c).In contrast, ter-butanol did not show any reactivity for oxidation at all (Figure 1d).A similar trend was also observed in alkaline media on Pt and Pd previously. 11he n-BtOH and iso-BtOH showed two anodic peaks a 1 and a 2 (at ∼0.65 and ∼1.00 V, respectively) during the positivegoing potential scan (PGPS) and one anodic peak a 3 (∼0.35V) during the negative going potential scan (NGPS) (Figure 1a  and b).These peaks are typical for the primary alcohol molecules in acidic media 1,12,37 and have been attributed to alcohol oxidation by two kinds of chemisorbed oxygen species on Pt 38 during PGPS and the reoxidation of the alcohol molecule during NGPS.It is to be noted that the characteristic CV features of Pt in acid at the hydrogen adsorption/ desorption region 39 (−0.20−0.10V) were altered in the CV of n-BtOH and iso-BtOH, indicating that some of the Pt surface active sites were covered by the adsorbates of butanol or butanol oxidation products.It is well documented that CO ads is the major poisoning species formed during the oxidation of methanol and ethanol, which block the Pt active sites and prevent further adsorption of alcohol molecules onto Pt.Also, most of the primary alcohols form adsorbates that are susceptible to reduction at the potential range of the hydrogen region. 40It was found previously that ethanol 41 and propanol 42 form ethane and propane, respectively, in addition to methane and ethane as product; this indicates that a nondissociative adsorption may also be active in the alcohol oxidation reaction. 40rom the mechanistic studies of alcohol oxidation reactions, it is known that proton removal from the αC−H bond is the first step in the oxidation of alcohol; 13,30,38 this occurs at a low potential, leading to the dissociative adsorption of the alcohol molecule on Pt.In general, the alcohol oxidation mechanism has been described as two parallel reaction pathways (a dualpath mechanism) consisting of (i) dehydrogenation of the alcohol molecule (C−C bond cleavage) to form CO ads and its further oxidation to CO 2 and (ii) the formation of an intermediate product species (without C−C bond cleavage), such as an aldehydic and carboxylic species (Scheme 1). 22,38e dissociative adsorption was found to be the fastest reaction step, and generally occurs at lower potential, forming CO ads .A parallel path to give intermediate species occurs with consecutive dehydrogenation steps involving C−H bonds and O−H bonds.Since the C−C bond cleavage is energetically more difficult than the C−H bond cleavage, the mechanism predominantly follows the second pathway to form partial oxidation products such as aldehyde or acid.The oxidation of these intermediate species to CO 2 is difficult and is generally considered as the rate-determining step in the overall oxidation reaction to CO 2 . 5,38In the case of butanol, C1, C2, C3, and C4 intermediate species could be formed during the oxidation. 40i et al. 4,37 observed the formation of CO ads at E < 0.33 V and CO 2 at E > 0.43 V during n-butanol oxidation on Pt in acidic media using in situ FT-IR, which indicated that the dissociative adsorption (dehydrogenation and C−C bond cleavage) of n-butanol occurs at the double layer region to form CO ads (eq 3), which is then further oxidized at potential where Pt oxide formed (>0.43) to produce CO 2 37,44 (eq 5).
The CO ads formed on the Pt, blocks the active sites and inhibits further butanol adsorption. 4This was confirmed in the present study, by varying the anodic potential limit (E end ) during the CV analysis of n-butanol oxidation (Figure 2).As the forward potential limit was increased, the reoxidation peak (peak a 3 ) current increases and the peak potential shifts slightly to more negative.This indicates that Pt surface was progressively Scheme 1.General Mechanism of Alcohol Oxidation on Pt Electrode 43

ACS Applied Materials & Interfaces
Research Article blocked by the strongly adsorbed species and a high positive potential was required to oxidize the intermediates and clear the Pt active sites for further butanol adsorption. 13,45At higher potentials, water is oxidized on Pt, producing OH ads (eq 4) which helps in the oxidation of CO ads to CO 2 (eq 5).This is clearly seen from the n-butanol and iso-butanol CV, as the oxidation of these isomers occurs only at the potential region where Pt−OH ads is formed (0.50−0.75 V in Figure 1 a and b). 22he poisoning was also confirmed using in situ FTIR analysis (Figure S2).At E ≥ 0.50 V, a negative feature (associated with product) appears at ∼2343 cm −1 in the FTIR spectra, which was attributed to the CO 2 asymmetric stretch.A further negative band at ∼3743 cm −1 also appears in the same potential range, which can be attributed to the OH ads on Pt.It is noted that the OH ads and CO 2 peaks appear at the same potential and both peaks increased with an increase in the potential, supporting the proposal that the CO 2 was produced by the CO ads oxidation with the assistance of OH ads .A positive peak at ∼1595 cm −1 also appears at potentials >0.00 V.This peak could be attributed to the consumption of water in the thin liquid layer between the CaF 2 window and the electrode. 37The intensity of this peak increased with the increase in potential, indicating an increased consumption of water following the reaction shown in Equation 4. These results clearly validate the influence of OH ads in the oxidation of alcohol molecule on Pt.Both pathways i and ii of Scheme 1 can thus occur at high potentials. 38

+
Both CO ads oxidation and direct alcohol oxidation might contribute to peak a 1 for n-butanol and iso-butanol. 4The CO ads oxidation to CO 2 frees the Pt sites for further butanol adsorption which could then be oxidized to give intermediate species (peak a 2 ).In ethanol oxidation, the second peak is attributed to the production of acetic acid/acetaldehyde, together with some CO 2 . 46,47This incomplete oxidation was also thought to be due to C−C bond cleavage being hindered when OH ads is formed on Pt. 48Li and Sun 37 observed both CO 2 and butyric acid at potentials >0.43 V during n-butanol oxidation.However, the butyric acid was difficult to oxidized further to CO 2 6,37 and most of the CO 2 produced during n-BtOH oxidation was thus assumed to originate from the dissociative adsorption of butanol (eq 3). 37At potentials >1.00 V, the Pt surface is covered by the oxide species (Equation 6) and leads to a decrease in the oxidation current 49,50 (Figure 1a−c).
The reduction of the oxide species during the NGPS allows the reoxidation of the intermediate species formed during PGPS, as well as the oxidation of the freshly adsorbed nbutanol, giving rise to peak a 3 .It was reported that the reoxidation peak preferentially gives the partial intermediate product rather than CO 2 for ethanol oxidation, as studied by Wang et al. 48using differential electrochemical mass spectroscopy (DEMS).This was attributed to the poor C−C splitting rate in the potential region of peak a 3 .The peak current for peak a 1 during PGPS was significantly lower than found for peak a 2 , as well as a 3 indicating poor kinetics of n-butanol oxidation on Pt, that is, lower yield of CO 2 .It has been reported elsewhere that the anodic peak current decreases with increase in the carbon chain and the activities of primary alcohols were in the order of methanol > ethanol > propanol > n-butanol. 1,4,51In our previous study 11 of butanol isomers in alkaline media, the primary isomers showed an increase in oxidation current just after the hydrogen desorption region, indicating the effect of OH ads on the alcohol oxidation as the Pt surface was already covered by OH ads in the hydrogen region in alkaline media.Also here, the ratio of the peak a 2 to peak a 1 is higher for n-butanol and iso-butanol compared to that for 2°a lcohol, which could indicate that for 1°butanol isomers, the direct oxidation pathway of alcohol could be more prominent relative to the CO pathway. 46In alkaline media, the peak a 2 to peak a 1 ratio was significantly lower 11 indicating direct alcohol oxidation pathway is less prominent.In alkaline media, kinetic factors may improve the efficiency of the CO route due to easy OH adsorption.This could decrease the direct oxidation of alcohol molecules, whereas the CO route will be unaffected. 46n order to make use of the fuel in a fuel cell, a complete conversion to CO 2 has to be achieved by making the reaction mechanism preferentially follow the CO pathway at a lower potential.From the above results, it is clear that for primary alcohols, the CO pathway is less prominent but occurs at lower potential, whereas the partial oxidation pathway is dominant and occurs at higher anodic potential.In contrast to the 1°butanol isomers, the 2°alcohol, 2butanol, showed quite a different CV feature (Figure 1 c).Two oxidation peaks were observed during PGPS and one oxidation peak during NGPS.The oxidation current increased just after the hydrogen desorption region during the PGPS, giving rise to a peak at ∼0.35 V (peak a 1 ) and another peak at ∼1.00 V (peak a 2 ).During NGPS, an oxidation peak was observed at ∼0.30 V (peak a 3 ).The peak a 1 could be attributed to the dehydrogenation of 2-butanol, whereas peak a 2 could be due to the direct oxidation of 2-butanol. 52The hydrogen desorption region was not suppressed as much as n-butanol and iso-butanol, which indicates that the dissociative adsorption (C−C bond breaking) did not occur for 2-butanol to form strongly adsorbed intermediates such as CO ads . 13,49,53Thus, oxidation of 2butanol occurs once the hydrogen is desorbed from the Pt surface.It is clear that the 2°alcohols have a different oxidation mechanism compared to the 1°alcohols.This might indicate a relatively high activation energy requirement for the C−C bond cleavage in 2°alcohols compared to the 1°alcohols. 50An absence of CO ads during 2°alcohol oxidation has been reported for 2-propanol oxidation based on FT-IR analysis 44,54−56 whereby acetone and CO 2 were the major products, 54,57 albeit with CO 2 only formed in negligible amounts. 57The FTIR analysis of 2-butanol on Pt showed similar features, as found during n-BtOH oxidation with the CO 2 peak appearing in potential region where Pt−OH/O x was formed (Figure S4), indicating that peak a 1 is not associated with CO 2 formation and could be a direct oxidation of 2-butanol, as mentioned above.It is worth pointing out that the formation of ketone species from 2°alcohol does not require water and thus direct oxidation can occur before the water oxidation occurs on Pt. 57 Oxidation of 2-butanol to 2-butanone can occur as given in eq 7.During the NGPS, a reoxidation peak was observed, as in the case of n-BtOH and iso-BtOH, in a similar potential region and can be attributed to the reoxidation of the butanol molecule. 38n increasing the anodic potential limit, oxidation current peaks a 1 , a 2 , and a 3 all increased for 2-butanol (Figure S3).A negative potential shift of the peak a 3 was also observed, indicating the formation of PtO x and blocking of alcohol adsorption at the higher potentials.A more negative potential was required to reduce the PtO x formed at higher potentials and then the surface could be freed up for further fuel adsorption and oxidation.When the potential limit was lower than the PtO x formation region (<∼0.70V), both peak a 1 and a 3 superimpose, indicating a reversible reaction, confirming the lack of poisoning of Pt electrode during 2-BtOH oxidation. 49As the potential was increased beyond the PtO x region, the intermediates were oxidized and the reduction of Pt oxide during NGPS, which released the Pt sites free for further 2butanol adsorption and oxidation.This resulted in the increased NGPS oxidation peak current density and also explained its peak potential shift.On Pt and Pd in alkaline media, 2-butanol showed a lower onset potential as well as multiple oxidation peaks during PGPS. 11But in contrast to acidic media, the oxidation current was significantly lower for 2-butanol in alkaline media in comparison to the 1°alcohols showing the influence of the electrolyte media on the oxidation mechanism for 2-butanol.
Ter-butanol did not show any reactivity toward oxidation and the CVs were similar to that of Pt in the acidic supporting electrolyte at room temperature (Figure 1 d).However, a small improvement in the ter-butanol oxidation activity on Pt at high temperature in acidic media has been reported elsewhere. 12he inactivity of ter-butanol is anticipated, as no αC−H bond is present in ter-butanol which is the first step in the oxidation of alcohol molecules.A similar inactivity of ter-butanol was also observed in alkaline media on Pt and Pd. 11A lower activation energy of 2.1 kJ mol −1 for 2-butanol oxidation on Pt/C microporous electrode in acidic media (at the first anodic peak of ∼0.35 V) compared to the first anodic peaks for ethanol (22.1 kJ mol −1 ) and 2-propanol (10.4 kJ mol −1 ) 49 has been reported, indicating facile reaction kinetics for 2-butanol oxidation.This indicates that the long chain 2°alcohols can give better performance, even without C−C bond cleavage, but the complete oxidation to CO 2 does not occur at lower potential as they follow the nondissociative pathway.On the other hand, for 1°alcohol, the partial oxidation occurs at high potential only as the CO formed by dissociative adsorption blocks the Pt sites at a lower potential.
The peak current of a 1 can generally be correlated with the oxidation activity of the alcohol molecule.On the basis of this, it is clear that both 1°and 2°isomers on Pt in acidic media have a similar activity.2-Butanol, on the other hand, showed a higher current for peak a 1 than the 1°alcohol.However, the peak a 1 for 2-butanol oxidation is associated with a partial oxidation reaction without involving C−C bond cleavage, which thus reduces the conversion efficiency of 2-butanol when used as fuel.Ter-butanol, show no activity for oxidation on Pt.The activity of the butanol isomers for oxidation on Pt in acidic media can thus be given in the order 2-BtOH > n-BtOH> iso-BtOH ≫ ter-BtOH.
Thus, it is clear that 1°isomers are potentially more active for oxidation to give completely oxidized product CO 2 at a lower potential, but the CO 2 production is inhibited by the poisoning species CO.The FTIR and CV analysis indicate that OH ads is essential for the CO oxidation and to release Pt sites.Modification of the Pt-based catalyst to provide OH ads at lower potentials has the potential to effectively oxidize the 1°alcohols to give CO 2 .This strategy, however, may not be relevant to 2butanol, where the mechanism follows a different pathway at lower potentials without CO ads formation.The addition of oxophilic metals to Pt were reported to enhance the alcohol oxidation reaction. 15,22This was explained by the ability of the oxophilic metal to oxidize water at lower potential, providing OH ads species in comparison to bare Pt, where a high overpotential is required for H 2 O oxidation (bifunctional mechanism).The activity for chemisorption of water for various metals are in the order Cu < Pd < Rh < Pt < Ru < Sn. 58 As Sn is the most active metal for water decomposition, a PtSn bimetallic system was studied for butanol oxidation, herein.
3.2.PtSn Bimetallic Catalyst for Butanol Isomer Oxidation in Acidic Media.In our previous study, 33 a higher activity of PtSn than Pt for n-butanol oxidation in acidic media was reported.Here, the reactivity of PtSn for the electrooxidation of all four butanol isomers was compared to Pt in acidic media.Sn was electrodeposited on Pt as described in the Experimental Section.The Sn, especially on the surface, is likely to be mostly present as oxide 3,59 because of the exposure to atmosphere, as well as the charge transfer from Sn to Pt caused by the electronegativity difference between the two metal atoms. 5,21,30,60

Research Article
The morphology of the Pt was not modified significantly by the Sn addition and a spherical cauliflower type of morphology of Pt was preserved for PtSn, as reported in our previous study. 33The current density value for PtSn electrodes was normalized by the A r calculated from the CV of PtSn in 0.1 M H 2 SO 4 .The composition of PtSn was difficult to determine from EDX and XRD analysis due to the low Sn coverages, and also, it is likely that not all the Sn is being present in crystalline form. 21Thus, the Sn coverage (θ Sn ) was calculated using the electrochemical method from the difference in the hydrogen desorption charge before (Q H ) and after the Sn deposition (Q H Sn ), as given in eq 8. 21 This method also allows the determination of the active area without modifying the Pt−Sn surface before testing it in butanol solution.Suppression of the hydrogen desorption region, as well as an increased doublelayer current for the PtSn (because of the oxide formation) electrode, is consistent with the presence of Sn on Pt (Figure S5).This method has been reported in literature to estimate the Sn coverage on Pt. 21,33,35,59 During the PGPS in H 2 SO 4 (Figure S5), an oxidation peak appears with an onset potential of ∼0.15 V and the peak potential at ∼0.50 V for PtSn, indicating the oxidation of adsorbed Sn species by the dissociation of water on Sn. 21,39,59 A small reduction peak at ∼0.35 V could be attributed to the reduction of oxidized Sn, as at the upper potential in the CV, Pt surface is not oxidized. 59The upper potential in CV analysis was limited to a maximum of 0.60 V for PtSn to avoid dissolution of Sn into solution at higher potentials. 61The lower onset potential of tin oxidation (∼0.15 V) than the Pt oxidation potential (∼0.55 V) also confirms the oxophilic nature of Sn.
Figure 3a shows the PGPS of the Pt and PtSn electrode in 0.1 M n-BtOH + 0.1 M H 2 SO 4 solution.The Pt shows characteristic features of butanol oxidation with an onset potential of ∼0.55 V. 33 However, for the PtSn electrode, a peak at lower potential of ∼0.27 V was observed which is at significantly lower potential than the peak a 1 for Pt (∼0.65 V).Similar behavior was also observed for iso-butanol (Figure 3 b).This lower potential peak was not observed in the supporting electrolyte (0.1 M H 2 SO 4 ), but only in n-butanol and isobutanol containing solutions, indicating that the peak originated from the butanol oxidation.This was also further confirmed by gradually adding n-butanol to 0.1 M H 2 SO 4 supporting electrolyte while running the CV, the lower potential peak appears only when butanol was added to the solution (not shown).Since this peak appears at a potential region far below PtOH/PtO x formation, the active oxygen species for the n-BtOH and iso-BtOH must originate from the Sn.The oxygenate species formed on Sn could be either an OH ad species or the SnO 2 itself. 25This may be attributed to the low onset potential for OH ads formation on Sn as observed previously. 25,62A similarity between the primary butanol on PtSn and 2-butanol on Pt is notable.Both show an increase in oxidation current after the hydrogen desorption region, indicating that poisoning is not dominant and the oxidation of the alcohol occurs in this potential region.A similar lower potential peak at ∼0.23−0.29 V was also observed for ethanol oxidation on PtSn 25,30,33,62 and methanol oxidation on PtRu. 15n addition to the lower onset potential, a higher current efficiency of CO 2 production was also observed on PtRu and PtSn for the methanol oxidation reaction and was attributed to electronic modification of Pt by Ru in addition to the bifunctional mechanism. 15It is noted that the onset for nbutanol and iso-butanol oxidation on PtSn was at significantly lower potential (∼0.0−0.05V) compared to that on Pt (∼0.55 V).A lower onset of 150−300 mV for CO oxidation on PtSn compared to Pt was observed in CO stripping experiments, 21,26 confirming the positive effect of Sn on the CO oxidation reaction on Pt.Also, a lower onset potential of about 100−200 and 200−300 mV, respectively, for methanol 39 and ethanol 25,26,33 oxidation on PtSn compared to Pt has been reported and explained by the bifunctional mechanism.The Sn adsorbs oxygenated species at lower potentials leading to the easy removal of strongly adsorbed CO ads as given in eq 9−12, 25,26 which helps in the further adsorption of butanol.This is a significant observation as it indicates that even long chain alcohol, such as butanol, could be effectively oxidized on bimetallic PtSn catalyst, at even lower potential than ethanol on Pt electrode.
The effect of temperature on n-butanol oxidation on electrodeposited Pt and PtSn electrodes was reported in our previous work 33 and a lower activation energy on PtSn compared to Pt was observed at the oxidation peak region.Gonzaĺez 3 observed that alcohols with H atoms on the β carbon can be oxidized on PtSn at lower potential than on Pt.They proposed that H abstraction from α and β carbons could lead to the formation of a stabilizing enol structure which could then convert to an aldehyde.This conversion would be facilitated by the O-rich surface of the Pt−Sn, as the attack on enol by adsorbed H 2 O could easily form a hydrated aldehyde. 3t was observed in our previous experiments on n-butanol oxidation that, at high Sn coverage (>40%), the anodic peak current at ∼0.60 V was suppressed significantly 33 and was assumed to be the blocking of Pt active sites by the Sn adatoms. 15However, with an increase in number of cycles between the potential ranges −0.22 to 0.75 V, the peak at ∼0.60 V starts to appear, indicating that dissolution of Sn may be occurring at higher potentials, freeing up the Pt active sites for butanol adsorption.It is obvious that the Pt active sites are required for the butanol adsorption as Sn does not adsorb CO 31 but only helps in the water adsorption at low overpotentials. 21he PtSn electrode for the oxidation reaction of iso-butanol also showed a similar feature to that of n-butanol (Figure 3b), whereas 2-butanol and ter-butanol did not show any significant activity on the PtSn electrode.As discussed previously for the Pt electrode, CO ads was not formed from 2-butanol and thus no significant improvement was observed on PtSn compared to Pt.Similar behavior was also observed for 2-propanol oxidation on PtRu with no difference in the activity compared to pure Pt. 52 The inactivity of ter-butanol on PtSn has also been reported. 3s discussed in the previous section, the primary isomers of butanol are more active for the oxidation reaction, but the CO poisoning increases the overpotential.It was clear from this study that using bimetallic catalyst such as PtSn, the poisoning species can be removed at lower potential and thus can facilitate the oxidation of butanol at a lower potential.
3.3.Carbon-Supported PtSn Catalyst for n-Butanol Oxidation.To further confirm the Sn effect on Pt for butanol oxidation, and also to control the Sn composition more accurately, commercial Pt/C (40%) was modified by Sn using a chemical reduction method described in the Experimental Section.The XRD spectra of the PtSn/C catalysts are given in Figure 4.The XRD shows typical peaks for the face centered cubic (fcc) structure of crystalline Pt. 63 The particle size of Pt was in the range of ∼4.1−4.4 nm for all the samples and was calculated using the Scherrer equation. 34Only PtSn with high Sn content showed Sn related peaks in the XRD which were not observed at low Sn contents. 32−65 However, these peaks were relatively broad, which could indicate the amorphous nature of Sn as the catalysts were used as prepared and not subjected to further heat treatment.
For the PtSn (3:1)-alloy catalyst, all the diffraction peaks were slightly shifted to lower 2θ values compared to the Pt/C (40%), which confirm alloy formation; 5,25 whereas for all other Sn-modified Pt/C catalysts, no such peak shifts were observed, confirming the nonalloy nature of the PtSn particle, as expected.Also the particle size for the alloy was lower than that of the Sn modified Pt/C catalysts, which is typical for alloy catalysts. 25The BET surface areas of these catalysts were not significantly different after Sn addition, although a slight increase in the surface area was observed with increase in Sn content for the PtSn/C catalysts (Table 1).The alloy catalyst, on the other hand, showed a higher surface area than all other catalysts, which may explain the slightly greater current density associated with the PtSn(3:1) alloy catalyst (Figure S6) compared to the Sn modified PtSn(3:1) catalyst.
The TEM images of the PtSn(3:1) and PtSn(2:1) are given in Figure 5.A uniform distribution of the spherical particles on the carbon support is evident from the TEM.The average particle size from TEM and XRD was similar, with a slightly higher value obtained from XRD.This could be due to the fact that the TEM particle size was calculated from the average 50− 80 clearly distinguishable particles, whereas XRD represents the bulk sample and the response is dominated by the large crystallites present.An EDS analysis was also carried out for the TEM samples and the compositions obtained for the various samples are given in Table 1.The composition obtained was more or less similar to that expected.However, the possibility of some Sn being deposited on carbon cannot be discarded.
The PGPS voltammogram of PtSn/C nanoparticles in nbutanol-containing solution is compared in Figure 6.For all PtSn catalysts, an oxidation peak between 0.1−0.3V was observed as found for the electrodeposited PtSn catalyst in Figure 3.However, the current density was found to vary with the composition of the catalysts.The maximum current density for the lower potential peak was found for PtSn(3:1).This could be the result of the Pt active sites being blocked by excess Sn for butanol adsorption at higher Sn contents; 32 whereas, at lower Sn content, there was not sufficient OH ads species on Sn sites for CO ads oxidation.Thus, it may be assumed that there is an optimum Sn coverage required for an effective butanol oxidation.The PtSn electrodeposited catalyst also showed a higher current for ∼25% coverage and thus about 20−30% Sn could be considered as an optimum Sn content for the PtSn catalyst.The PtSn(3:1)-alloy catalyst also showed a clear lower potential peak (Figure S6), confirming this assumption.A slightly higher peak current was observed for PtSn(3:1)-alloy catalyst (Figure S6) compared to the nonalloyed catalyst (Figure 6b), which is in contrast with some of the previous reports, where poor activity has been observed for alloy PtSn catalysts, and had been attributed to the electronic interaction between Pt and Sn in the alloy phase. 25,66On the contrary, the electronic effect can also be advantageous, as the charge transfer to Pt by Sn can weaken the Pt-CO bond, which helps in the removal of CO as to be oxidized to CO 2 . 67,68Silva et al. 69 observed a higher current density during ethanol oxidation for PtSn/C alloy catalyst compared to the nonalloyed one which was attributed to the CO 2 formation with slow kinetics on nonalloyed catalyst vs acetic acid formation with faster kinetics for alloyed catalyst.However, as mentioned before the higher surface area could also be the reason for the higher current in the case of alloy catalyst.Further studies are required to clearly distinguish the difference in activity/mechanism in alloy and nonalloyed catalyst.
The Arrhenius plots of the butanol oxidation on Pt/C (40%) commercial catalyst and PtSn(3:1) are given in Figures S7 and  S8.The activation energy for n-butanol oxidation on PtSn(3:1) at 0.20 and 0.30 V was significantly lower (15 kJ mol −1 ) than found for Pt/C (40%) at 0.62 V (37 kJ mol −1 ).Similar results were also observed for electrodeposited PtSn in our previous study. 33Since the first peak on Pt is attributed to the butanol oxidation after the removal of CO ads species, the lower activation energy on PtSn can be attributed to the effectiveness of the catalyst in CO ads removal by the bifunctional mechanism which helps in the adsorption of butanol molecules on Pt.An increase in the lower potential oxidation peak current with increase in n-butanol concentration was observed for PtSn(3:1)/C (Figure S9).Also, with increase in the BtOH concentration, the peak becomes more distinguishable at higher BtOH concentration.A similar behavior was also reported for ethanol oxidation reaction on PtSn. 70All of these confirm the fact that the lower potential peak originates from the butanol oxidation reaction.

CONCLUSIONS
A series of long chain C4 alcohols have been studied for electrochemical oxidation in acidic media on a Pt electrode.It was demonstrated that the different butanol isomers behave differently in their electrochemical oxidation.Both 1°alcohols, n-butanol and iso-butanol, have a similar reactivity for oxidation, whereas 2-butanol, a 2°alcohol, is quite different in its electrochemical oxidation behavior.This indicates a difference in the mechanism of the 1°and 2°isomers.From the CV and FTIR results, it was proposed that 2-butanol does not undergo C−C bond cleavage and thus not produce poisoning species such as CO ads .The oxidation current was also higher for 2butanol compared to that of 1°alcohols, indicating its effectiveness in oxidation without C−C cleavage to give partial oxidation products, though the partial oxidation will reduce the conversion efficiency of the fuel.The ter-butanol, on the other hand, is not reactive for oxidation at all.The 1°and 2°isomers   of butanol showed a similar current density, indicating a similar reactivity in acidic media; whereas in alkaline media the activity of 2°isomers was lower than that of 1°, as reported in our previous study.Thus, in both media, primary butanol isomers could be considered as suitable fuels for DAFCs.In addition, both the 1°butanol isomers can be produced from biomass which makes them an attractive fuel for a sustainable energy future.The in situ FTIR data provides evidence of the effect of OH ads in removing CO ads , and it was concluded that the OH ads is essential in the oxidation of alcohol on Pt.
To reduce the CO ads poisoning effect by forming OH ads at a lower potential, PtSn bimetallic catalysts/electrodes were studied, and a significant improvement in the performance was observed for the 1°isomers of butanol, with an oxidation peak at ∼0.25−0.30V which is at a significantly lower overpotential than that on bare Pt.However, no significant effect with Sn addition to Pt was observed for 2°and 3°b utanol.The higher activity on Sn addition to Pt for the 1°b utanol could be attributed to the bifunctional mechanism associated with the bimetallic electrode.The higher activity for PtSn was also confirmed for carbon supported PtSn nanoparticle catalysts prepared by modifying commercial Pt/C with Sn.The peak at lower potential was also present in the PtSn/C electrode and a high activity was observed for PtSn(3:1)/C catalyst.The activation energy for butanol oxidation was also observed to be lower on PtSn(3:1)/C (∼15 kJ mol −1 ) compared to that of Pt/C catalyst (∼37 kJ mol −1 ).
Overall, we have successfully demonstrated that higher alcohols, especially biobutanol, have the potential to be used as fuel for DAFCs, especially on multifunctional catalysts such as PtSn.Nevertheless, a detailed further study is ongoing regarding the oxidation mechanism of butanol over bimetallic catalysts which will help in the further development of multifunctional catalysts for complete electro-oxidation of biobutanol.*E-mail: w.lin@lboro.ac.uk.*E-mail: c.hardacre@manchester.ac.uk.

Notes
The authors declare no competing financial interest.■ ACKNOWLEDGMENTS UK Catalysis Hub is kindly thanked for resources and support provided via our membership of the UK Catalysis Hub Consortium and funded by EPSRC (Grant no.EP/K014706/ 1).Material Chemistry Centre, Dept. of Chemistry, UCL, and Dr. Ana Jorge Sobrido, Dept.Of Chemical Engineering, UCL, are kindly acknowledged for their help and support in the TEM analysis.
studied the single cell performance of direct ethanol fuel cell using PtSn as the anode catalysts with various Sn content.All the PtSn catalysts studied (Pt 1 Sn 1 /C, Pt 3 Sn 2 /C, ACS Applied Materials & Interfaces Research Article Pt 2 Sn 1 /C, Pt 3 Sn 1 /C, Pt 4 Sn 1 /C) showed a better performance than pure Pt, with Pt 3 Sn 2 and Pt 2 Sn 1 giving the maximum power density at 60 and 75 °C, respectively.

Figure 2 .
Figure 2. Effect of varying anodic potential limit on the CV of Pt/GC in 0.1 M BtOH + 0.1 M H 2 SO 4 at room temperature.The anodic potential limit varied from 0.5 to 1.3 V with 100 mV increment.The cathodic potential limit was fixed at −0.22 V. Scan rate 20 mV s −1 .

Figure 3 .
Figure 3. CVs of Pt and PtSn in solutions of 0.1 M butanol isomer +0.1 M H 2 SO 4 : (a) n-butanol, (b) iso-butanol, (c) 2-butanol, and (d) ter-butanol.The current values were normalized by A r of Pt for both Pt and PtSn electrodes.The Sn coverage (θ Sn ) is also given in the respective figure.

a
Crystallite size was calculated from the average of the crystallite size of Pt(111), Pt(200) and Pt(220) planes.Sn mol % calculated from the average of 4−5 EDS spectra.

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ASSOCIATED CONTENT * S Supporting Information The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acsami.6b02863.Experimental set up of in situ FTIR, FTIR spectra of n-BtOH and 2-BtOH oxidation on Pt in acidic media, CVs of Pt and PtSn in 0.1 M H 2 SO 4 , CV of PtSn(3:1) alloy in n-BtOH containing solution, and Arrhenius plot of butanol oxidation on Pt/C(40%) commercial and PtSn(3:1)/C catalysts (PDF) ■ AUTHOR INFORMATION Corresponding Authors

Table 1 .
Physical Properties of the PtSn Nanoparticle Catalysts Studied a