One-Pot Synthesis of PtNi Alloy Nanoparticle-Supported Multiwalled Carbon Nanotubes in an Ionic Liquid Using a Staircase Heating ProcessClick to copy article linkArticle link copied!
- Yu YaoYu YaoDepartment of Applied Chemistry, Graduate School of Engineering, Osaka University, 2-1 Yamada-oka, Suita, Osaka 565-0871, JapanMore by Yu Yao
- Reiko IzumiReiko IzumiDepartment of Applied Chemistry, Graduate School of Engineering, Osaka University, 2-1 Yamada-oka, Suita, Osaka 565-0871, JapanMore by Reiko Izumi
- Tetsuya Tsuda*Tetsuya Tsuda*Email: [email protected]Department of Applied Chemistry, Graduate School of Engineering, Osaka University, 2-1 Yamada-oka, Suita, Osaka 565-0871, JapanMore by Tetsuya Tsuda
- Kohei AsoKohei AsoSchool of Materials Science, Japan Advanced Institute of Science and Technology, 1-1 Asahidai, Nomi, Ishikawa 923-1292, JapanMore by Kohei Aso
- Yoshifumi OshimaYoshifumi OshimaSchool of Materials Science, Japan Advanced Institute of Science and Technology, 1-1 Asahidai, Nomi, Ishikawa 923-1292, JapanMore by Yoshifumi Oshima
- Susumu Kuwabata*Susumu Kuwabata*Email: [email protected]Department of Applied Chemistry, Graduate School of Engineering, Osaka University, 2-1 Yamada-oka, Suita, Osaka 565-0871, JapanMore by Susumu Kuwabata
Abstract
High-performance PtNi alloy nanoparticle-supported multiwalled carbon nanotube composite (PtNi/MWCNT) electrocatalysts can be prepared via one-pot preparation for oxygen reduction reaction. This route of preparation utilizes the pyrolytic decomposition of metal precursors, such as Pt(acac)2 with Ni precursors, nickel bis(trifluoromethanesulfonyl)amide (Ni[Tf2N]2) or nickel acetylacetonate (Ni(acac)2), in an ionic liquid (IL), N,N,N-trimethyl-N-propylammonium bis(trifluoromethanesulfonyl)amide ([N1,1,1,3][Tf2N]). Currently, there is insufficient information concerning the effect of difference in preparation conditions on the formation mechanism and catalytic activity of PtNi/MWCNT. In this article, a staircase heating process was used to investigate the PtNi alloy nanoparticle formation mechanism and catalytic activity of the resulting PtNi/MWCNT. We found that the alloy formation process, composition, and crystal structure, which directly affect the electrocatalytic activity, strongly depended on the Ni precursor species and heating process. The catalytic performance of certain PtNi/MWCNTs collected during the staircase heating process was better than that of PtNi/MWCNTs produced via the conventional heating process.
Introduction
Results and Discussion
Figure 1
Figure 1. Heating profile (black solid line) employed for the staircase heating process and TG measurement results of Pt(acac)2 (gray solid line), Ni[Tf2N]2 (red dashed line), and Ni(acac)2 (blue dash-dotted line) obtained using the staircase heating process. Samples were taken from the IL mixtures containing the metal precursors and MWCNTs at points A–L as shown on the top axis.
Figure 2
Figure 3
sampling point | condition | mean particle size (nm) | Pt loading amount (wt %) | Ni content in nanoparticles (atom %) | ECSA (m2 gPt–1) | current density at 0.90 V (mA cm–2) |
---|---|---|---|---|---|---|
C | 473 K | 1.0 (0.3)a | 1.0 | 0 | ||
D | 473 K, 1 h | 1.9 (0.6)a | 12.5 | 4 | ||
E | 573 K | 2.4 (0.5)a | 26.4 | 6 | 46.1 | 0.397 |
I | 573 K, 1 h | 2.7 (0.4)a | 28.7 | 18 | 80.0 | 0.895 |
J | 573 K, 2 h | 2.8 (0.4)a | 27.0 | 26 | 66.2 | 1.102 |
K | 573 K, 3 h | 2.4 (0.5)a | 26.6 | 34 | 46.8 | 1.431 |
L | 573 K, 4 h | 2.6 (0.5)a | 23.3 | 30 | 50.8 | 2.123 |
The values in parentheses are standard deviations.
Figure 4
Figure 4. Ni contents of the nanoparticles deposited onto MWCNTs in the IL-MWCNT mixtures containing Pt(acac)2 and either Ni[Tf2N]2 (red solid line with solid square) or Ni(acac)2 (blue dashed line with open square). The Ni contents were determined using ICP-AES.
Figure 5
Figure 5. X-ray diffraction patterns of the PtNi/MWCNTs prepared with (a) Ni[Tf2N]2 or (b) Ni(acac)2. The sampling points and PtNi alloy nanoparticle compositions of the specimens are denoted on the graph.
Figure 6
Figure 6. Schematic illustration of plausible PtNi alloy formation mechanisms derived from the detailed analysis of the PtNi/MWCNTs prepared via the staircase heating process.
Figure 7
Figure 7. Cyclic voltammograms recorded using glassy carbon electrodes with PtNi/MWCNTs in a N2-saturated 0.1 M HClO4 aqueous solution. The Ni precursors used for preparing the PtNi/MWCNTs were either (a) Ni[Tf2N]2 or (b) Ni(acac)2. The sampling points during the staircase heating process were E (black dashed line), F (red dashed line), G (blue dashed line), H (green dashed line), I (black solid line), J (red solid line), K (blue solid line), and L (green solid line). The scan rate was 10 mV s–1.
Figure 8
Figure 8. Mean particle size (black solid square) and ECSA change (red solid square) of the PtNi nanoparticles in PtNi/MWCNTs prepared with either (a) Ni[Tf2N]2 or (b) Ni(acac)2. The sampling points taken during the staircase heating process are denoted on these figures.
Figure 9
Figure 9. Hydrodynamic voltammograms recorded at glassy carbon electrodes with the PtNi/MWCNTs and a commercially available Pt/C catalyst (gray dotted line) in an O2-saturated 0.1 M HClO4 aqueous solution. The Ni precursors used for preparing the PtNi/MWCNTs were (a) Ni[Tf2N]2 and (b) Ni(acac)2. The sampling points during the staircase heating process were E (black dashed line), F (red dashed line), G (blue dashed line), H (green dashed line), I (black solid line), J (red solid line), K (blue solid line), and L (green solid line). The revolution speeds were 1600 rpm. The scan rates were 10 mV s–1.
Conclusions
Experimental Methods
Synthesis of Ni[Tf2N]2
Preparation of PtNi/MWCNTs
Characterization
Electrochemical Measurements

Supporting Information
The Supporting Information is available free of charge at https://pubs.acs.org/doi/10.1021/acsomega.0c02951.
TG measurement results for metal precursors (Figure S1); particle size distributions of nanoparticles (Figures S2 and S5); TEM images (Figure S4), BF-STEM and HAADF-STEM images (Figures S3, S6, and S7), EDS mappings (Figures S3, S6, and S7), and SAED patterns (Figure S8) of the PtNi/MWCNTs; summary of PtNi/MWCNTs prepared in [N1,1,1,3][Tf2N] with Pt(acac)2, Ni(acac)2, and MWCNT (Table S1) (PDF)
Terms & Conditions
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Acknowledgments
This research was partially supported by JSPS KAKENHI (grant number JP19H02814). A part of this work was conducted in JAIST, supported by Nanotechnology Platform Program (Molecule and Material Synthesis) of the Ministry of Education, Culture, Sports, Science and Technology (MEXT), Japan.
References
This article references 37 other publications.
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- 5Escudero-Escribano, M.; Malacrida, P.; Hansen, M. H.; Vej-Hansen, U. G.; Velazquez-Palenzuela, A.; Tripkovic, V.; Schiøtz, J.; Rossmeisl, J.; Stephens, I. E. L.; Chorkendorff, I. Tuning the activity of Pt alloy electrocatalysts by means of the lanthanide contraction. Science 2016, 352, 73– 76, DOI: 10.1126/science.aad8892Google Scholar5https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC28XlsFSmu7c%253D&md5=f59ab36fab568dfd01b4661f8282a8eeTuning the activity of Pt alloy electrocatalysts by means of the lanthanide contractionEscudero-Escribano, Maria; Malacrida, Paolo; Hansen, Martin H.; Vej-Hansen, Ulrik G.; Velazquez-Palenzuela, Amado; Tripkovic, Vladimir; Schiotz, Jakob; Rossmeisl, Jan; Stephens, Ifan E. L.; Chorkendorff, IbScience (Washington, DC, United States) (2016), 352 (6281), 73-76CODEN: SCIEAS; ISSN:0036-8075. (American Association for the Advancement of Science)The high platinum loadings required to compensate for the slow kinetics of the oxygen redn. reaction (ORR) impede the widespread uptake of low-temp. fuel cells in automotive vehicles. We have studied the ORR on eight platinum (Pt)-lanthanide and Pt-alk. earth electrodes, Pt5M, where M is lanthanum, cerium, samarium, gadolinium, terbium, dysprosium, thulium, or calcium. The materials are among the most active polycryst. Pt-based catalysts reported, presenting activity enhancement by a factor of 3 to 6 over Pt. The active phase consists of a Pt overlayer formed by acid leaching. The ORR activity vs. the bulk lattice parameter follows a high peaked "volcano" relation. We demonstrate how the lanthanide contraction can be used to control strain effects and tune the activity, stability, and reactivity of these materials.
- 6Shao, M.; Odell, J. H.; Peles, A.; Su, D. The role of transition metals in the catalytic activity of Pt alloys: quantification of strain and ligand effects. Chem. Commun. 2014, 50, 2173– 2176, DOI: 10.1039/c3cc47341dGoogle Scholar6https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC2cXhsFCnsLo%253D&md5=00b9dcedef30fab01bdb0e1386bd31c1The role of transition metals in the catalytic activity of Pt alloys: quantification of strain and ligand effectsShao, Minhua; Odell, Jonathan H.; Peles, Amra; Su, DongChemical Communications (Cambridge, United Kingdom) (2014), 50 (17), 2173-2176CODEN: CHCOFS; ISSN:1359-7345. (Royal Society of Chemistry)The oxygen redn. reaction (ORR) activity as a function of thickness of the Pt shell on Pt-Ni alloy nanoparticles was established. We demonstrated that the effects of transition metals could only extend to a very thin Pt shell, which was 0.9-1.0 nm for Pt3Ni.
- 7Asano, M.; Kawamura, R.; Sasakawa, R.; Todoroki, N.; Wadayama, T. Oxygen Reduction Reaction Activity for Strain-Controlled Pt-Based Model Alloy Catalysts: Surface Strains and Direct Electronic Effects Induced by Alloying Elements. ACS Catal. 2016, 6, 5285– 5289, DOI: 10.1021/acscatal.6b01466Google Scholar7https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC28XhtFGjs73K&md5=a1b70c859dae994e151075285436d087Oxygen Reduction Reaction Activity for Strain-Controlled Pt-Based Model Alloy Catalysts: Surface Strains and Direct Electronic Effects Induced by Alloying ElementsAsano, Masato; Kawamura, Ryutaro; Sasakawa, Ren; Todoroki, Naoto; Wadayama, ToshimasaACS Catalysis (2016), 6 (8), 5285-5289CODEN: ACCACS; ISSN:2155-5435. (American Chemical Society)Surface strain and electronic interactions (i.e., strain and ligand effects) play key roles in enhancing the oxygen redn. reaction (ORR) catalytic activity of Pt-based alloy catalysts. Herein, we evaluate the ORR activity enhancement factors for Pt(111)-shell layers on Pt25Ni75(111) single-crystal surfaces prepd. by mol. beam epitaxy under ultrahigh vacuum (UHV). Scanning tunneling microscopy images of the pristine surfaces collected under UHV revealed periodic surface modulations, known as Moire patterns, suggesting that the topmost Pt(111)-shell layers are compressively strained by the influence of the underlying Ni atoms. The correlation between the ORR activities and estd. strains for 3-ML- and 4-ML-thick Pt shells (where ML represents monolayer), each having -1.7% and -1.2% strained Pt-shells, correspond well to the strain-based theory predictions. On the other hand, a 2-ML-thick Pt shell, with -2.8% strain, exhibits a remarkable ORR activity enhancement, i.e., 25 times higher than the pristine Pt(111): the enhancement factor anomalously deviates from the value predicted by the strain-based theory. Therefore, the activity enhancement of the 2-ML-thick Pt sample can be ascribed to a ligand effect induced by the Ni atoms just below the topmost Pt(111)-shell layer. The results obtained in this study provide a fundamental insight into the ORR activity enhancement mechanisms of Pt-based electrocatalysts.
- 8Tian, X.; Zhao, X.; Su, Y.-Q.; Wang, L.; Wang, H.; Dang, D.; Chi, B.; Liu, H.; Hensen, E. J. M.; Lou, X. W. D.; Xia, B. Y. Engineering bunched Pt-Ni alloy nanocages for efficient oxygen reduction in practical fuel cells. Science 2019, 366, 850– 856, DOI: 10.1126/science.aaw7493Google Scholar8https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC1MXitFOnu7rK&md5=1bb23a5a32c576f8beea3b83a4925a8aEngineering bunched Pt-Ni alloy nanocages for efficient oxygen reduction in practical fuel cellsTian, Xinlong; Zhao, Xiao; Su, Ya-Qiong; Wang, Lijuan; Wang, Hongming; Dang, Dai; Chi, Bin; Liu, Hongfang; Hensen, Emiel J. M.; Lou, Xiong Wen; Xia, Bao YuScience (Washington, DC, United States) (2019), 366 (6467), 850-856CODEN: SCIEAS; ISSN:1095-9203. (American Association for the Advancement of Science)The expense and scarcity of platinum has driven efforts to improve oxygen-redn. catalysts in proton-exchange membrane fuel cells. Tian et al. synthesized chains of platinum-nickel alloy nanospheres connected by necking regions. These structures can be etched to form nanocages with platinum-rich surfaces that are highly active for oxygen redn. In fuel cells running on air and hydrogen, these catalysts operated for at least 180 h.
- 9Wang, W.; Wang, Z.; Wang, J.; Zhong, C.-J.; Liu, C.-J. Highly Active and Stable Pt-Pd Alloy Catalysts Synthesized by Room-Temperature Electron Reduction for Oxygen Reduction Reaction. Adv. Sci. 2017, 4, 1600486, DOI: 10.1002/advs.201600486Google Scholar9https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A280%3ADC%252BC1crgsVClsg%253D%253D&md5=4b4ec1338ffcf19f203b80afab5a56efHighly Active and Stable Pt-Pd Alloy Catalysts Synthesized by Room-Temperature Electron Reduction for Oxygen Reduction ReactionWang Wei; Wang Zongyuan; Wang Jiajun; Liu Chang-Jun; Zhong Chuan-JianAdvanced science (Weinheim, Baden-Wurttemberg, Germany) (2017), 4 (4), 1600486 ISSN:2198-3844.Carbon-supported platinum (Pt) and palladium (Pd) alloy catalyst has become a promising alternative electrocatalyst for oxygen reduction reaction (ORR) in proton exchange membrane fuel cells. In this work, the synthesis of highly active and stable carbon-supported Pt-Pd alloy catalysts is reported with a room-temperature electron reduction method. The alloy nanoparticles thus prepared show a particle size around 2.6 nm and a core-shell structure with Pt as the shell. With this structure, the breaking of O-O bands and desorption of OH are both promoted in electrocatalysis of ORR. In comparison with the commercial Pt/C catalyst prepared by conventional method, the mass activity of the Pt-Pd/C catalyst for ORR is shown to increase by a factor of ≈4. After 10 000-cycle durability test, the Pt-Pd/C catalyst is shown to retain 96.5% of the mass activity, which is much more stable than that of the commercial Pt/C catalyst.
- 10Burk, J. J.; Buratto, S. K. Electrodeposition of Pt Nanoparticle Catalysts from H2Pt(OH)6 and Their Application in PEM Fuel Cells. J. Phys. Chem. C 2013, 117, 18957– 18966, DOI: 10.1021/jp405302xGoogle Scholar10https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC3sXht12htL3L&md5=73f68f3bb358d63bae84bbdb125af0ebElectrodeposition of Pt Nanoparticle Catalysts from H2Pt(OH)6 and their Application in PEM Fuel CellsBurk, Jonathan J.; Buratto, Steven K.Journal of Physical Chemistry C (2013), 117 (37), 18957-18966CODEN: JPCCCK; ISSN:1932-7447. (American Chemical Society)The authors report the electrochem. deposition of Pt nanoparticles from platinic acid H2[Pt(OH)6] using pulse potential deposition (PPD). The authors are able to control the size, morphol., and loading of Pt nanoparticles from H2[Pt(OH)6] by controlling the deposition parameters such as the pH of the plating soln., the pulse potential, the pulse width, and the duty cycle of the pulse sequence. A high d. of Pt nanoparticles electrodeposited can be produced on both planar and nonplanar electrode supports with high surface area and high catalytic activity. Finally, fuel cell electrodes can be produced using H2[Pt(OH)6] as the source of Pt via the optimized PPD technique. The fuel cells produced from these electrodes are highly efficient with less than half the Pt content of com. available fuel cells, which results in a gravimetric power more than twice that of fuel cells produced by using com. available electrodes.
- 11Hussein, H. E. M.; Maurer, R. J.; Amari, H.; Peters, J. J. P.; Meng, L.; Beanland, R.; Newton, M. E.; Macpherson, J. V. Tracking Metal Electrodeposition Dynamics from Nucleation and Growth of a Single Atom to a Crystalline Nanoparticle. ACS Nano 2018, 12, 7388– 7396, DOI: 10.1021/acsnano.8b04089Google Scholar11https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC1cXht1Kns7fP&md5=3c3a6309b58178bef3d9a0aa5258f767Tracking Metal Electrodeposition Dynamics from Nucleation and Growth of a Single Atom to a Crystalline NanoparticleHussein, Haytham E. M.; Maurer, Reinhard J.; Amari, Houari; Peters, Jonathan J. P.; Meng, Lingcong; Beanland, Richard; Newton, Mark E.; Macpherson, Julie V.ACS Nano (2018), 12 (7), 7388-7396CODEN: ANCAC3; ISSN:1936-0851. (American Chemical Society)In electrodeposition the key challenge is to obtain better control over nanostructure morphol. Currently, a lack of understanding exists concerning the initial stages of nucleation and growth, which ultimately impact the physicochem. properties of the resulting entities. Using identical location scanning TEM (STEM), with B-doped diamond (BDD) serving as both an electron-transparent TEM substrate and electrode, the authors follow this process, from the formation of an individual metal atom through to a cryst. metal nanoparticle, under potential pulsed conditions. In doing so, the authors reveal the importance of electrochem. driven atom transport, atom cluster formation, cluster progression to a nanoparticle, and the mechanism by which neighboring particles interact during growth. Such information will help formulate improved nucleation and growth models and promote wider uptake of electrodeposited structures in a wide range of societally important applications. This type of measurement is possible in the TEM because the BDD possesses inherent stability, has an extremely high thermal cond., is electron beam transparent, is free from contamination, and is robust enough for multiple deposition and imaging cycles. Also, the platform can be operated under conditions such that the authors have confidence that the dynamic atom events the authors image are truly due to electrochem. driven deposition and no other factors, such as electron-beam-induced movement.
- 12Wang, Y.; Hall, A. S. Pulsed electrodeposition of metastable Pd31Bi12 nanoparticles for oxygen reduction electrocatalysis. ACS Energy Lett. 2020, 5, 17– 22, DOI: 10.1021/acsenergylett.9b02219Google Scholar12https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC1MXit1SqsbvI&md5=63580ffd2434529ccc1f28f51e762f6ePulsed Electrodeposition of Metastable Pd31Bi12 Nanoparticles for Oxygen Reduction ElectrocatalysisWang, Yunfei; Hall, Anthony ShojiACS Energy Letters (2020), 5 (1), 17-22CODEN: AELCCP; ISSN:2380-8195. (American Chemical Society)Metastable alloys have recently emerged as high-performance catalysts, extending the toolbox of binary alloy materials that can be utilized to mediate electrocatalytic reactions. In particular, nanostructured metastable ordered intermetallic compds. are challenging to synthesize. Here a method is reported for synthesizing sub-15 nm metastable ordered intermetallic Pd31Bi12 nanoparticles at room temp., in a single step, by pulsed electrochem. deposition onto high surface area carbon supports. The resulting Pd31Bi12 nanoparticles display a 7× enhancement of the mass activity relative to Pt/C and a 4× enhancement relative to Pd/C for the oxygen redn. reaction (ORR). The high performance of Pd31Bi12 nanoparticles is demonstrated to arise from reduced oxygen binding caused by alloying of Pd with Bi. It is also demonstrate that the isolation of Pd sites from each other facilitates methanol-tolerant ORR behavior.
- 13Wang, X.; Orikasa, Y.; Inaba, M.; Uchimoto, Y. Reviving Galvanic Cells To Synthesize Core-Shell Nanoparticles with a Quasi-Monolayer Pt Shell for Electrocatalytic Oxygen Reduction. ACS Catal. 2020, 10, 430– 434, DOI: 10.1021/acscatal.9b03672Google Scholar13https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC1MXitlWktrfF&md5=705b12935fb7af3460cd9d92afd0edddReviving Galvanic Cells To Synthesize Core-Shell Nanoparticles with a Quasi-Monolayer Pt Shell for Electrocatalytic Oxygen ReductionWang, Xiaoming; Orikasa, Yuki; Inaba, Minoru; Uchimoto, YoshiharuACS Catalysis (2020), 10 (1), 430-434CODEN: ACCACS; ISSN:2155-5435. (American Chemical Society)The use of core-shell nanoparticles composed of metal core (Mc, representing Pd, Au, Ru, etc.) and quasi-monolayer Pt shell (Ptqms) facilitates the achievement of cost and activity targets in many important electrocatalytic energy-conversion processes, such as the oxygen-redn. reaction (ORR). Here, inspired by the principle of galvanic cells, we report a generalized spontaneous strategy involving the growth of Cu on Mc ((-) bulk Cu(s) | Cu2+(c) | monolayer Cu/M(s) (+)) and the displacement of Cu by Pt (Cu + PtCl42- = Pt + Cu2+ + 4Cl-) to synthesize McPtqms. Exemplified by PdcPtqms, we demonstrate that this method requires no special control, electrochem. equipment, or reducing/stabilizing agents, which allows for the scalable prepn. of McPtqms. Meanwhile, it is able to produce homogeneous Ptqms, leading to high electrocatalytic activity for the ORR. This work paves the way for the practical application of McPtqms in electrocatalytic and related fields.
- 14Kanady, J. S.; Leidinger, P.; Haas, A.; Titlbach, S.; Schunk, S.; Schierle-Arndt, K.; Crumlin, E. J.; Wu, C. H.; Alivisatos, A. P. Synthesis of Pt3Y and Other Early-Late Intermetallic Nanoparticles by Way of a Molten Reducing Agent. J. Am. Chem. Soc. 2017, 139, 5672– 5675, DOI: 10.1021/jacs.7b01366Google Scholar14https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC2sXlt1yqsr0%253D&md5=a0c0235879d77d4062f930f47004e36cSynthesis of Pt3Y and Other Early-Late Intermetallic Nanoparticles by Way of a Molten Reducing AgentKanady, Jacob S.; Leidinger, Peter; Haas, Andreas; Titlbach, Sven; Schunk, Stephan; Schierle-Arndt, Kerstin; Crumlin, Ethan J.; Wu, Cheng Hao; Alivisatos, A. PaulJournal of the American Chemical Society (2017), 139 (16), 5672-5675CODEN: JACSAT; ISSN:0002-7863. (American Chemical Society)Early-late intermetallic phases have garnered increased attention recently for their catalytic properties. To achieve the high surface areas needed for industrially relevant applications, these phases must be synthesized as nanoparticles in a scalable fashion. Herein, Pt3Y-targeted as a prototypical example of an early-late intermetallic-was synthesized as nanoparticles ∼5-20 nm in diam. via a soln. process and characterized by XRD, TEM, EDS, and XPS. The key development is the use of a molten borohydride (MEt3BH, M = Na, K) as both the reducing agent and reaction medium. Readily available halide precursors of the two metals were used. Accordingly, no org. ligands are necessary, as the resulting halide salt byproduct prevents sintering, which further permits dispersion of the nanoscale intermetallic onto a support. The versatility of this approach was validated by the synthesis of other intermetallic phases such as Pt3Sc, Pt3Lu, Pt2Na, and Au2Y.
- 15Poerwoprajitno, A. R.; Gloag, L.; Cheong, S.; Gooding, J. J.; Tilley, R. D. Synthesis of low- and high-index faceted metal (Pt, Pd, Ru, Ir, Rh) nanoparticles for improved activity and stability in electrocatalysis. Nanoscale 2019, 11, 18995– 19011, DOI: 10.1039/C9NR05802HGoogle Scholar15https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC1MXhsFamu7%252FJ&md5=62ec9cb407d935044e286d84c17e850fSynthesis of low- and high-index faceted metal (Pt, Pd, Ru, Ir, Rh) nanoparticles for improved activity and stability in electrocatalysisPoerwoprajitno, Agus R.; Gloag, Lucy; Cheong, Soshan; Gooding, J. Justin; Tilley, Richard D.Nanoscale (2019), 11 (41), 18995-19011CODEN: NANOHL; ISSN:2040-3372. (Royal Society of Chemistry)A review. Driven by the quest for future energy soln., faceted metal nanoparticles are being pursued as the next generation electrocatalysts for renewable energy applications. Thanks to recent advancement in soln. phase synthesis, different low- and high-index facets on metal nanocrystals become accessible and are tested for specific electrocatalytic reactions. This minireview summarises the key approaches to prep. nanocrystals contg. the most catalytically active platinum group metals (Pt, Pd, Ru, Ir and Rh) exposed with low- and high-index facets using soln. phase synthesis. Electrocatalytic studies related to the different facets are highlighted to emphasize the importance of exposing facets for catalyzing these reactions, namely oxygen redn. reaction (ORR), hydrogen oxidn. reaction (HOR), alc. oxidn. including methanol (MOR) and ethanol oxidn. reactions (EOR), formic acid oxidn. reaction (FAOR), oxygen evolution reaction (OER), and hydrogen evolution reaction (HER). The future outlook discusses the challenges and opportunities for making electrocatalysts that are even more active and stable.
- 16Li, J.; Sharma, S.; Liu, X.; Pan, Y.-T.; Spendelow, J. S.; Chi, M.; Jia, Y.; Zhang, P.; Cullen, D. A.; Xi, Z.; Lin, H.; Yin, Z.; Shen, B.; Muzzio, M.; Yu, C.; Kim, Y. S.; Peterson, A. A.; More, K. L.; Zhu, H.; Sun, S. Hard-Magnet L10-CoPt Nanoparticles Advance Fuel Cell Catalysis. Joule 2019, 3, 124– 135, DOI: 10.1016/j.joule.2018.09.016Google Scholar16https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC1MXhsValtb8%253D&md5=97f930a346cafb0cd05b33c5e21133adHard-Magnet L10-CoPt Nanoparticles Advance Fuel Cell CatalysisLi, Junrui; Sharma, Shubham; Liu, Xiaoming; Pan, Yung-Tin; Spendelow, Jacob S.; Chi, Miaofang; Jia, Yukai; Zhang, Peng; Cullen, David A.; Xi, Zheng; Lin, Honghong; Yin, Zhouyang; Shen, Bo; Muzzio, Michelle; Yu, Chao; Kim, Yu Seung; Peterson, Andrew A.; More, Karren L.; Zhu, Huiyuan; Sun, ShouhengJoule (2019), 3 (1), 124-135CODEN: JOULBR; ISSN:2542-4351. (Cell Press)Stabilizing transition metals (M) in MPt alloy under acidic conditions is challenging, yet crucial to boost Pt catalysis toward oxygen redn. reaction (ORR). We synthesized ∼9 nm hard-magnet core/shell L10-CoPt/Pt nanoparticles with 2-3 at. layers of strained Pt shell for ORR. At 60°C in acid, the hard-magnet L10-CoPt better stabilizes Co (5% loss after 24 h) than soft-magnet A1-CoPt (34% loss in 7 h). L10-CoPt/Pt achieves mass activities (MA) of 0.56 A/mgPt initially and 0.45 A/mgPt after 30,000 voltage cycles in the membrane electrode assembly at 80°C, exceeding the DOE 2020 targets on Pt activity and durability (0.44 A/mgPt in MA and <40% loss in MA after 30,000 cycles). D. functional theory calcns. suggest that the ligand effect of Co and the biaxial strain (-4.50%/-4.25%) of the Pt shell weaken the binding of oxygenated species, leading to enhanced ORR performance in fuel cells.
- 17Liu, J.; Li, W.; Cheng, R.; Wu, Q.; Zhao, J.; He, D.; Mu, S. Stabilizing Pt Nanocrystals Encapsulated in N-Doped Carbon as Double-Active Sites for Catalyzing Oxygen Reduction Reaction. Langmuir 2019, 35, 2580– 2586, DOI: 10.1021/acs.langmuir.8b03947Google Scholar17https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC1MXitVCgs74%253D&md5=e93c86b2039325e39140652d2e18cab4Stabilizing Pt Nanocrystals Encapsulated in N-Doped Carbon as Double-Active Sites for Catalyzing Oxygen Reduction ReactionLiu, Jing; Li, Wenqiang; Cheng, Ruilin; Wu, Qian; Zhao, Jiahuan; He, Daping; Mu, ShichunLangmuir (2019), 35 (7), 2580-2586CODEN: LANGD5; ISSN:0743-7463. (American Chemical Society)Polypropylene fiber, a cheap source of N-doped C, is introduced to design robust N-doped C-encapsulated small Pt nanocrystals with Pt and N-C double-active centers toward O redn. reaction (ORR). Ascribed to the sepn. effect of the polypropylene fiber, even suffering from a high-temp. carbonization treatment at 720° for 90 min, the polypropylene fiber-derived C-encapsulated Pt nanocrystal maintains a small particle size (3 nm diam. on av.). As expected, its ORR mass activity is up to 116.5 mA/mg at 0.9 V. After 8000 cycles, the half-wave potential of the prepd. catalyst declines only by 14 mV compared with 43 mV for the com. Pt/C catalyst. The significantly improved electrochem. properties of the as-prepd. catalyst are resulted from the N-doped C-encapsulated Pt nanocrystal structure, which is benefited to adsorption and activation of O due to the presence of N-doped C as the important active site for ORR besides Pt metal. The migration, aggregation, and growth of Pt nanoparticles are prohibited in terms of the outer N-doped C protection layer, greatly enhancing the stability of the catalyst.
- 18Zaleska-Medynska, A.; Marchelek, M.; Diak, M.; Grabowska, E. Noble metal-based bimetallic nanoparticles: the effect of the structure on the optical, catalytic and photocatalytic properties. Adv. Colloid Interface Sci. 2016, 229, 80– 107, DOI: 10.1016/j.cis.2015.12.008Google Scholar18https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC2MXitFSnurjN&md5=93e47260901e2fd7aed43988c16d3e3eNoble metal-based bimetallic nanoparticles: the effect of the structure on the optical, catalytic and photocatalytic propertiesZaleska-Medynska, Adriana; Marchelek, Martyna; Diak, Magdalena; Grabowska, EwelinaAdvances in Colloid and Interface Science (2016), 229 (), 80-107CODEN: ACISB9; ISSN:0001-8686. (Elsevier B.V.)Nanoparticles composed of two different metal elements show novel electronic, optical, catalytic or photocatalytic properties from monometallic nanoparticles. Bimetallic nanoparticles could show not only the combination of the properties related to the presence of two individual metals, but also new properties due to a synergy between two metals. The structure of bimetallic nanoparticles can be oriented in random alloy, alloy with an intermetallic compd., cluster-in-cluster or core-shell structures and is strictly dependent on the relative strengths of metal-metal bond, surface energies of bulk elements, relative at. sizes, prepn. method and conditions, etc. In this review, selected properties, such as structure, optical, catalytic and photocatalytic of noble metals-based bimetallic nanoparticles, are discussed together with prepn. routes. The effects of prepn. method conditions as well as metal properties on the final structure of bimetallic nanoparticles (from alloy to core-shell structure) are followed. The role of bimetallic nanoparticles in heterogeneous catalysis and photocatalysis are discussed. Furthermore, structure and optical characteristics of bimetallic nanoparticles are described in relation to the some features of monometallic NPs. Such a complex approach allows to systematize knowledge and to identify the future direction of research.
- 19Li, R.; Wei, Z.; Huang, T.; Yu, A. Ultrasonic-assisted synthesis of Pd-Ni alloy catalysts supported on multi-walled carbon nanotubes for formic acid electrooxidation. Electrochim. Acta 2011, 56, 6860– 6865, DOI: 10.1016/j.electacta.2011.05.097Google Scholar19https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC3MXovFaksbo%253D&md5=86f7fb99cb21d6d29fa4aa4d014c6049Ultrasonic-assisted synthesis of Pd-Ni alloy catalysts supported on multi-walled carbon nanotubes for formic acid electrooxidationLi, Ruoshi; Wei, Zhen; Huang, Tao; Yu, AishuiElectrochimica Acta (2011), 56 (19), 6860-6865CODEN: ELCAAV; ISSN:0013-4686. (Elsevier Ltd.)Pd-Ni alloys with different compns. (i.e. Pd2Ni, PdNi, PdNi2) dispersed on multi-walled C nanotubes (MWCNTs) were prepd. by ultrasonic-assisted chem. redn. The XRD patterns indicate that all Pd and Pd-Ni nanoparticles exist as Pd fcc. structure, while Ni alloys with Pd. The TEM images show the addn. of Ni decreases the particle size and improves the dispersion. The XPS spectra demonstrate the electronic modification of Pd by Ni doping. The electrochem. measurements reveal that the PdNi catalysts have better catalytic activity and stability for formic acid electrooxidn., among them PdNi/MWCNTs is the best. The performance enhancement is ascribed to the increase of electroactive surface area (EASA) and Ni doping effect which might modify the electronic structure.
- 20Qin, F.; Ma, Y.; Miao, L.; Wang, Z.; Gan, L. Influence of Metal-Ligand Coordination on the Elemental Growth and Alloying Composition of Pt-Ni Octahedral Nanoparticles for Oxygen Reduction Electrocatalysis. ACS Omega 2019, 4, 8305– 8311, DOI: 10.1021/acsomega.8b03366Google Scholar20https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC1MXptVGhsbk%253D&md5=5368e0521da9b76486586463299dae29Influence of Metal-Ligand Coordination on the Elemental Growth and Alloying Composition of Pt-Ni Octahedral Nanoparticles for Oxygen Reduction ElectrocatalysisQin, Fei; Ma, Yangbo; Miao, Linqin; Wang, Zhongxiang; Gan, LinACS Omega (2019), 4 (5), 8305-8311CODEN: ACSODF; ISSN:2470-1343. (American Chemical Society)Understanding the role of surfactants or ligands on the growth mechanism of metal/alloy nanoparticles (NPs) is important for controlled synthesis of functional metallic NPs with tailored structures and properties. There were nos. of works showing the significant impact of surfactants/ligands on the shape-controlled synthesis of nanocrystals with well-defined surfaces. Beyond the morphol. shape control, impact of the surfactants/ligands on the alloying structure of bimetallic nanocrystals still remains largely unaddressed. A significant effect of HOBz ligand on the elemental growth and alloying phase structure of octahedral Pt-Ni NPs, a class of highly active electrocatalyst for O redn. reaction in fuel cells, is revealed. Contrary to previous reports showing the crit. role of HOBz in directing the growth of octahedral Pt-Ni NPs, HOBz played a minor role in forming the octahedral shape; instead, it can strongly coordinate with Ni cation and significantly slows down its redn. rate, leading to a phase sepn. in the Pt-Ni NP products (a mixt. of Pt-rich octahedral NPs and nearly pure Ni NPs). Such phase sepn. further resulted in a lower catalytic activity and stability. These results help one comprehensively understand the effect of metal-ligand coordination chem. on the elemental growth mechanism and alloying phase structure of bimetallic nanoparticles, complementing previous emphasis on the role of surfactants in purely morphol. shape control.
- 21Wegener, E. C.; Wu, Z.; Tseng, H.-T.; Gallagher, J. R.; Ren, Y.; Diaz, R. E.; Ribeiro, F. H.; Miller, J. T. Structure and reactivity of Pt-In intermetallic alloy nanoparticles: Highly selective catalysts for ethane dehydrogenation. Catal. Today 2018, 299, 146– 153, DOI: 10.1016/j.cattod.2017.03.054Google Scholar21https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC2sXmtFGntbo%253D&md5=ac6e07b5286f27e6bc164955c2ebebc9Structure and reactivity of Pt-In intermetallic alloy nanoparticles: Highly selective catalysts for ethane dehydrogenationWegener, Evan C.; Wu, Zhenwei; Tseng, Han-Ting; Gallagher, James R.; Ren, Yang; Diaz, Rosa E.; Ribeiro, Fabio H.; Miller, Jeffrey T.Catalysis Today (2018), 299 (), 146-153CODEN: CATTEA; ISSN:0920-5861. (Elsevier B.V.)The structure of silica supported Pt and Pt-In bimetallic catalysts with nominal In:Pt at. ratios of 0.7 and 1.4 were detd. by in situ synchrotron XAS and XRD. It was seen that the addn. of In led to the formation of two different intermetallic alloy phases. At an In:Pt ratio of 0.7 the Pt3In phase with a Cu3Au structure was formed. When the ratio was increased to 1.4 a shell of PtIn2 having a CaF2 structure formed around a core of Pt3In. The catalysts were tested for ethane dehydrogenation at 600 °C to det. the effect of alloying on ethylene selectivity and turnover rate (TOR). The monometallic Pt catalysts was 73% selective for ethylene and had an initial TOR of 0.7 s-1. Both alloy catalysts were ≈100% selective for dehydrogenation and had higher initial TOR, 2.8 s-1 and 1.6 s-1 for In:Pt ratio of 0.7 and 1.4, resp. The increase in selectivity is attributed to the elimination of large Pt ensembles resulting from geometric changes to the catalyst surface upon alloying. Electronic changes due to the formation of Pt-In bonds are thought to be responsible for the increases in TOR in the alloy catalysts.
- 22Zhang, L.; Roling, L. T.; Wang, X.; Vara, M.; Chi, M.; Liu, J.; Choi, S.-I.; Park, J.; Herron, J. A.; Xie, Z.; Mavrikakis, M.; Xia, Y. Platinum-based nanocages with subnanometer-thick walls and well-defined, controllable facets. Science 2015, 349, 412– 416, DOI: 10.1126/science.aab0801Google Scholar22https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC2MXhtF2mtr%252FI&md5=15174b6852405ed48717c20f1c81012dPlatinum-based nanocages with subnanometer-thick walls and well-defined, controllable facetsZhang, Lei; Roling, Luke T.; Wang, Xue; Vara, Madeline; Chi, Miaofang; Liu, Jingyue; Choi, Sang-Il; Park, Jinho; Herron, Jeffrey A.; Xie, Zhaoxiong; Mavrikakis, Manos; Xia, YounanScience (Washington, DC, United States) (2015), 349 (6246), 412-416CODEN: SCIEAS; ISSN:0036-8075. (American Association for the Advancement of Science)A cost-effective catalyst should have a high dispersion of the active atoms, together with a controllable surface structure for the optimization of activity, selectivity, or both. We fabricated nanocages by depositing a few at. layers of platinum (Pt) as conformal shells on palladium (Pd) nanocrystals with well-defined facets and then etching away the Pd templates. D. functional theory calcns. suggest that the etching is initiated via a mechanism that involves the formation of vacancies through the removal of Pd atoms incorporated into the outermost layer during the deposition of Pt. With the use of Pd nanoscale cubes and octahedra as templates, we obtained Pt cubic and octahedral nanocages enclosed by {100} and {111} facets, resp., which exhibited distinctive catalytic activities toward oxygen redn.
- 23Torimoto, T.; Okazaki, K.-i.; Kiyama, T.; Hirahara, K.; Tanaka, N.; Kuwabata, S. Sputter deposition onto ionic liquids: Simple and clean synthesis of highly dispersed ultrafine metal nanoparticles. Appl. Phys. Lett. 2006, 89, 243117, DOI: 10.1063/1.2404975Google Scholar23https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BD2sXislGqtA%253D%253D&md5=f5c381c5f8fdb8dc8193db838a20c8b5Sputter deposition onto ionic liquids: Simple and clean synthesis of highly dispersed ultrafine metal nanoparticlesTorimoto, Tsukasa; Okazaki, Ken-ichi; Kiyama, Tomonori; Hirahara, Kaori; Tanaka, Nobuo; Kuwabata, SusumuApplied Physics Letters (2006), 89 (24), 243117/1-243117/3CODEN: APPLAB; ISSN:0003-6951. (American Institute of Physics)Sputter deposition of gold (Au) onto ionic liqs. (ILs) gave highly dispersed Au nanoparticles without addnl. chem. species, such as reducing and/or stabilizing agents. The Au nanoparticles in 1-ethyl-3-methylimidazolium tetrafluoroborate had an av. diam. (dav) of 5.5 nm with a std. deviation (σ) of 0.86 nm, while sputter deposition onto N,N,N-trimethyl-N-propylammonium bis(trifluoromethanesulfonyl)imide gave much smaller Au nanoparticles with dav of 1.9 nm and σ of 0.46 nm. Prolongation of sputtering time results in a higher concn. of Au nanoparticles in ILs, but did not cause a remarkable change in their size.
- 24Tsuda, T.; Yoshii, K.; Torimoto, T.; Kuwabata, S. Oxygen reduction catalytic ability of platinum nanoparticles prepared by room-temperature ionic liquid-sputtering method. J. Power Sources 2010, 195, 5980– 5985, DOI: 10.1016/j.jpowsour.2009.11.027Google Scholar24https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC3cXmtlGhsbg%253D&md5=c099a8d988636c66899e64c983c6229bOxygen reduction catalytic ability of platinum nanoparticles prepared by room-temperature ionic liquid-sputtering methodTsuda, Tetsuya; Yoshii, Kazuki; Torimoto, Tsukasa; Kuwabata, SusumuJournal of Power Sources (2010), 195 (18), 5980-5985CODEN: JPSODZ; ISSN:0378-7753. (Elsevier B.V.)Pt nanoparticles can be produced by a Pt sputtering method onto trimethyl-n-propylammonium bis((trifluoromethyl)sulfonyl)amide (Me3PrNTf2N) room-temp. ionic liq. (RTIL) without stabilizing agents. Pt nanoparticles obtained by the Pt sputtering method showed mean particle size of ∼2.3-2.4 nm independently of sputtering time. A Pt-embedded glassy C electrode (Pt-GCE) consisting of the Pt-sputtered RTIL and a glassy C plate showed a favorable catalytic activity to oxygen redn. reaction. The catalytic ability was enhanced by Me3PrNTf2N modification of the Pt-GCE. CO never absorbed onto the RTIL-modified Pt-GCE.
- 25Yoshii, K.; Tsuda, T.; Arimura, T.; Imanishi, A.; Torimoto, T.; Kuwabata, S. Platinum nanoparticle immobilization onto carbon nanotubes using Pt-sputtered room-temperature ionic liquid. RSC Adv. 2012, 2, 8262– 8264, DOI: 10.1039/c2ra21243aGoogle Scholar25https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC38Xht1yks7%252FI&md5=bb7ef9ed2fddff2a1eb8e54037f40fdfPlatinum nanoparticle immobilization onto carbon nanotubes using Pt-sputtered room-temperature ionic liquidYoshii, Kazuki; Tsuda, Tetsuya; Arimura, Takashi; Imanishi, Akihito; Torimoto, Tsukasa; Kuwabata, SusumuRSC Advances (2012), 2 (22), 8262-8264CODEN: RSCACL; ISSN:2046-2069. (Royal Society of Chemistry)Establishment of a facile Pt nanoparticle-SWCNT composite fabrication method that never requires a laborious pretreatment of SWCNTs or any chem. reagent was achieved by using Pt-sputtered RTILs.
- 26Izumi, R.; Yao, Y.; Tsuda, T.; Torimoto, T.; Kuwabata, S. Oxygen reduction electrocatalysts sophisticated by using Pt nanoparticle-dispersed ionic liquids with electropolymerizable additives. J. Mater. Chem. A 2018, 6, 11853– 11862, DOI: 10.1039/C8TA03465FGoogle Scholar26https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC1cXhtVGgurzI&md5=1c672084af27ed8734e9eca4426e8c46Oxygen reduction electrocatalysts sophisticated by using Pt nanoparticle-dispersed ionic liquids with electropolymerizable additivesIzumi, Reiko; Yao, Yu; Tsuda, Tetsuya; Torimoto, Tsukasa; Kuwabata, SusumuJournal of Materials Chemistry A: Materials for Energy and Sustainability (2018), 6 (25), 11853-11862CODEN: JMCAET; ISSN:2050-7496. (Royal Society of Chemistry)The electropolymn. reaction of protic org. salt (POS) diphenylammonium hydrogen sulfate ([DPA][HSO4]) in the solid state proceeds in a N2-satd. 0.1 M HClO4 aq. soln., and conductive poly(diphenylamine) is formed without difficulty. This reaction has also been obsd. at the thin ionic liq. (IL) layer between Pt nanoparticles and carbon support on Pt nanoparticle-modified carbon electrocatalysts prepd. using a N,N-diethyl-N-methylammonium hydrogen sulfate ([DEMA][HSO4]) protic IL with a [DPA][HSO4] POS. Similar Pt nanoparticle electrocatalysts are fabricated using different electropolymerizable additives, including phenylammonium hydrogen sulfate ([PhNH3][HSO4]). A local electropolymn. reaction at the IL layer can confer a better electrochem. surface area and mass activity retention rates on oxygen redn. electrocatalysts. The performance of the resulting electrocatalysts is dependent on the electropolymerizable species.
- 27Yao, Y.; Izumi, R.; Tsuda, T.; Oshima, Y.; Imanishi, A.; Oda, N.; Kuwabata, S. Platinum and PtNi nanoparticle-supported multiwalled carbon nanotube electrocatalysts prepared by one-pot pyrolytic synthesis with an ionic liquid. ACS Appl. Energy Mater. 2019, 2, 4865– 4872, DOI: 10.1021/acsaem.9b00561Google Scholar27https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC1MXhtFWqs77K&md5=daef508fa4a5bfe5d611212fd1278cddPlatinum and PtNi Nanoparticle-Supported Multiwalled Carbon Nanotube Electrocatalysts Prepared by One-Pot Pyrolytic Synthesis with an Ionic LiquidYao, Yu; Izumi, Reiko; Tsuda, Tetsuya; Oshima, Yoshifumi; Imanishi, Akihito; Oda, Naoko; Kuwabata, SusumuACS Applied Energy Materials (2019), 2 (7), 4865-4872CODEN: AAEMCQ; ISSN:2574-0962. (American Chemical Society)Pt and PtNi alloy nanoparticle-supported multiwalled C nanotubes (Pt/MWCNTs and PtNi/MWCNTs) were prepd. by a 1-pot pyrolysis method with the N,N,N-trimethyl-N-propylammonium bis(trifluoromethanesulfonyl)amide ionic liq. (IL) contg. Pt and Ni precursors, Pt(acac)2, Ni[Tf2N]2, and Ni(acac)2, with suspended MWCNTs. The composite materials can be prepd. by simply heating the IL soln. at 573 K. The resulting materials show favorable catalytic activity toward the O redn. reaction and durability superior to those of typical com. available electrocatalysts. The catalytic activity of the PtNi/MWCNTs depends on the Ni content of the PtNi alloy nanoparticles. One of the PtNi/MWCNTs shows 1.4 times higher mass activity than a typical com. electrocatalyst. A plot of the mass activity as a function of the Ni content gives a mountain-shaped curve with a vertex at ∼25 at percent Ni. This 1-pot process can readily control the catalytic properties of the PtNi/MWCNTs by changing the molar fraction of Pt and Ni precursors.
- 28Kusada, K.; Kobayashi, H.; Ikeda, R.; Kubota, Y.; Takata, M.; Toh, S.; Yamamoto, T.; Matsumura, S.; Sumi, N.; Sato, K.; Nagaoka, K.; Kitagawa, H. Solid Solution Alloy Nanoparticles of Immiscible Pd and Ru Elements Neighboring on Rh: Changeover of the Thermodynamic Behavior for Hydrogen Storage and Enhanced CO-Oxidizing Ability. J. Am. Chem. Soc. 2014, 136, 1864– 1871, DOI: 10.1021/ja409464gGoogle Scholar28https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC2cXht1eitb0%253D&md5=aca030edfa0e4dca5dc64b8282defb10Solid Solution Alloy Nanoparticles of Immiscible Pd and Ru Elements Neighboring on Rh: Changeover of the Thermodynamic Behavior for Hydrogen Storage and Enhanced CO-Oxidizing AbilityKusada, Kohei; Kobayashi, Hirokazu; Ikeda, Ryuichi; Kubota, Yoshiki; Takata, Masaki; Toh, Shoichi; Yamamoto, Tomokazu; Matsumura, Syo; Sumi, Naoya; Sato, Katsutoshi; Nagaoka, Katsutoshi; Kitagawa, HiroshiJournal of the American Chemical Society (2014), 136 (5), 1864-1871CODEN: JACSAT; ISSN:0002-7863. (American Chemical Society)PdxRu1-x solid soln. alloy nanoparticles were successfully synthesized over the whole compn. range through a chem. redn. method, although Ru and Pd are immiscible at the at. level in the bulk state. From the XRD measurement, it was found that the dominant structure of PdxRu1-x changes from fcc to hcp with increasing Ru content. The structures of PdxRu1-x nanoparticles in the Pd compn. range of 30-70% consisted of both solid soln. fcc and hcp structures, and both phases coexist in a single particle. In addn., the reaction of hydrogen with the PdxRu1-x nanoparticles changed from exothermic to endothermic as the Ru content increased. Furthermore, the prepd. PdxRu1-x nanoparticles demonstrated enhanced CO-oxidizing catalytic activity; Pd0.5Ru0.5 nanoparticles exhibit the highest catalytic activity. This activity is much higher than that of the practically used CO-oxidizing catalyst Ru and that of the neighboring Rh, between Ru and Pd.
- 29Fan, C.; Wang, G.; Zou, L.; Fang, J.; Zou, Z.; Yang, H. Composition- and shape-controlled synthesis of the PtNi alloy nanotubes with enhanced activity and durability toward oxygen reduction reaction. J. Power Sources 2019, 429, 1– 8, DOI: 10.1016/j.jpowsour.2019.04.073Google Scholar29https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC1MXovVCku7g%253D&md5=8a1148a96923a70f0e293ee14ce3c945Composition- and shape-controlled synthesis of the PtNi alloy nanotubes with enhanced activity and durability toward oxygen reduction reactionFan, Chuanting; Wang, Guoliang; Zou, Liangliang; Fang, Jianhui; Zou, Zhiqing; Yang, HuiJournal of Power Sources (2019), 429 (), 1-8CODEN: JPSODZ; ISSN:0378-7753. (Elsevier B.V.)The development of the fuel cell catalysts with high durability and high activity for oxygen reaction redn. remains a great challenge. Various material designs such as alloys, core@shell structure and shape control provide the promising ways to improve the electrocatalytic performance. Herein, on the basis of both the alloy effect and the nanotube structure effect, we demonstrate a high-performance PtNi alloy catalyst with one-dimensional nanotube structure via a galvanic replacement reaction combined with Kirkendall effect. Meanwhile, the PtNi alloy phase and the tube structure are selectively controlled by tuning the PtNi at. ratio and the wall thickness of the nanotube, resp. Subsequently, the understanding of the compn. effect and the shape effect on the activity and the durability is systematically investigated. The optimized PtNi nanotube catalyst shows significant improvements on the activity (6.2-fold increase in specific activity compared to the com. Pt/C) and the durability (only 8.6% loss in mass activity after 10000 cycles), attributing to the alloy effect by introducing Ni to the Pt lattice, the Pt-rich surface and the shape effect of the unique one-dimensional hollow tube structure.
- 30Liu, Y.; Kou, W.; Li, X.; Huang, C.; Shui, R.; He, G. Constructing Patch-Ni-Shelled Pt@Ni Nanoparticles within Confined Nanoreactors for Catalytic Oxidation of Insoluble Polysulfides in Li-S Batteries. Small 2019, 15, 1902431, DOI: 10.1002/smll.201902431Google ScholarThere is no corresponding record for this reference.
- 31Qi, X.; Li, X.; Chen, B.; Lu, H.; Wang, L.; He, G. Highly Active Nanoreactors: Patchlike or Thick Ni Coating on Pt Nanoparticles Based on Confined Catalysis. ACS Appl. Mater. Interfaces 2016, 8, 1922– 1928, DOI: 10.1021/acsami.5b10083Google Scholar31https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC28XhtlSrsw%253D%253D&md5=f72cf59f9344a09073ef8925225571eaHighly Active Nanoreactors: Patchlike or Thick Ni Coating on Pt Nanoparticles Based on Confined CatalysisQi, Xinhong; Li, Xiangcun; Chen, Bo; Lu, Huilan; Wang, Le; He, GaohongACS Applied Materials & Interfaces (2016), 8 (3), 1922-1928CODEN: AAMICK; ISSN:1944-8244. (American Chemical Society)Catalyst-contg. nanoreactors have attracted considerable attention for specific applications. Here, the authors initially report prepn. of PtNi@SiO2 hollow microspheres based on confined catalysis. The previous encapsulation of dispersed Pt nanoparticles (NPs) in hollow SiO2 microspheres ensures the formation of Pt@Ni coreshell NPs inside the SiO2 porous shell. Thus, the Pt NPs not only catalyze the redn. of Ni ions but also direct Ni deposition on the Pt cores to obtain Pt@Ni core-shell catalyst. It is worthy to point out that this synthetic approach helps to form a patchlike or thick Ni coating on Pt cores by controlling the penetration time of Ni ions from the bulk soln. into the SiO2 microspheres (0.5, 1, 2, or 4 h). Notably, the Pt@Ni core-shell NPs with a patch-like Ni layer on Pt cores (0.5 and 1 h) show a higher H2 generation rate of 1221 - 1475 H2 mL min-1 g-1cat than the Pt@Ni NPs with a thick Ni layer (2 and 4 h, 920 - 1183 H2 mL min-1 g-1cat), and much higher than that of pure Pt NPs (224 H2 mL min-1 g-1cat). The catalyst possesses good stability and recyclability for H2 generation. The Pt@Ni core-shell NPs confined inside SiO2 nanocapsules, with well-defined compns. and morphologies, high H2 generation rate, and recyclability, should be an ideal catalyst for specific applications in liq. phase reaction.
- 32Okamoto, H. Phase Digrams for Binary Alloys; 2nd ed.; ASM International: Materials Park, OH, 2010.Google ScholarThere is no corresponding record for this reference.
- 33Garsany, Y.; Baturina, O. A.; Swider-Lyons, K. E.; Kocha, S. S. Experimental Methods for Quantifying the Activity of Platinum Electrocatalysts for the Oxygen Reduction Reaction. Anal. Chem. 2010, 82, 6321– 6328, DOI: 10.1021/ac100306cGoogle Scholar33https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC3cXot1amsLw%253D&md5=b5a5f6d35a0bb9cced6a4d6797911590Experimental Methods for Quantifying the Activity of Platinum Electrocatalysts for the Oxygen Reduction ReactionGarsany, Yannick; Baturina, Olga A.; Swider-Lyons, Karen E.; Kocha, Shyam S.Analytical Chemistry (Washington, DC, United States) (2010), 82 (15), 6321-6328CODEN: ANCHAM; ISSN:0003-2700. (American Chemical Society)A review. A tutorial is provided for methods to accurately and reproducibly det. the activity of Pt-based electrocatalysts for the oxygen redn. in proton-exchange membrane fuel cells and other applications. The impact of various exptl. parameters on electrocatalyst activity if demonstrated and explicit exptl. procedures and measurement protocols are given for comparison of the electrocatalyst activity to fuel cell stds.
- 34Shinozaki, K.; Zack, J. W.; Richards, R. M.; Pivovar, B. S.; Kocha, S. S. Oxygen Reduction Reaction Measurements on Platinum Electrocatalysts Utilizing Rotating Disk Electrode Technique. J. Electrochem. Soc. 2015, 162, F1144– F1158, DOI: 10.1149/2.1071509jesGoogle Scholar34https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC2MXhtlOnur7I&md5=22846d5016b89ed7dd2fe27d7710070bOxygen Reduction Reaction Measurements on Platinum Electrocatalysts Utilizing Rotating Disk Electrode TechniqueShinozaki, Kazuma; Zack, Jason W.; Richards, Ryan M.; Pivovar, Bryan S.; Kocha, Shyam S.Journal of the Electrochemical Society (2015), 162 (10), F1144-F1158CODEN: JESOAN; ISSN:0013-4651. (Electrochemical Society)The rotating disk electrode (RDE) technique is being extensively used as a screening tool to est. the activity of novel PEMFC electrocatalysts synthesized in lab.-scale (mg) quantities. Discrepancies in measured activity attributable to glassware and electrolyte impurity levels, as well as conditioning, protocols and corrections are prevalent in the literature. The electrochem. response to a broad spectrum of com. sourced HClO4 and the effect of acid molarity on impurity levels and soln. resistance were also assessed. The authors' findings reveal that an area specific activity (SA) exceeding 2.0 mA/cm2 (20 mV/s, 25°, 100 kPa, 0.1 M HClO4) for polished poly-Pt is an indicator of impurity levels that do not impede the accurate measurement of the ORR activity of Pt based catalysts. After exploring various conditioning protocols to approach max. use of the electrochem. area (ECA) and peak ORR activity without introducing catalyst degrdn., a study of measurement protocols for ECA and ORR activity was conducted. Down-selected protocols were based on the criteria of reproducibility, duration of expts., impurity effects and magnitude of pseudo-capacitive background correction. Statistical reproducibility of ORR activity for poly-Pt and Pt supported on high surface area C was demonstrated.
- 35Earle, M. J.; Hakala, U.; McAuley, B. J.; Nieuwenhuyzen, M.; Ramani, A.; Seddon, K. R. Metal bis{(trifluoromethyl)sulfonyl}amide complexes: highly efficient Friedel-Crafts acylation catalysts. Chem. Commun. 2004, 1368– 1369, DOI: 10.1039/B403650FGoogle Scholar35https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BD2cXks1Sqsr4%253D&md5=b6a3ac125266824a00b886979e9e9d63Metal bis[(trifluoromethyl)sulfonyl]amide complexes: highly efficient Friedel-Crafts acylation catalystsEarle, Martyn J.; Hakala, Ullastiina; McAuley, Barry J.; Nieuwenhuyzen, Mark; Ramani, Alwar; Seddon, Kenneth R.Chemical Communications (Cambridge, United Kingdom) (2004), (12), 1368-1369CODEN: CHCOFS; ISSN:1359-7345. (Royal Society of Chemistry)The title complexes were evaluated as Friedel-Crafts acylation catalysts. These reactions were carried out in ionic liqs., which allows the catalysts to be recovered and reused.
- 36Katase, T.; Imashuku, S.; Murase, K.; Hirato, T.; Awakura, Y. Water content and related physical properties of aliphatic quaternary ammonium imide-type ionic liquid containing metal ions. Sci. Technol. Adv. Mater. 2006, 7, 502– 510, DOI: 10.1016/j.stam.2006.02.017Google Scholar36https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BD28XhtFWitbfJ&md5=17118994e86fafa2e6ee4b8e0f9890e9Water content and related physical properties of aliphatic quaternary ammonium imide-type ionic liquid containing metal ionsKatase, Takuma; Imashuku, Susumu; Murase, Kuniaki; Hirato, Tetsuji; Awakura, YasuhiroScience and Technology of Advanced Materials (2006), 7 (6), 502-510CODEN: STAMCV; ISSN:1468-6996. (Elsevier Ltd.)The ionic liq., trimethyl-n-hexylammonium bis((trifluoromethyl)sulfonyl)amide (TMHA-Tf2N), has a wide electrochem. window of more than 5 V and is considered to be hydrophobic because of two -CF3 groups in its Tf2N- anion. However, a small amt. of water remains in the ionic liq. even after dehydration in vacuo, which causes some problems in metal electrodeposition when using the ionic liq. as a solvent. We measured the water content of the ionic liqs., TMHA-Tf2N contg. M(Tf2N)n (M=H, Li, Mg, Ni, Cu, Zn, La, and Dy; n=1, 2, or 3), as well as their kinematic viscosity and elec. cond. in the temp. range of 25-130°C. Furthermore, differential scanning calorimetry was performed for these ionic liqs. to find their glass transition temp., crystn. temp., and melting temp. The water content of TMHA-Tf2N contg. M(Tf2N)n salts decreased with an increase in temp. At the same time, the kinematic viscosity decreased and the elec. cond. increased. By measuring the optical absorption spectrum, it was found that the metal ions in TMHA-Tf2N were hydrated. The addn. of M(Tf2N)n to TMHA-Tf2N, increased the water content at a const. temp., which resulted in slight increases in the kinematic viscosity and decrease in the elec. cond. A Walden-like plot of the elec. conductivities against the kinematic viscosities, measured over various temps. and water contents, gave a single straight line.
- 37Yamamoto, K.; Kolb, D. M.; Kötz, R.; Lehmpfuhl, G. Hydrogen Adsorption and Oxide Formation on Platinum Single-Crystal Electrodes. J. Electroanal. Chem. 1979, 96, 233– 239, DOI: 10.1016/S0022-0728(79)80380-0Google ScholarThere is no corresponding record for this reference.
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Abstract
Figure 1
Figure 1. Heating profile (black solid line) employed for the staircase heating process and TG measurement results of Pt(acac)2 (gray solid line), Ni[Tf2N]2 (red dashed line), and Ni(acac)2 (blue dash-dotted line) obtained using the staircase heating process. Samples were taken from the IL mixtures containing the metal precursors and MWCNTs at points A–L as shown on the top axis.
Figure 2
Figure 3
Figure 4
Figure 4. Ni contents of the nanoparticles deposited onto MWCNTs in the IL-MWCNT mixtures containing Pt(acac)2 and either Ni[Tf2N]2 (red solid line with solid square) or Ni(acac)2 (blue dashed line with open square). The Ni contents were determined using ICP-AES.
Figure 5
Figure 5. X-ray diffraction patterns of the PtNi/MWCNTs prepared with (a) Ni[Tf2N]2 or (b) Ni(acac)2. The sampling points and PtNi alloy nanoparticle compositions of the specimens are denoted on the graph.
Figure 6
Figure 6. Schematic illustration of plausible PtNi alloy formation mechanisms derived from the detailed analysis of the PtNi/MWCNTs prepared via the staircase heating process.
Figure 7
Figure 7. Cyclic voltammograms recorded using glassy carbon electrodes with PtNi/MWCNTs in a N2-saturated 0.1 M HClO4 aqueous solution. The Ni precursors used for preparing the PtNi/MWCNTs were either (a) Ni[Tf2N]2 or (b) Ni(acac)2. The sampling points during the staircase heating process were E (black dashed line), F (red dashed line), G (blue dashed line), H (green dashed line), I (black solid line), J (red solid line), K (blue solid line), and L (green solid line). The scan rate was 10 mV s–1.
Figure 8
Figure 8. Mean particle size (black solid square) and ECSA change (red solid square) of the PtNi nanoparticles in PtNi/MWCNTs prepared with either (a) Ni[Tf2N]2 or (b) Ni(acac)2. The sampling points taken during the staircase heating process are denoted on these figures.
Figure 9
Figure 9. Hydrodynamic voltammograms recorded at glassy carbon electrodes with the PtNi/MWCNTs and a commercially available Pt/C catalyst (gray dotted line) in an O2-saturated 0.1 M HClO4 aqueous solution. The Ni precursors used for preparing the PtNi/MWCNTs were (a) Ni[Tf2N]2 and (b) Ni(acac)2. The sampling points during the staircase heating process were E (black dashed line), F (red dashed line), G (blue dashed line), H (green dashed line), I (black solid line), J (red solid line), K (blue solid line), and L (green solid line). The revolution speeds were 1600 rpm. The scan rates were 10 mV s–1.
References
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- 1Huang, X.; Zhao, Z.; Cao, L.; Chen, Y.; Zhu, E.; Lin, Z.; Li, M.; Yan, A.; Zettl, A.; Wang, Y. M.; Duan, X.; Mueller, T.; Huang, Y. High-performance transition metal-doped Pt3Ni octahedra for oxygen reduction reaction. Science 2015, 348, 1230– 1234, DOI: 10.1126/science.aaa87651https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC2MXps1OltLw%253D&md5=b988fb9393a7e5d3709fbe54e8aa30acHigh-performance transition metal-doped Pt3Ni octahedra for oxygen reduction reactionHuang, Xiaoqing; Zhao, Zipeng; Cao, Liang; Chen, Yu; Zhu, Enbo; Lin, Zhaoyang; Li, Mufan; Yan, Aiming; Zettl, Alex; Wang, Y. Morris; Duan, Xiangfeng; Mueller, Tim; Huang, YuScience (Washington, DC, United States) (2015), 348 (6240), 1230-1234CODEN: SCIEAS; ISSN:0036-8075. (American Association for the Advancement of Science)Bimetallic platinum-nickel (Pt-Ni) nanostructures represent an emerging class of electrocatalysts for oxygen redn. reaction (ORR) in fuel cells, but practical applications were limited by catalytic activity and durability. The authors surface-doped Pt3Ni octahedra supported on carbon with transition metals, termed M-Pt3Ni/C, where M is vanadium, chromium, manganese, iron, cobalt, molybdenum (Mo), tungsten, or rhenium. The Mo-Pt3Ni/C showed the best ORR performance, with a specific activity of 10.3 mA/cm2 and mass activity of 6.98 A/mgPt, which are 81- and 73-fold enhancements compared with the com. Pt/C catalyst (0.127 mA/cm2 and 0.096 A/mgPt). Theor. calcns. suggest that Mo prefers subsurface positions near the particle edges in vacuum and surface vertex/edge sites in oxidizing conditions, where it enhances both the performance and the stability of the Pt3Ni catalyst.
- 2Čolić, V.; Bandarenka, A. S. Pt Alloy Electrocatalysts for the Oxygen Reduction Reaction: From Model Surfaces to Nanostructured Systems. ACS Catal. 2016, 6, 5378– 5385, DOI: 10.1021/acscatal.6b009972https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC28XhtFers7fJ&md5=924cebf9902cdb1b094a347a6c41d2ecPt Alloy Electrocatalysts for the Oxygen Reduction Reaction: From Model Surfaces to Nanostructured SystemsColic, Viktor; Bandarenka, Aliaksandr S.ACS Catalysis (2016), 6 (8), 5378-5385CODEN: ACCACS; ISSN:2155-5435. (American Chemical Society)A review. Polymer electrolyte membrane fuel cells are a promising alternative for future energy provision. However, their wider utilization is hindered by the slow rate of the oxygen redn. reaction (ORR) taking place at the cathode. In order to improve the ORR kinetics, alloys of Pt with late transition metals and lanthanides have been studied extensively, as they offer enhanced activity and in some cases acceptable stability. Nevertheless, many of these alloys are far from being "model objects"; and their surface compn. and structure are not stable under operating conditions in PEMFCs. The solute metal can dissolve from the surface and near-surface layers. This process often results in a structure in which several Pt-enriched layers cover the bulk alloy and protect it from further dissoln. In this work, we analyze the literature results on the properties of these alloys, from single crystals and polycryst. materials to nanoparticles, gathered in the recent decades. As a result of this anal., we addnl. propose a relatively simple method to overview the activities of dealloyed PtnX-type alloys toward the ORR. Given that the Pt overlayer is several at. layers thick, the so-called strain effects should primarily det. the behavior of these catalysts. The strain in the system is the result of the differences between the lattice parameters of the alloy and Pt-rich overlayers, causing dissimilar compressive strains in the lattice of the Pt-rich layer. This causes changes in the electronic structure and, consequently, in the binding properties of the surface. We propose that the at. radius of the solute metal can be used in some particularly complex systems (e.g., polycryst. and nanostructured alloys) as a simple semiempirical descriptor, statistically connected to the resulting lattice strain. The implications of this phenomenon can be used to qual. explain the behavior of e.g. some active Pt-alloy nanoparticles so far considered "anomalous".
- 3Wang, Y.-J.; Zhao, N.; Fang, B.; Li, H.; Bi, X. T.; Wang, H. Carbon-Supported Pt-Based Alloy Electrocatalysts for the Oxygen Reduction Reaction in Polymer Electrolyte Membrane Fuel Cells: Particle Size, Shape, and Composition Manipulation and Their Impact to Activity. Chem. Rev. 2015, 115, 3433– 3467, DOI: 10.1021/cr500519c3https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC2MXmsVSrtr0%253D&md5=a9b6cf1ed63cc892d7d681e348adf0f4Carbon-supported Pt-based alloy electrocatalysts for the oxygen redn. reaction in polymer electrolyte membrane fuel cells: particle size, shape, and compn. manipulation and their impact to activityWang, Yan-Jie; Zhao, Nana; Fang, Baizeng; Li, Hui; Bi, Xiaotao T.; Wang, HaijiangChemical Reviews (Washington, DC, United States) (2015), 115 (9), 3433-3467CODEN: CHREAY; ISSN:0009-2665. (American Chemical Society)A review. This review addresses the current development of size dependent, shape-selected, and compn.-controlled carbon supported Pt-alloy electrocatalysts for enhancing electrochem. catalytic performance in PEMFCs.
- 4Kuttiyiel, K. A.; Choi, Y.; Hwang, S.-M.; Park, G.-G.; Yang, T.-H.; Su, D.; Sasaki, K.; Liu, P.; Adzic, R. R. Enhancement of the oxygen reduction on nitride stabilized pt-M (M= Fe, Co, and Ni) core–shell nanoparticle electrocatalysts. Nano Energy 2015, 13, 442– 449, DOI: 10.1016/j.nanoen.2015.03.0074https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC2MXks1yktrc%253D&md5=1132a9bc23261e5cece061683f846724Enhancement of the oxygen reduction on nitride stabilized pt-M (M=Fe, Co, and Ni) core-shell nanoparticle electrocatalystsKuttiyiel, Kurian A.; Choi, YongMan; Hwang, Sun-Mi; Park, Gu-Gon; Yang, Tae-Hyun; Su, Dong; Sasaki, Kotaro; Liu, Ping; Adzic, Radoslav R.Nano Energy (2015), 13 (), 442-449CODEN: NEANCA; ISSN:2211-2855. (Elsevier Ltd.)Given the harsh operating conditions in hydrogen/oxygen fuel cells, the stability of catalysts is one of the crit. questions affecting their commercialization. We describe a distinct class of oxygen redn. (ORR) core-shell electrocatalysts comprised of nitride metal cores enclosed by thin Pt shells that is easily synthesized. The synthesis is reproducible and amenable to scale up. Our theor. anal. and the exptl. data indicate that metal nitride nanoparticle cores could significantly enhance the ORR activity as well as the durability of the core-shell catalysts as a consequence of combined geometrical, electronic and segregation effects on the Pt shells. In addn. to its fuel cells application, this class of catalysts holds promise to significantly contribute in resolving the problem of platinum scarcity and furthermore indicates the guidelines for future research and development.
- 5Escudero-Escribano, M.; Malacrida, P.; Hansen, M. H.; Vej-Hansen, U. G.; Velazquez-Palenzuela, A.; Tripkovic, V.; Schiøtz, J.; Rossmeisl, J.; Stephens, I. E. L.; Chorkendorff, I. Tuning the activity of Pt alloy electrocatalysts by means of the lanthanide contraction. Science 2016, 352, 73– 76, DOI: 10.1126/science.aad88925https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC28XlsFSmu7c%253D&md5=f59ab36fab568dfd01b4661f8282a8eeTuning the activity of Pt alloy electrocatalysts by means of the lanthanide contractionEscudero-Escribano, Maria; Malacrida, Paolo; Hansen, Martin H.; Vej-Hansen, Ulrik G.; Velazquez-Palenzuela, Amado; Tripkovic, Vladimir; Schiotz, Jakob; Rossmeisl, Jan; Stephens, Ifan E. L.; Chorkendorff, IbScience (Washington, DC, United States) (2016), 352 (6281), 73-76CODEN: SCIEAS; ISSN:0036-8075. (American Association for the Advancement of Science)The high platinum loadings required to compensate for the slow kinetics of the oxygen redn. reaction (ORR) impede the widespread uptake of low-temp. fuel cells in automotive vehicles. We have studied the ORR on eight platinum (Pt)-lanthanide and Pt-alk. earth electrodes, Pt5M, where M is lanthanum, cerium, samarium, gadolinium, terbium, dysprosium, thulium, or calcium. The materials are among the most active polycryst. Pt-based catalysts reported, presenting activity enhancement by a factor of 3 to 6 over Pt. The active phase consists of a Pt overlayer formed by acid leaching. The ORR activity vs. the bulk lattice parameter follows a high peaked "volcano" relation. We demonstrate how the lanthanide contraction can be used to control strain effects and tune the activity, stability, and reactivity of these materials.
- 6Shao, M.; Odell, J. H.; Peles, A.; Su, D. The role of transition metals in the catalytic activity of Pt alloys: quantification of strain and ligand effects. Chem. Commun. 2014, 50, 2173– 2176, DOI: 10.1039/c3cc47341d6https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC2cXhsFCnsLo%253D&md5=00b9dcedef30fab01bdb0e1386bd31c1The role of transition metals in the catalytic activity of Pt alloys: quantification of strain and ligand effectsShao, Minhua; Odell, Jonathan H.; Peles, Amra; Su, DongChemical Communications (Cambridge, United Kingdom) (2014), 50 (17), 2173-2176CODEN: CHCOFS; ISSN:1359-7345. (Royal Society of Chemistry)The oxygen redn. reaction (ORR) activity as a function of thickness of the Pt shell on Pt-Ni alloy nanoparticles was established. We demonstrated that the effects of transition metals could only extend to a very thin Pt shell, which was 0.9-1.0 nm for Pt3Ni.
- 7Asano, M.; Kawamura, R.; Sasakawa, R.; Todoroki, N.; Wadayama, T. Oxygen Reduction Reaction Activity for Strain-Controlled Pt-Based Model Alloy Catalysts: Surface Strains and Direct Electronic Effects Induced by Alloying Elements. ACS Catal. 2016, 6, 5285– 5289, DOI: 10.1021/acscatal.6b014667https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC28XhtFGjs73K&md5=a1b70c859dae994e151075285436d087Oxygen Reduction Reaction Activity for Strain-Controlled Pt-Based Model Alloy Catalysts: Surface Strains and Direct Electronic Effects Induced by Alloying ElementsAsano, Masato; Kawamura, Ryutaro; Sasakawa, Ren; Todoroki, Naoto; Wadayama, ToshimasaACS Catalysis (2016), 6 (8), 5285-5289CODEN: ACCACS; ISSN:2155-5435. (American Chemical Society)Surface strain and electronic interactions (i.e., strain and ligand effects) play key roles in enhancing the oxygen redn. reaction (ORR) catalytic activity of Pt-based alloy catalysts. Herein, we evaluate the ORR activity enhancement factors for Pt(111)-shell layers on Pt25Ni75(111) single-crystal surfaces prepd. by mol. beam epitaxy under ultrahigh vacuum (UHV). Scanning tunneling microscopy images of the pristine surfaces collected under UHV revealed periodic surface modulations, known as Moire patterns, suggesting that the topmost Pt(111)-shell layers are compressively strained by the influence of the underlying Ni atoms. The correlation between the ORR activities and estd. strains for 3-ML- and 4-ML-thick Pt shells (where ML represents monolayer), each having -1.7% and -1.2% strained Pt-shells, correspond well to the strain-based theory predictions. On the other hand, a 2-ML-thick Pt shell, with -2.8% strain, exhibits a remarkable ORR activity enhancement, i.e., 25 times higher than the pristine Pt(111): the enhancement factor anomalously deviates from the value predicted by the strain-based theory. Therefore, the activity enhancement of the 2-ML-thick Pt sample can be ascribed to a ligand effect induced by the Ni atoms just below the topmost Pt(111)-shell layer. The results obtained in this study provide a fundamental insight into the ORR activity enhancement mechanisms of Pt-based electrocatalysts.
- 8Tian, X.; Zhao, X.; Su, Y.-Q.; Wang, L.; Wang, H.; Dang, D.; Chi, B.; Liu, H.; Hensen, E. J. M.; Lou, X. W. D.; Xia, B. Y. Engineering bunched Pt-Ni alloy nanocages for efficient oxygen reduction in practical fuel cells. Science 2019, 366, 850– 856, DOI: 10.1126/science.aaw74938https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC1MXitFOnu7rK&md5=1bb23a5a32c576f8beea3b83a4925a8aEngineering bunched Pt-Ni alloy nanocages for efficient oxygen reduction in practical fuel cellsTian, Xinlong; Zhao, Xiao; Su, Ya-Qiong; Wang, Lijuan; Wang, Hongming; Dang, Dai; Chi, Bin; Liu, Hongfang; Hensen, Emiel J. M.; Lou, Xiong Wen; Xia, Bao YuScience (Washington, DC, United States) (2019), 366 (6467), 850-856CODEN: SCIEAS; ISSN:1095-9203. (American Association for the Advancement of Science)The expense and scarcity of platinum has driven efforts to improve oxygen-redn. catalysts in proton-exchange membrane fuel cells. Tian et al. synthesized chains of platinum-nickel alloy nanospheres connected by necking regions. These structures can be etched to form nanocages with platinum-rich surfaces that are highly active for oxygen redn. In fuel cells running on air and hydrogen, these catalysts operated for at least 180 h.
- 9Wang, W.; Wang, Z.; Wang, J.; Zhong, C.-J.; Liu, C.-J. Highly Active and Stable Pt-Pd Alloy Catalysts Synthesized by Room-Temperature Electron Reduction for Oxygen Reduction Reaction. Adv. Sci. 2017, 4, 1600486, DOI: 10.1002/advs.2016004869https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A280%3ADC%252BC1crgsVClsg%253D%253D&md5=4b4ec1338ffcf19f203b80afab5a56efHighly Active and Stable Pt-Pd Alloy Catalysts Synthesized by Room-Temperature Electron Reduction for Oxygen Reduction ReactionWang Wei; Wang Zongyuan; Wang Jiajun; Liu Chang-Jun; Zhong Chuan-JianAdvanced science (Weinheim, Baden-Wurttemberg, Germany) (2017), 4 (4), 1600486 ISSN:2198-3844.Carbon-supported platinum (Pt) and palladium (Pd) alloy catalyst has become a promising alternative electrocatalyst for oxygen reduction reaction (ORR) in proton exchange membrane fuel cells. In this work, the synthesis of highly active and stable carbon-supported Pt-Pd alloy catalysts is reported with a room-temperature electron reduction method. The alloy nanoparticles thus prepared show a particle size around 2.6 nm and a core-shell structure with Pt as the shell. With this structure, the breaking of O-O bands and desorption of OH are both promoted in electrocatalysis of ORR. In comparison with the commercial Pt/C catalyst prepared by conventional method, the mass activity of the Pt-Pd/C catalyst for ORR is shown to increase by a factor of ≈4. After 10 000-cycle durability test, the Pt-Pd/C catalyst is shown to retain 96.5% of the mass activity, which is much more stable than that of the commercial Pt/C catalyst.
- 10Burk, J. J.; Buratto, S. K. Electrodeposition of Pt Nanoparticle Catalysts from H2Pt(OH)6 and Their Application in PEM Fuel Cells. J. Phys. Chem. C 2013, 117, 18957– 18966, DOI: 10.1021/jp405302x10https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC3sXht12htL3L&md5=73f68f3bb358d63bae84bbdb125af0ebElectrodeposition of Pt Nanoparticle Catalysts from H2Pt(OH)6 and their Application in PEM Fuel CellsBurk, Jonathan J.; Buratto, Steven K.Journal of Physical Chemistry C (2013), 117 (37), 18957-18966CODEN: JPCCCK; ISSN:1932-7447. (American Chemical Society)The authors report the electrochem. deposition of Pt nanoparticles from platinic acid H2[Pt(OH)6] using pulse potential deposition (PPD). The authors are able to control the size, morphol., and loading of Pt nanoparticles from H2[Pt(OH)6] by controlling the deposition parameters such as the pH of the plating soln., the pulse potential, the pulse width, and the duty cycle of the pulse sequence. A high d. of Pt nanoparticles electrodeposited can be produced on both planar and nonplanar electrode supports with high surface area and high catalytic activity. Finally, fuel cell electrodes can be produced using H2[Pt(OH)6] as the source of Pt via the optimized PPD technique. The fuel cells produced from these electrodes are highly efficient with less than half the Pt content of com. available fuel cells, which results in a gravimetric power more than twice that of fuel cells produced by using com. available electrodes.
- 11Hussein, H. E. M.; Maurer, R. J.; Amari, H.; Peters, J. J. P.; Meng, L.; Beanland, R.; Newton, M. E.; Macpherson, J. V. Tracking Metal Electrodeposition Dynamics from Nucleation and Growth of a Single Atom to a Crystalline Nanoparticle. ACS Nano 2018, 12, 7388– 7396, DOI: 10.1021/acsnano.8b0408911https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC1cXht1Kns7fP&md5=3c3a6309b58178bef3d9a0aa5258f767Tracking Metal Electrodeposition Dynamics from Nucleation and Growth of a Single Atom to a Crystalline NanoparticleHussein, Haytham E. M.; Maurer, Reinhard J.; Amari, Houari; Peters, Jonathan J. P.; Meng, Lingcong; Beanland, Richard; Newton, Mark E.; Macpherson, Julie V.ACS Nano (2018), 12 (7), 7388-7396CODEN: ANCAC3; ISSN:1936-0851. (American Chemical Society)In electrodeposition the key challenge is to obtain better control over nanostructure morphol. Currently, a lack of understanding exists concerning the initial stages of nucleation and growth, which ultimately impact the physicochem. properties of the resulting entities. Using identical location scanning TEM (STEM), with B-doped diamond (BDD) serving as both an electron-transparent TEM substrate and electrode, the authors follow this process, from the formation of an individual metal atom through to a cryst. metal nanoparticle, under potential pulsed conditions. In doing so, the authors reveal the importance of electrochem. driven atom transport, atom cluster formation, cluster progression to a nanoparticle, and the mechanism by which neighboring particles interact during growth. Such information will help formulate improved nucleation and growth models and promote wider uptake of electrodeposited structures in a wide range of societally important applications. This type of measurement is possible in the TEM because the BDD possesses inherent stability, has an extremely high thermal cond., is electron beam transparent, is free from contamination, and is robust enough for multiple deposition and imaging cycles. Also, the platform can be operated under conditions such that the authors have confidence that the dynamic atom events the authors image are truly due to electrochem. driven deposition and no other factors, such as electron-beam-induced movement.
- 12Wang, Y.; Hall, A. S. Pulsed electrodeposition of metastable Pd31Bi12 nanoparticles for oxygen reduction electrocatalysis. ACS Energy Lett. 2020, 5, 17– 22, DOI: 10.1021/acsenergylett.9b0221912https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC1MXit1SqsbvI&md5=63580ffd2434529ccc1f28f51e762f6ePulsed Electrodeposition of Metastable Pd31Bi12 Nanoparticles for Oxygen Reduction ElectrocatalysisWang, Yunfei; Hall, Anthony ShojiACS Energy Letters (2020), 5 (1), 17-22CODEN: AELCCP; ISSN:2380-8195. (American Chemical Society)Metastable alloys have recently emerged as high-performance catalysts, extending the toolbox of binary alloy materials that can be utilized to mediate electrocatalytic reactions. In particular, nanostructured metastable ordered intermetallic compds. are challenging to synthesize. Here a method is reported for synthesizing sub-15 nm metastable ordered intermetallic Pd31Bi12 nanoparticles at room temp., in a single step, by pulsed electrochem. deposition onto high surface area carbon supports. The resulting Pd31Bi12 nanoparticles display a 7× enhancement of the mass activity relative to Pt/C and a 4× enhancement relative to Pd/C for the oxygen redn. reaction (ORR). The high performance of Pd31Bi12 nanoparticles is demonstrated to arise from reduced oxygen binding caused by alloying of Pd with Bi. It is also demonstrate that the isolation of Pd sites from each other facilitates methanol-tolerant ORR behavior.
- 13Wang, X.; Orikasa, Y.; Inaba, M.; Uchimoto, Y. Reviving Galvanic Cells To Synthesize Core-Shell Nanoparticles with a Quasi-Monolayer Pt Shell for Electrocatalytic Oxygen Reduction. ACS Catal. 2020, 10, 430– 434, DOI: 10.1021/acscatal.9b0367213https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC1MXitlWktrfF&md5=705b12935fb7af3460cd9d92afd0edddReviving Galvanic Cells To Synthesize Core-Shell Nanoparticles with a Quasi-Monolayer Pt Shell for Electrocatalytic Oxygen ReductionWang, Xiaoming; Orikasa, Yuki; Inaba, Minoru; Uchimoto, YoshiharuACS Catalysis (2020), 10 (1), 430-434CODEN: ACCACS; ISSN:2155-5435. (American Chemical Society)The use of core-shell nanoparticles composed of metal core (Mc, representing Pd, Au, Ru, etc.) and quasi-monolayer Pt shell (Ptqms) facilitates the achievement of cost and activity targets in many important electrocatalytic energy-conversion processes, such as the oxygen-redn. reaction (ORR). Here, inspired by the principle of galvanic cells, we report a generalized spontaneous strategy involving the growth of Cu on Mc ((-) bulk Cu(s) | Cu2+(c) | monolayer Cu/M(s) (+)) and the displacement of Cu by Pt (Cu + PtCl42- = Pt + Cu2+ + 4Cl-) to synthesize McPtqms. Exemplified by PdcPtqms, we demonstrate that this method requires no special control, electrochem. equipment, or reducing/stabilizing agents, which allows for the scalable prepn. of McPtqms. Meanwhile, it is able to produce homogeneous Ptqms, leading to high electrocatalytic activity for the ORR. This work paves the way for the practical application of McPtqms in electrocatalytic and related fields.
- 14Kanady, J. S.; Leidinger, P.; Haas, A.; Titlbach, S.; Schunk, S.; Schierle-Arndt, K.; Crumlin, E. J.; Wu, C. H.; Alivisatos, A. P. Synthesis of Pt3Y and Other Early-Late Intermetallic Nanoparticles by Way of a Molten Reducing Agent. J. Am. Chem. Soc. 2017, 139, 5672– 5675, DOI: 10.1021/jacs.7b0136614https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC2sXlt1yqsr0%253D&md5=a0c0235879d77d4062f930f47004e36cSynthesis of Pt3Y and Other Early-Late Intermetallic Nanoparticles by Way of a Molten Reducing AgentKanady, Jacob S.; Leidinger, Peter; Haas, Andreas; Titlbach, Sven; Schunk, Stephan; Schierle-Arndt, Kerstin; Crumlin, Ethan J.; Wu, Cheng Hao; Alivisatos, A. PaulJournal of the American Chemical Society (2017), 139 (16), 5672-5675CODEN: JACSAT; ISSN:0002-7863. (American Chemical Society)Early-late intermetallic phases have garnered increased attention recently for their catalytic properties. To achieve the high surface areas needed for industrially relevant applications, these phases must be synthesized as nanoparticles in a scalable fashion. Herein, Pt3Y-targeted as a prototypical example of an early-late intermetallic-was synthesized as nanoparticles ∼5-20 nm in diam. via a soln. process and characterized by XRD, TEM, EDS, and XPS. The key development is the use of a molten borohydride (MEt3BH, M = Na, K) as both the reducing agent and reaction medium. Readily available halide precursors of the two metals were used. Accordingly, no org. ligands are necessary, as the resulting halide salt byproduct prevents sintering, which further permits dispersion of the nanoscale intermetallic onto a support. The versatility of this approach was validated by the synthesis of other intermetallic phases such as Pt3Sc, Pt3Lu, Pt2Na, and Au2Y.
- 15Poerwoprajitno, A. R.; Gloag, L.; Cheong, S.; Gooding, J. J.; Tilley, R. D. Synthesis of low- and high-index faceted metal (Pt, Pd, Ru, Ir, Rh) nanoparticles for improved activity and stability in electrocatalysis. Nanoscale 2019, 11, 18995– 19011, DOI: 10.1039/C9NR05802H15https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC1MXhsFamu7%252FJ&md5=62ec9cb407d935044e286d84c17e850fSynthesis of low- and high-index faceted metal (Pt, Pd, Ru, Ir, Rh) nanoparticles for improved activity and stability in electrocatalysisPoerwoprajitno, Agus R.; Gloag, Lucy; Cheong, Soshan; Gooding, J. Justin; Tilley, Richard D.Nanoscale (2019), 11 (41), 18995-19011CODEN: NANOHL; ISSN:2040-3372. (Royal Society of Chemistry)A review. Driven by the quest for future energy soln., faceted metal nanoparticles are being pursued as the next generation electrocatalysts for renewable energy applications. Thanks to recent advancement in soln. phase synthesis, different low- and high-index facets on metal nanocrystals become accessible and are tested for specific electrocatalytic reactions. This minireview summarises the key approaches to prep. nanocrystals contg. the most catalytically active platinum group metals (Pt, Pd, Ru, Ir and Rh) exposed with low- and high-index facets using soln. phase synthesis. Electrocatalytic studies related to the different facets are highlighted to emphasize the importance of exposing facets for catalyzing these reactions, namely oxygen redn. reaction (ORR), hydrogen oxidn. reaction (HOR), alc. oxidn. including methanol (MOR) and ethanol oxidn. reactions (EOR), formic acid oxidn. reaction (FAOR), oxygen evolution reaction (OER), and hydrogen evolution reaction (HER). The future outlook discusses the challenges and opportunities for making electrocatalysts that are even more active and stable.
- 16Li, J.; Sharma, S.; Liu, X.; Pan, Y.-T.; Spendelow, J. S.; Chi, M.; Jia, Y.; Zhang, P.; Cullen, D. A.; Xi, Z.; Lin, H.; Yin, Z.; Shen, B.; Muzzio, M.; Yu, C.; Kim, Y. S.; Peterson, A. A.; More, K. L.; Zhu, H.; Sun, S. Hard-Magnet L10-CoPt Nanoparticles Advance Fuel Cell Catalysis. Joule 2019, 3, 124– 135, DOI: 10.1016/j.joule.2018.09.01616https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC1MXhsValtb8%253D&md5=97f930a346cafb0cd05b33c5e21133adHard-Magnet L10-CoPt Nanoparticles Advance Fuel Cell CatalysisLi, Junrui; Sharma, Shubham; Liu, Xiaoming; Pan, Yung-Tin; Spendelow, Jacob S.; Chi, Miaofang; Jia, Yukai; Zhang, Peng; Cullen, David A.; Xi, Zheng; Lin, Honghong; Yin, Zhouyang; Shen, Bo; Muzzio, Michelle; Yu, Chao; Kim, Yu Seung; Peterson, Andrew A.; More, Karren L.; Zhu, Huiyuan; Sun, ShouhengJoule (2019), 3 (1), 124-135CODEN: JOULBR; ISSN:2542-4351. (Cell Press)Stabilizing transition metals (M) in MPt alloy under acidic conditions is challenging, yet crucial to boost Pt catalysis toward oxygen redn. reaction (ORR). We synthesized ∼9 nm hard-magnet core/shell L10-CoPt/Pt nanoparticles with 2-3 at. layers of strained Pt shell for ORR. At 60°C in acid, the hard-magnet L10-CoPt better stabilizes Co (5% loss after 24 h) than soft-magnet A1-CoPt (34% loss in 7 h). L10-CoPt/Pt achieves mass activities (MA) of 0.56 A/mgPt initially and 0.45 A/mgPt after 30,000 voltage cycles in the membrane electrode assembly at 80°C, exceeding the DOE 2020 targets on Pt activity and durability (0.44 A/mgPt in MA and <40% loss in MA after 30,000 cycles). D. functional theory calcns. suggest that the ligand effect of Co and the biaxial strain (-4.50%/-4.25%) of the Pt shell weaken the binding of oxygenated species, leading to enhanced ORR performance in fuel cells.
- 17Liu, J.; Li, W.; Cheng, R.; Wu, Q.; Zhao, J.; He, D.; Mu, S. Stabilizing Pt Nanocrystals Encapsulated in N-Doped Carbon as Double-Active Sites for Catalyzing Oxygen Reduction Reaction. Langmuir 2019, 35, 2580– 2586, DOI: 10.1021/acs.langmuir.8b0394717https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC1MXitVCgs74%253D&md5=e93c86b2039325e39140652d2e18cab4Stabilizing Pt Nanocrystals Encapsulated in N-Doped Carbon as Double-Active Sites for Catalyzing Oxygen Reduction ReactionLiu, Jing; Li, Wenqiang; Cheng, Ruilin; Wu, Qian; Zhao, Jiahuan; He, Daping; Mu, ShichunLangmuir (2019), 35 (7), 2580-2586CODEN: LANGD5; ISSN:0743-7463. (American Chemical Society)Polypropylene fiber, a cheap source of N-doped C, is introduced to design robust N-doped C-encapsulated small Pt nanocrystals with Pt and N-C double-active centers toward O redn. reaction (ORR). Ascribed to the sepn. effect of the polypropylene fiber, even suffering from a high-temp. carbonization treatment at 720° for 90 min, the polypropylene fiber-derived C-encapsulated Pt nanocrystal maintains a small particle size (3 nm diam. on av.). As expected, its ORR mass activity is up to 116.5 mA/mg at 0.9 V. After 8000 cycles, the half-wave potential of the prepd. catalyst declines only by 14 mV compared with 43 mV for the com. Pt/C catalyst. The significantly improved electrochem. properties of the as-prepd. catalyst are resulted from the N-doped C-encapsulated Pt nanocrystal structure, which is benefited to adsorption and activation of O due to the presence of N-doped C as the important active site for ORR besides Pt metal. The migration, aggregation, and growth of Pt nanoparticles are prohibited in terms of the outer N-doped C protection layer, greatly enhancing the stability of the catalyst.
- 18Zaleska-Medynska, A.; Marchelek, M.; Diak, M.; Grabowska, E. Noble metal-based bimetallic nanoparticles: the effect of the structure on the optical, catalytic and photocatalytic properties. Adv. Colloid Interface Sci. 2016, 229, 80– 107, DOI: 10.1016/j.cis.2015.12.00818https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC2MXitFSnurjN&md5=93e47260901e2fd7aed43988c16d3e3eNoble metal-based bimetallic nanoparticles: the effect of the structure on the optical, catalytic and photocatalytic propertiesZaleska-Medynska, Adriana; Marchelek, Martyna; Diak, Magdalena; Grabowska, EwelinaAdvances in Colloid and Interface Science (2016), 229 (), 80-107CODEN: ACISB9; ISSN:0001-8686. (Elsevier B.V.)Nanoparticles composed of two different metal elements show novel electronic, optical, catalytic or photocatalytic properties from monometallic nanoparticles. Bimetallic nanoparticles could show not only the combination of the properties related to the presence of two individual metals, but also new properties due to a synergy between two metals. The structure of bimetallic nanoparticles can be oriented in random alloy, alloy with an intermetallic compd., cluster-in-cluster or core-shell structures and is strictly dependent on the relative strengths of metal-metal bond, surface energies of bulk elements, relative at. sizes, prepn. method and conditions, etc. In this review, selected properties, such as structure, optical, catalytic and photocatalytic of noble metals-based bimetallic nanoparticles, are discussed together with prepn. routes. The effects of prepn. method conditions as well as metal properties on the final structure of bimetallic nanoparticles (from alloy to core-shell structure) are followed. The role of bimetallic nanoparticles in heterogeneous catalysis and photocatalysis are discussed. Furthermore, structure and optical characteristics of bimetallic nanoparticles are described in relation to the some features of monometallic NPs. Such a complex approach allows to systematize knowledge and to identify the future direction of research.
- 19Li, R.; Wei, Z.; Huang, T.; Yu, A. Ultrasonic-assisted synthesis of Pd-Ni alloy catalysts supported on multi-walled carbon nanotubes for formic acid electrooxidation. Electrochim. Acta 2011, 56, 6860– 6865, DOI: 10.1016/j.electacta.2011.05.09719https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC3MXovFaksbo%253D&md5=86f7fb99cb21d6d29fa4aa4d014c6049Ultrasonic-assisted synthesis of Pd-Ni alloy catalysts supported on multi-walled carbon nanotubes for formic acid electrooxidationLi, Ruoshi; Wei, Zhen; Huang, Tao; Yu, AishuiElectrochimica Acta (2011), 56 (19), 6860-6865CODEN: ELCAAV; ISSN:0013-4686. (Elsevier Ltd.)Pd-Ni alloys with different compns. (i.e. Pd2Ni, PdNi, PdNi2) dispersed on multi-walled C nanotubes (MWCNTs) were prepd. by ultrasonic-assisted chem. redn. The XRD patterns indicate that all Pd and Pd-Ni nanoparticles exist as Pd fcc. structure, while Ni alloys with Pd. The TEM images show the addn. of Ni decreases the particle size and improves the dispersion. The XPS spectra demonstrate the electronic modification of Pd by Ni doping. The electrochem. measurements reveal that the PdNi catalysts have better catalytic activity and stability for formic acid electrooxidn., among them PdNi/MWCNTs is the best. The performance enhancement is ascribed to the increase of electroactive surface area (EASA) and Ni doping effect which might modify the electronic structure.
- 20Qin, F.; Ma, Y.; Miao, L.; Wang, Z.; Gan, L. Influence of Metal-Ligand Coordination on the Elemental Growth and Alloying Composition of Pt-Ni Octahedral Nanoparticles for Oxygen Reduction Electrocatalysis. ACS Omega 2019, 4, 8305– 8311, DOI: 10.1021/acsomega.8b0336620https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC1MXptVGhsbk%253D&md5=5368e0521da9b76486586463299dae29Influence of Metal-Ligand Coordination on the Elemental Growth and Alloying Composition of Pt-Ni Octahedral Nanoparticles for Oxygen Reduction ElectrocatalysisQin, Fei; Ma, Yangbo; Miao, Linqin; Wang, Zhongxiang; Gan, LinACS Omega (2019), 4 (5), 8305-8311CODEN: ACSODF; ISSN:2470-1343. (American Chemical Society)Understanding the role of surfactants or ligands on the growth mechanism of metal/alloy nanoparticles (NPs) is important for controlled synthesis of functional metallic NPs with tailored structures and properties. There were nos. of works showing the significant impact of surfactants/ligands on the shape-controlled synthesis of nanocrystals with well-defined surfaces. Beyond the morphol. shape control, impact of the surfactants/ligands on the alloying structure of bimetallic nanocrystals still remains largely unaddressed. A significant effect of HOBz ligand on the elemental growth and alloying phase structure of octahedral Pt-Ni NPs, a class of highly active electrocatalyst for O redn. reaction in fuel cells, is revealed. Contrary to previous reports showing the crit. role of HOBz in directing the growth of octahedral Pt-Ni NPs, HOBz played a minor role in forming the octahedral shape; instead, it can strongly coordinate with Ni cation and significantly slows down its redn. rate, leading to a phase sepn. in the Pt-Ni NP products (a mixt. of Pt-rich octahedral NPs and nearly pure Ni NPs). Such phase sepn. further resulted in a lower catalytic activity and stability. These results help one comprehensively understand the effect of metal-ligand coordination chem. on the elemental growth mechanism and alloying phase structure of bimetallic nanoparticles, complementing previous emphasis on the role of surfactants in purely morphol. shape control.
- 21Wegener, E. C.; Wu, Z.; Tseng, H.-T.; Gallagher, J. R.; Ren, Y.; Diaz, R. E.; Ribeiro, F. H.; Miller, J. T. Structure and reactivity of Pt-In intermetallic alloy nanoparticles: Highly selective catalysts for ethane dehydrogenation. Catal. Today 2018, 299, 146– 153, DOI: 10.1016/j.cattod.2017.03.05421https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC2sXmtFGntbo%253D&md5=ac6e07b5286f27e6bc164955c2ebebc9Structure and reactivity of Pt-In intermetallic alloy nanoparticles: Highly selective catalysts for ethane dehydrogenationWegener, Evan C.; Wu, Zhenwei; Tseng, Han-Ting; Gallagher, James R.; Ren, Yang; Diaz, Rosa E.; Ribeiro, Fabio H.; Miller, Jeffrey T.Catalysis Today (2018), 299 (), 146-153CODEN: CATTEA; ISSN:0920-5861. (Elsevier B.V.)The structure of silica supported Pt and Pt-In bimetallic catalysts with nominal In:Pt at. ratios of 0.7 and 1.4 were detd. by in situ synchrotron XAS and XRD. It was seen that the addn. of In led to the formation of two different intermetallic alloy phases. At an In:Pt ratio of 0.7 the Pt3In phase with a Cu3Au structure was formed. When the ratio was increased to 1.4 a shell of PtIn2 having a CaF2 structure formed around a core of Pt3In. The catalysts were tested for ethane dehydrogenation at 600 °C to det. the effect of alloying on ethylene selectivity and turnover rate (TOR). The monometallic Pt catalysts was 73% selective for ethylene and had an initial TOR of 0.7 s-1. Both alloy catalysts were ≈100% selective for dehydrogenation and had higher initial TOR, 2.8 s-1 and 1.6 s-1 for In:Pt ratio of 0.7 and 1.4, resp. The increase in selectivity is attributed to the elimination of large Pt ensembles resulting from geometric changes to the catalyst surface upon alloying. Electronic changes due to the formation of Pt-In bonds are thought to be responsible for the increases in TOR in the alloy catalysts.
- 22Zhang, L.; Roling, L. T.; Wang, X.; Vara, M.; Chi, M.; Liu, J.; Choi, S.-I.; Park, J.; Herron, J. A.; Xie, Z.; Mavrikakis, M.; Xia, Y. Platinum-based nanocages with subnanometer-thick walls and well-defined, controllable facets. Science 2015, 349, 412– 416, DOI: 10.1126/science.aab080122https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC2MXhtF2mtr%252FI&md5=15174b6852405ed48717c20f1c81012dPlatinum-based nanocages with subnanometer-thick walls and well-defined, controllable facetsZhang, Lei; Roling, Luke T.; Wang, Xue; Vara, Madeline; Chi, Miaofang; Liu, Jingyue; Choi, Sang-Il; Park, Jinho; Herron, Jeffrey A.; Xie, Zhaoxiong; Mavrikakis, Manos; Xia, YounanScience (Washington, DC, United States) (2015), 349 (6246), 412-416CODEN: SCIEAS; ISSN:0036-8075. (American Association for the Advancement of Science)A cost-effective catalyst should have a high dispersion of the active atoms, together with a controllable surface structure for the optimization of activity, selectivity, or both. We fabricated nanocages by depositing a few at. layers of platinum (Pt) as conformal shells on palladium (Pd) nanocrystals with well-defined facets and then etching away the Pd templates. D. functional theory calcns. suggest that the etching is initiated via a mechanism that involves the formation of vacancies through the removal of Pd atoms incorporated into the outermost layer during the deposition of Pt. With the use of Pd nanoscale cubes and octahedra as templates, we obtained Pt cubic and octahedral nanocages enclosed by {100} and {111} facets, resp., which exhibited distinctive catalytic activities toward oxygen redn.
- 23Torimoto, T.; Okazaki, K.-i.; Kiyama, T.; Hirahara, K.; Tanaka, N.; Kuwabata, S. Sputter deposition onto ionic liquids: Simple and clean synthesis of highly dispersed ultrafine metal nanoparticles. Appl. Phys. Lett. 2006, 89, 243117, DOI: 10.1063/1.240497523https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BD2sXislGqtA%253D%253D&md5=f5c381c5f8fdb8dc8193db838a20c8b5Sputter deposition onto ionic liquids: Simple and clean synthesis of highly dispersed ultrafine metal nanoparticlesTorimoto, Tsukasa; Okazaki, Ken-ichi; Kiyama, Tomonori; Hirahara, Kaori; Tanaka, Nobuo; Kuwabata, SusumuApplied Physics Letters (2006), 89 (24), 243117/1-243117/3CODEN: APPLAB; ISSN:0003-6951. (American Institute of Physics)Sputter deposition of gold (Au) onto ionic liqs. (ILs) gave highly dispersed Au nanoparticles without addnl. chem. species, such as reducing and/or stabilizing agents. The Au nanoparticles in 1-ethyl-3-methylimidazolium tetrafluoroborate had an av. diam. (dav) of 5.5 nm with a std. deviation (σ) of 0.86 nm, while sputter deposition onto N,N,N-trimethyl-N-propylammonium bis(trifluoromethanesulfonyl)imide gave much smaller Au nanoparticles with dav of 1.9 nm and σ of 0.46 nm. Prolongation of sputtering time results in a higher concn. of Au nanoparticles in ILs, but did not cause a remarkable change in their size.
- 24Tsuda, T.; Yoshii, K.; Torimoto, T.; Kuwabata, S. Oxygen reduction catalytic ability of platinum nanoparticles prepared by room-temperature ionic liquid-sputtering method. J. Power Sources 2010, 195, 5980– 5985, DOI: 10.1016/j.jpowsour.2009.11.02724https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC3cXmtlGhsbg%253D&md5=c099a8d988636c66899e64c983c6229bOxygen reduction catalytic ability of platinum nanoparticles prepared by room-temperature ionic liquid-sputtering methodTsuda, Tetsuya; Yoshii, Kazuki; Torimoto, Tsukasa; Kuwabata, SusumuJournal of Power Sources (2010), 195 (18), 5980-5985CODEN: JPSODZ; ISSN:0378-7753. (Elsevier B.V.)Pt nanoparticles can be produced by a Pt sputtering method onto trimethyl-n-propylammonium bis((trifluoromethyl)sulfonyl)amide (Me3PrNTf2N) room-temp. ionic liq. (RTIL) without stabilizing agents. Pt nanoparticles obtained by the Pt sputtering method showed mean particle size of ∼2.3-2.4 nm independently of sputtering time. A Pt-embedded glassy C electrode (Pt-GCE) consisting of the Pt-sputtered RTIL and a glassy C plate showed a favorable catalytic activity to oxygen redn. reaction. The catalytic ability was enhanced by Me3PrNTf2N modification of the Pt-GCE. CO never absorbed onto the RTIL-modified Pt-GCE.
- 25Yoshii, K.; Tsuda, T.; Arimura, T.; Imanishi, A.; Torimoto, T.; Kuwabata, S. Platinum nanoparticle immobilization onto carbon nanotubes using Pt-sputtered room-temperature ionic liquid. RSC Adv. 2012, 2, 8262– 8264, DOI: 10.1039/c2ra21243a25https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC38Xht1yks7%252FI&md5=bb7ef9ed2fddff2a1eb8e54037f40fdfPlatinum nanoparticle immobilization onto carbon nanotubes using Pt-sputtered room-temperature ionic liquidYoshii, Kazuki; Tsuda, Tetsuya; Arimura, Takashi; Imanishi, Akihito; Torimoto, Tsukasa; Kuwabata, SusumuRSC Advances (2012), 2 (22), 8262-8264CODEN: RSCACL; ISSN:2046-2069. (Royal Society of Chemistry)Establishment of a facile Pt nanoparticle-SWCNT composite fabrication method that never requires a laborious pretreatment of SWCNTs or any chem. reagent was achieved by using Pt-sputtered RTILs.
- 26Izumi, R.; Yao, Y.; Tsuda, T.; Torimoto, T.; Kuwabata, S. Oxygen reduction electrocatalysts sophisticated by using Pt nanoparticle-dispersed ionic liquids with electropolymerizable additives. J. Mater. Chem. A 2018, 6, 11853– 11862, DOI: 10.1039/C8TA03465F26https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC1cXhtVGgurzI&md5=1c672084af27ed8734e9eca4426e8c46Oxygen reduction electrocatalysts sophisticated by using Pt nanoparticle-dispersed ionic liquids with electropolymerizable additivesIzumi, Reiko; Yao, Yu; Tsuda, Tetsuya; Torimoto, Tsukasa; Kuwabata, SusumuJournal of Materials Chemistry A: Materials for Energy and Sustainability (2018), 6 (25), 11853-11862CODEN: JMCAET; ISSN:2050-7496. (Royal Society of Chemistry)The electropolymn. reaction of protic org. salt (POS) diphenylammonium hydrogen sulfate ([DPA][HSO4]) in the solid state proceeds in a N2-satd. 0.1 M HClO4 aq. soln., and conductive poly(diphenylamine) is formed without difficulty. This reaction has also been obsd. at the thin ionic liq. (IL) layer between Pt nanoparticles and carbon support on Pt nanoparticle-modified carbon electrocatalysts prepd. using a N,N-diethyl-N-methylammonium hydrogen sulfate ([DEMA][HSO4]) protic IL with a [DPA][HSO4] POS. Similar Pt nanoparticle electrocatalysts are fabricated using different electropolymerizable additives, including phenylammonium hydrogen sulfate ([PhNH3][HSO4]). A local electropolymn. reaction at the IL layer can confer a better electrochem. surface area and mass activity retention rates on oxygen redn. electrocatalysts. The performance of the resulting electrocatalysts is dependent on the electropolymerizable species.
- 27Yao, Y.; Izumi, R.; Tsuda, T.; Oshima, Y.; Imanishi, A.; Oda, N.; Kuwabata, S. Platinum and PtNi nanoparticle-supported multiwalled carbon nanotube electrocatalysts prepared by one-pot pyrolytic synthesis with an ionic liquid. ACS Appl. Energy Mater. 2019, 2, 4865– 4872, DOI: 10.1021/acsaem.9b0056127https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC1MXhtFWqs77K&md5=daef508fa4a5bfe5d611212fd1278cddPlatinum and PtNi Nanoparticle-Supported Multiwalled Carbon Nanotube Electrocatalysts Prepared by One-Pot Pyrolytic Synthesis with an Ionic LiquidYao, Yu; Izumi, Reiko; Tsuda, Tetsuya; Oshima, Yoshifumi; Imanishi, Akihito; Oda, Naoko; Kuwabata, SusumuACS Applied Energy Materials (2019), 2 (7), 4865-4872CODEN: AAEMCQ; ISSN:2574-0962. (American Chemical Society)Pt and PtNi alloy nanoparticle-supported multiwalled C nanotubes (Pt/MWCNTs and PtNi/MWCNTs) were prepd. by a 1-pot pyrolysis method with the N,N,N-trimethyl-N-propylammonium bis(trifluoromethanesulfonyl)amide ionic liq. (IL) contg. Pt and Ni precursors, Pt(acac)2, Ni[Tf2N]2, and Ni(acac)2, with suspended MWCNTs. The composite materials can be prepd. by simply heating the IL soln. at 573 K. The resulting materials show favorable catalytic activity toward the O redn. reaction and durability superior to those of typical com. available electrocatalysts. The catalytic activity of the PtNi/MWCNTs depends on the Ni content of the PtNi alloy nanoparticles. One of the PtNi/MWCNTs shows 1.4 times higher mass activity than a typical com. electrocatalyst. A plot of the mass activity as a function of the Ni content gives a mountain-shaped curve with a vertex at ∼25 at percent Ni. This 1-pot process can readily control the catalytic properties of the PtNi/MWCNTs by changing the molar fraction of Pt and Ni precursors.
- 28Kusada, K.; Kobayashi, H.; Ikeda, R.; Kubota, Y.; Takata, M.; Toh, S.; Yamamoto, T.; Matsumura, S.; Sumi, N.; Sato, K.; Nagaoka, K.; Kitagawa, H. Solid Solution Alloy Nanoparticles of Immiscible Pd and Ru Elements Neighboring on Rh: Changeover of the Thermodynamic Behavior for Hydrogen Storage and Enhanced CO-Oxidizing Ability. J. Am. Chem. Soc. 2014, 136, 1864– 1871, DOI: 10.1021/ja409464g28https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC2cXht1eitb0%253D&md5=aca030edfa0e4dca5dc64b8282defb10Solid Solution Alloy Nanoparticles of Immiscible Pd and Ru Elements Neighboring on Rh: Changeover of the Thermodynamic Behavior for Hydrogen Storage and Enhanced CO-Oxidizing AbilityKusada, Kohei; Kobayashi, Hirokazu; Ikeda, Ryuichi; Kubota, Yoshiki; Takata, Masaki; Toh, Shoichi; Yamamoto, Tomokazu; Matsumura, Syo; Sumi, Naoya; Sato, Katsutoshi; Nagaoka, Katsutoshi; Kitagawa, HiroshiJournal of the American Chemical Society (2014), 136 (5), 1864-1871CODEN: JACSAT; ISSN:0002-7863. (American Chemical Society)PdxRu1-x solid soln. alloy nanoparticles were successfully synthesized over the whole compn. range through a chem. redn. method, although Ru and Pd are immiscible at the at. level in the bulk state. From the XRD measurement, it was found that the dominant structure of PdxRu1-x changes from fcc to hcp with increasing Ru content. The structures of PdxRu1-x nanoparticles in the Pd compn. range of 30-70% consisted of both solid soln. fcc and hcp structures, and both phases coexist in a single particle. In addn., the reaction of hydrogen with the PdxRu1-x nanoparticles changed from exothermic to endothermic as the Ru content increased. Furthermore, the prepd. PdxRu1-x nanoparticles demonstrated enhanced CO-oxidizing catalytic activity; Pd0.5Ru0.5 nanoparticles exhibit the highest catalytic activity. This activity is much higher than that of the practically used CO-oxidizing catalyst Ru and that of the neighboring Rh, between Ru and Pd.
- 29Fan, C.; Wang, G.; Zou, L.; Fang, J.; Zou, Z.; Yang, H. Composition- and shape-controlled synthesis of the PtNi alloy nanotubes with enhanced activity and durability toward oxygen reduction reaction. J. Power Sources 2019, 429, 1– 8, DOI: 10.1016/j.jpowsour.2019.04.07329https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC1MXovVCku7g%253D&md5=8a1148a96923a70f0e293ee14ce3c945Composition- and shape-controlled synthesis of the PtNi alloy nanotubes with enhanced activity and durability toward oxygen reduction reactionFan, Chuanting; Wang, Guoliang; Zou, Liangliang; Fang, Jianhui; Zou, Zhiqing; Yang, HuiJournal of Power Sources (2019), 429 (), 1-8CODEN: JPSODZ; ISSN:0378-7753. (Elsevier B.V.)The development of the fuel cell catalysts with high durability and high activity for oxygen reaction redn. remains a great challenge. Various material designs such as alloys, core@shell structure and shape control provide the promising ways to improve the electrocatalytic performance. Herein, on the basis of both the alloy effect and the nanotube structure effect, we demonstrate a high-performance PtNi alloy catalyst with one-dimensional nanotube structure via a galvanic replacement reaction combined with Kirkendall effect. Meanwhile, the PtNi alloy phase and the tube structure are selectively controlled by tuning the PtNi at. ratio and the wall thickness of the nanotube, resp. Subsequently, the understanding of the compn. effect and the shape effect on the activity and the durability is systematically investigated. The optimized PtNi nanotube catalyst shows significant improvements on the activity (6.2-fold increase in specific activity compared to the com. Pt/C) and the durability (only 8.6% loss in mass activity after 10000 cycles), attributing to the alloy effect by introducing Ni to the Pt lattice, the Pt-rich surface and the shape effect of the unique one-dimensional hollow tube structure.
- 30Liu, Y.; Kou, W.; Li, X.; Huang, C.; Shui, R.; He, G. Constructing Patch-Ni-Shelled Pt@Ni Nanoparticles within Confined Nanoreactors for Catalytic Oxidation of Insoluble Polysulfides in Li-S Batteries. Small 2019, 15, 1902431, DOI: 10.1002/smll.201902431There is no corresponding record for this reference.
- 31Qi, X.; Li, X.; Chen, B.; Lu, H.; Wang, L.; He, G. Highly Active Nanoreactors: Patchlike or Thick Ni Coating on Pt Nanoparticles Based on Confined Catalysis. ACS Appl. Mater. Interfaces 2016, 8, 1922– 1928, DOI: 10.1021/acsami.5b1008331https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC28XhtlSrsw%253D%253D&md5=f72cf59f9344a09073ef8925225571eaHighly Active Nanoreactors: Patchlike or Thick Ni Coating on Pt Nanoparticles Based on Confined CatalysisQi, Xinhong; Li, Xiangcun; Chen, Bo; Lu, Huilan; Wang, Le; He, GaohongACS Applied Materials & Interfaces (2016), 8 (3), 1922-1928CODEN: AAMICK; ISSN:1944-8244. (American Chemical Society)Catalyst-contg. nanoreactors have attracted considerable attention for specific applications. Here, the authors initially report prepn. of PtNi@SiO2 hollow microspheres based on confined catalysis. The previous encapsulation of dispersed Pt nanoparticles (NPs) in hollow SiO2 microspheres ensures the formation of Pt@Ni coreshell NPs inside the SiO2 porous shell. Thus, the Pt NPs not only catalyze the redn. of Ni ions but also direct Ni deposition on the Pt cores to obtain Pt@Ni core-shell catalyst. It is worthy to point out that this synthetic approach helps to form a patchlike or thick Ni coating on Pt cores by controlling the penetration time of Ni ions from the bulk soln. into the SiO2 microspheres (0.5, 1, 2, or 4 h). Notably, the Pt@Ni core-shell NPs with a patch-like Ni layer on Pt cores (0.5 and 1 h) show a higher H2 generation rate of 1221 - 1475 H2 mL min-1 g-1cat than the Pt@Ni NPs with a thick Ni layer (2 and 4 h, 920 - 1183 H2 mL min-1 g-1cat), and much higher than that of pure Pt NPs (224 H2 mL min-1 g-1cat). The catalyst possesses good stability and recyclability for H2 generation. The Pt@Ni core-shell NPs confined inside SiO2 nanocapsules, with well-defined compns. and morphologies, high H2 generation rate, and recyclability, should be an ideal catalyst for specific applications in liq. phase reaction.
- 32Okamoto, H. Phase Digrams for Binary Alloys; 2nd ed.; ASM International: Materials Park, OH, 2010.There is no corresponding record for this reference.
- 33Garsany, Y.; Baturina, O. A.; Swider-Lyons, K. E.; Kocha, S. S. Experimental Methods for Quantifying the Activity of Platinum Electrocatalysts for the Oxygen Reduction Reaction. Anal. Chem. 2010, 82, 6321– 6328, DOI: 10.1021/ac100306c33https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC3cXot1amsLw%253D&md5=b5a5f6d35a0bb9cced6a4d6797911590Experimental Methods for Quantifying the Activity of Platinum Electrocatalysts for the Oxygen Reduction ReactionGarsany, Yannick; Baturina, Olga A.; Swider-Lyons, Karen E.; Kocha, Shyam S.Analytical Chemistry (Washington, DC, United States) (2010), 82 (15), 6321-6328CODEN: ANCHAM; ISSN:0003-2700. (American Chemical Society)A review. A tutorial is provided for methods to accurately and reproducibly det. the activity of Pt-based electrocatalysts for the oxygen redn. in proton-exchange membrane fuel cells and other applications. The impact of various exptl. parameters on electrocatalyst activity if demonstrated and explicit exptl. procedures and measurement protocols are given for comparison of the electrocatalyst activity to fuel cell stds.
- 34Shinozaki, K.; Zack, J. W.; Richards, R. M.; Pivovar, B. S.; Kocha, S. S. Oxygen Reduction Reaction Measurements on Platinum Electrocatalysts Utilizing Rotating Disk Electrode Technique. J. Electrochem. Soc. 2015, 162, F1144– F1158, DOI: 10.1149/2.1071509jes34https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC2MXhtlOnur7I&md5=22846d5016b89ed7dd2fe27d7710070bOxygen Reduction Reaction Measurements on Platinum Electrocatalysts Utilizing Rotating Disk Electrode TechniqueShinozaki, Kazuma; Zack, Jason W.; Richards, Ryan M.; Pivovar, Bryan S.; Kocha, Shyam S.Journal of the Electrochemical Society (2015), 162 (10), F1144-F1158CODEN: JESOAN; ISSN:0013-4651. (Electrochemical Society)The rotating disk electrode (RDE) technique is being extensively used as a screening tool to est. the activity of novel PEMFC electrocatalysts synthesized in lab.-scale (mg) quantities. Discrepancies in measured activity attributable to glassware and electrolyte impurity levels, as well as conditioning, protocols and corrections are prevalent in the literature. The electrochem. response to a broad spectrum of com. sourced HClO4 and the effect of acid molarity on impurity levels and soln. resistance were also assessed. The authors' findings reveal that an area specific activity (SA) exceeding 2.0 mA/cm2 (20 mV/s, 25°, 100 kPa, 0.1 M HClO4) for polished poly-Pt is an indicator of impurity levels that do not impede the accurate measurement of the ORR activity of Pt based catalysts. After exploring various conditioning protocols to approach max. use of the electrochem. area (ECA) and peak ORR activity without introducing catalyst degrdn., a study of measurement protocols for ECA and ORR activity was conducted. Down-selected protocols were based on the criteria of reproducibility, duration of expts., impurity effects and magnitude of pseudo-capacitive background correction. Statistical reproducibility of ORR activity for poly-Pt and Pt supported on high surface area C was demonstrated.
- 35Earle, M. J.; Hakala, U.; McAuley, B. J.; Nieuwenhuyzen, M.; Ramani, A.; Seddon, K. R. Metal bis{(trifluoromethyl)sulfonyl}amide complexes: highly efficient Friedel-Crafts acylation catalysts. Chem. Commun. 2004, 1368– 1369, DOI: 10.1039/B403650F35https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BD2cXks1Sqsr4%253D&md5=b6a3ac125266824a00b886979e9e9d63Metal bis[(trifluoromethyl)sulfonyl]amide complexes: highly efficient Friedel-Crafts acylation catalystsEarle, Martyn J.; Hakala, Ullastiina; McAuley, Barry J.; Nieuwenhuyzen, Mark; Ramani, Alwar; Seddon, Kenneth R.Chemical Communications (Cambridge, United Kingdom) (2004), (12), 1368-1369CODEN: CHCOFS; ISSN:1359-7345. (Royal Society of Chemistry)The title complexes were evaluated as Friedel-Crafts acylation catalysts. These reactions were carried out in ionic liqs., which allows the catalysts to be recovered and reused.
- 36Katase, T.; Imashuku, S.; Murase, K.; Hirato, T.; Awakura, Y. Water content and related physical properties of aliphatic quaternary ammonium imide-type ionic liquid containing metal ions. Sci. Technol. Adv. Mater. 2006, 7, 502– 510, DOI: 10.1016/j.stam.2006.02.01736https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BD28XhtFWitbfJ&md5=17118994e86fafa2e6ee4b8e0f9890e9Water content and related physical properties of aliphatic quaternary ammonium imide-type ionic liquid containing metal ionsKatase, Takuma; Imashuku, Susumu; Murase, Kuniaki; Hirato, Tetsuji; Awakura, YasuhiroScience and Technology of Advanced Materials (2006), 7 (6), 502-510CODEN: STAMCV; ISSN:1468-6996. (Elsevier Ltd.)The ionic liq., trimethyl-n-hexylammonium bis((trifluoromethyl)sulfonyl)amide (TMHA-Tf2N), has a wide electrochem. window of more than 5 V and is considered to be hydrophobic because of two -CF3 groups in its Tf2N- anion. However, a small amt. of water remains in the ionic liq. even after dehydration in vacuo, which causes some problems in metal electrodeposition when using the ionic liq. as a solvent. We measured the water content of the ionic liqs., TMHA-Tf2N contg. M(Tf2N)n (M=H, Li, Mg, Ni, Cu, Zn, La, and Dy; n=1, 2, or 3), as well as their kinematic viscosity and elec. cond. in the temp. range of 25-130°C. Furthermore, differential scanning calorimetry was performed for these ionic liqs. to find their glass transition temp., crystn. temp., and melting temp. The water content of TMHA-Tf2N contg. M(Tf2N)n salts decreased with an increase in temp. At the same time, the kinematic viscosity decreased and the elec. cond. increased. By measuring the optical absorption spectrum, it was found that the metal ions in TMHA-Tf2N were hydrated. The addn. of M(Tf2N)n to TMHA-Tf2N, increased the water content at a const. temp., which resulted in slight increases in the kinematic viscosity and decrease in the elec. cond. A Walden-like plot of the elec. conductivities against the kinematic viscosities, measured over various temps. and water contents, gave a single straight line.
- 37Yamamoto, K.; Kolb, D. M.; Kötz, R.; Lehmpfuhl, G. Hydrogen Adsorption and Oxide Formation on Platinum Single-Crystal Electrodes. J. Electroanal. Chem. 1979, 96, 233– 239, DOI: 10.1016/S0022-0728(79)80380-0There is no corresponding record for this reference.
Supporting Information
Supporting Information
The Supporting Information is available free of charge at https://pubs.acs.org/doi/10.1021/acsomega.0c02951.
TG measurement results for metal precursors (Figure S1); particle size distributions of nanoparticles (Figures S2 and S5); TEM images (Figure S4), BF-STEM and HAADF-STEM images (Figures S3, S6, and S7), EDS mappings (Figures S3, S6, and S7), and SAED patterns (Figure S8) of the PtNi/MWCNTs; summary of PtNi/MWCNTs prepared in [N1,1,1,3][Tf2N] with Pt(acac)2, Ni(acac)2, and MWCNT (Table S1) (PDF)
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