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Trimetallic PtRhNi alloy nanoassemblies as highly active electrocatalyst for ethanol electrooxidation
Abstract
Although nanostructures based on noble metal alloys are widely utilized in (electro)catalysis, their low-temperature synthesis remains an enormous challenge due to the different Nernst equilibrium potentials of metal precursors. Herein, we describe the successful synthesis of trimetallic PtRhNi alloy nanoassemblies (PtRhNi-ANAs) with tunable Pt/Rh ratios using a simple mixed cyanogel reduction method and provide a detailed characterization of their chemical composition, morphology, and structure. Additionally, the electrochemical properties of PtRhNi-ANAs are examined by cyclic voltammetry, revealing composition-dependent electrocatalytic activity in the ethanol oxidation reaction (EOR). Compared to a commercial Pt black electrocatalyst, optimized Pt3Rh1Ni2-ANAs display remarkably enhanced EOR electrocatalytic performance in alkaline media.
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1
Saleem, F.; Zhang, Z. C.; Xu, B.; Xu, X. B.; He, P. L.; Wang, X. Ultrathin Pt–Cu nanosheets and nanocones. J. Am. Chem. Soc. 2013, 135, 18304–18307.
2
Bianchini, C.; Shen, P. K. Palladium-based electrocatalysts for alcohol oxidation in half cells and in direct alcohol fuel cells. Chem. Rev. 2009, 109, 4183–4206.
3
Xu, Y.; Zhang, B. Recent advances in porous Pt-based nanostructures: Synthesis and electrochemical applications. Chem. Soc. Rev. 2014, 43, 2439–2450.
4
Puthiyapura, V. K.; Brett, D. J. L.; Russell, A. E.; Lin, W. -F.; Hardacre, C. Biobutanol as fuel for direct alcohol fuel cells-investigation of Sn-modified Pt catalyst for butanol electro-oxidation. ACS Appl. Mater. Interfaces 2016, 8, 12859–12870.
5
Huang, M. H.; Wu, W. L.; Wu, C. X.; Guan, L. H. Pt2SnCu nanoalloy with surface enrichment of Pt defects and SnO2 for highly efficient electrooxidation of ethanol. J. Mater. Chem. A 2015, 3, 4777–4781.
6
Gnanaprakasam, P.; Jeena, S. E.; Selvaraju, T. Hierarchical electroless Pt deposition at Au decorated reduced graphene oxide via a galvanic exchanged process: An electrocatalytic nanocomposite with enhanced mass activity for methanol and ethanol oxidation. J. Mater. Chem. A 2015, 3, 18010–18018.
7
Akhairi, M. A. F.; Kamarudin, S. K. Catalysts in direct ethanol fuel cell (DEFC): An overview. Int. J. Hydrogen Energ. 2016, 41, 4214–4228.
8
Kamarudin, M. Z. F.; Kamarudin, S. K.; Masdar, M. S.; Daud, W. R. W. Review: Direct ethanol fuel cells. Int. J. Hydrogen Energ. 2013, 38, 9438–9453.
9
Erini, N.; Rudi, S.; Beermann, V.; Krause, P.; Yang, R. Z.; Huang, Y. H.; Strasser, P. Exceptional activity of a Pt-Rh-Ni ternary nanostructured catalyst for the electrochemical oxidation of ethanol. ChemElectroChem 2015, 2, 903–908.
10
Li, H. J.; Wu, H. X.; Zhai, Y. J.; Xu, X. L.; Jin, Y. D. Synthesis of monodisperse plasmonic Au core-Pt shell concave nanocubes with superior catalytic and electrocatalytic activity. ACS Catal. 2013, 3, 2045–2051.
11
Guo, S. J.; Dong, S. J.; Wang, E. K. Pt/Pd bimetallic nanotubes with petal-like surfaces for enhanced catalytic activity and stability towards ethanol electrooxidation. Energy Environ. Sci. 2010, 3, 1307–1310.
12
Nosheen, F.; Zhang, Z. C.; Xiang, G. L.; Xu, B.; Yang, Y.; Saleem, F.; Xu, X. B.; Zhang, J. C.; Wang, X. Threedimensional hierarchical Pt-Cu superstructures. Nano Res. 2015, 8, 832–838.
13
Zhao, T. -T.; Wang, H.; Han, X.; Jiang, K.; Lin, H. X.; Xie, Z. X.; Cai, W. B. A comparative investigation of electrocatalysis at Pt monolayers on shape-controlled Au nanocrystals: Facet effect versus strain effect. J. Mater. Chem. A 2016, 4, 15845–15850.
14
de Souza, J. P. I.; Queiroz, S. L.; Bergamaski, K.; Gonzalez, E. R.; Nart, F. C. Electro-oxidation of ethanol on Pt, Rh, and PtRh electrodes. A study using DEMS and in-situ FTIR techniques. J. Phys. Chem. B 2002, 106, 9825–9830.
15
Delpeuch, A. B.; Asset, T.; Chatenet, M.; Cremers, C. Electrooxidation of ethanol at room temperature on carbonsupported Pt and Rh-containing catalysts: A DEMS study. J. Electrochem. Soc. 2014, 161, F918–F924.
16
Lima, F. H. B.; Profeti, D.; Lizcano-Valbuena, W. H.; Ticianelli, E. A.; Gonzalez, E. R. Carbon-dispersed Pt–Rh nanoparticles for ethanol electro-oxidation. Effect of the crystallite size and of temperature. J. Electroanal. Chem. 2008, 617, 121–129.
17
Bergamaski, K.; Gonzalez, E. R.; Nart, F. C. Ethanol oxidation on carbon supported platinum-rhodium bimetallic catalysts. Electrochim. Acta 2008, 53, 4396–4406.
18
Delpeuch, A. B.; Maillard, F.; Chatenet, M.; Soudant, P.; Cremers, C. Ethanol oxidation reaction (EOR) investigation on Pt/C, Rh/C, and Pt-based bi- and tri-metallic electrocatalysts: A DEMS and in situ FTIR study. Appl. Catal. B: Environ. 2016, 181, 672–680.
19
Mukherjee, P.; Roy, P. S.; Bhattacharya, S. K. Improved carbonate formation from ethanol oxidation on nickel supported Pt-Rh electrode in alkaline medium at room temperature. Int. J. Hydrogen Energ. 2015, 40, 13357–13367.
20
Mukherjee, P.; Bagchi, J.; Dutta, S.; Bhattacharya, S. K. The nickel supported platinum catalyst for anodic oxidation of ethanol in alkaline medium. Appl. Catal. A: Gen. 2015, 506, 220–227.
21
Rizo, R.; Sebastián, D.; Lázaro, M. J.; Pastor, E. On the design of Pt-Sn efficient catalyst for carbon monoxide and ethanol oxidation in acid and alkaline media. Appl. Catal. B: Environ. 2017, 200, 246–254.
22
Qu, Y. T.; Gao, Y. Z.; Wang, L.; Rao, J. C.; Yin, G. P. Mild synthesis of Pt/SnO2/graphene nanocomposites with remarkably enhanced ethanol electro-oxidation activity and durability. Chem. — Eur. J. 2016, 22, 193–198.
23
Mello, G. A. B.; Giz, M. J.; Chatenet, M.; Camara, G. A. The electrooxidation of acetaldehyde on platinum-rutheniumrhodium surfaces: A delicate balance between oxidation and carbon–carbon bond breaking. J. Electroanal. Chem. 2016, 765, 73–78.
24
Jeon, T. Y.; Kim, S. K.; Pinna, N.; Sharma, A.; Park, J.; Lee, S. Y.; Lee, H. C.; Kang, S. W.; Lee, H. K.; Lee, H. H. Selective dissolution of surface nickel close to platinum in PtNi nanocatalyst toward oxygen reduction reaction. Chem. Mater. 2016, 28, 1879–1887.
25
Li, H. -H.; Cui, C. -H.; Zhao, S.; Yao, H. -B.; Gao, M. -R.; Fan, F. -J.; Yu, S. -H. Mixed-PtPd-shell PtPdCu nanoparticle nanotubes templated from copper nanowires as efficient and highly durable electrocatalysts. Adv. Energy Mater. 2012, 2, 1182–1187.
26
Kowal, A.; Li, M.; Shao, M.; Sasaki, K.; Vukmirovic, M. B.; Zhang, J.; Marinkovic, N. S.; Liu, P.; Frenkel, A. I.; Adzic, R. R. Ternary Pt/Rh/SnO2 electrocatalysts for oxidizing ethanol to CO2. Nat. Mater. 2009, 8, 325–330.
27
Erini, N.; Loukrakpam, R.; Petkov, V.; Baranova, E. A.; Yang, R. Z.; Teschner, D.; Huang, Y. H.; Brankovic, S. R.; Strasser, P. Ethanol electro-oxidation on ternary platinumrhodium-tin nanocatalysts: Insights in the atomic 3D structure of the active catalytic phase. ACS Catal. 2014, 4, 1859–1867.
28
Soares, L. A.; Morais, C.; Napporn, T. W.; Kokoh, K. B.; Olivi, P. Beneficial effects of rhodium and tin oxide on carbon supported platinum catalysts for ethanol electrooxidation. J. Power Sources 2016, 315, 47–55.
29
Jiang, K. Z.; Bu, L. Z.; Wang, P. T.; Guo, S. J.; Huang, X. Q. Trimetallic PtSnRh wavy nanowires as efficient nanoelectrocatalysts for alcohol electrooxidation. ACS Appl. Mater. Interfaces 2015, 7, 15061–15067.
30
Yang, G. X.; Frenkel, A. I.; Su, D.; Teng, X. W. Enhanced electrokinetics of C–C bond splitting during ethanol oxidation by using a Pt/Rh/Sn catalyst with a partially oxidized Pt and Rh core and a SnO2 shell. ChemCatChem 2016, 8, 2876–2880.
31
Zhu, W.; Ke, J.; Wang, S. B.; Ren, J.; Wang, H. H.; Zhou, Z. Y.; Si, R.; Zhang, Y. W.; Yan, C. H. Shaping singlecrystalline trimetallic Pt-Pd-Rh nanocrystals toward highefficiency C–C splitting of ethanol in conversion to CO2. ACS Catal. 2015, 5, 1995–2008.
32
Liu, H. M.; Liu, X. Y.; Li, Y. M.; Jia, Y. F.; Tang, Y. W.; Chen, Y. Hollow PtNi alloy nanospheres with enhanced activity and methanol tolerance for the oxygen reduction reaction. Nano Res. 2016, 9, 3494–3503.
33
Liu, X. Y.; Xu, G. R.; Chen, Y.; Lu, T. H.; Tang, Y. W.; Xing, W. A strategy for fabricating porous PdNi@Pt core–shell nanostructures and their enhanced activity and durability for the methanol electrooxidation. Sci. Rep. 2015, 5, 7619.
34
Zhang, L.; Wan, L.; Ma, Y. R.; Chen, Y.; Zhou, Y. M.; Tang, Y. W.; Lu, T. H. Crystalline palladium–cobalt alloy nanoassemblies with enhanced activity and stability for the formic acid oxidation reaction. Appl. Catal. B: Environ. 2013, 138–139, 229–235.
35
Xu, J. F.; Liu, X. Y.; Chen, Y.; Zhou, Y. M.; Lu, T. H.; Tang, Y. W. Platinum-cobalt alloy networks for methanol oxidation electrocatalysis. J. Mater. Chem. 2012, 22, 23659–23667.
36
Vondrova, M.; McQueen, T. M.; Burgess, C. M.; Ho, D. M.; Bocarsly, A. B. Autoreduction of Pd?Co and Pt?Co cyanogels: Exploration of cyanometalate coordination chemistry at elevated temperatures. J. Am. Chem. Soc. 2008, 130, 5563–5572.
37
Deshpande, R. S.; Sharp-Goldman, S. L.; Willson, J. L.; Bocarsly, A. B.; Gross, J.; Finnefrock, A. C.; Gruner, S. M. Morphology and gas adsorption properties of palladium–cobalt-based cyanogels. Chem. Mater. 2003, 15, 4239–4246.
38
Burgess, C. M.; Vondrova, M.; Bocarsly, A. B. A versatile chemical method for the formation of macroporous transition metal alloys from cyanometalate coordination polymers. J. Mater. Chem. 2008, 18, 3694–3701.
39
Heibel, M.; Kumar, G.; Wyse, C.; Bukovec, P.; Bocarsly, A. B. Use of sol-gel chemistry for the preparation of cyanogels as ceramic and alloy precursors. Chem. Mater. 1996, 8, 1504–1511.
40
Pfennig, B. W.; Bocarsly, A. B.; Prud'homme, R. K. Synthesis of a novel hydrogel based on a coordinate covalent polymer network. J. Am. Chem. Soc. 1993, 115, 2661–2665.
41
Moulder, J. F.; Stickle, W. F.; Sobol, P. E.; Bomben, K. D. Handbook of X-ray Photoelectron Spectroscopy; Perkin-Elmer Corporation, Physical Electronics Division: Eden Prairie, MN, USA, 1992.
42
Wang, L. L.; Zhang, D. F.; Guo, L. Phase-segregated Pt-Ni chain-like nanohybrids with high electrocatalytic activity towards methanol oxidation reaction. Nanoscale 2014, 6, 4635–4641.
43
Zhang, J. F.; Li, K. D.; Zhang, B. Synthesis of dendritic Pt–Ni–P alloy nanoparticles with enhanced electrocatalytic properties. Chem. Commun. 2015, 51, 12012–12015.
44
Zhang, J. F.; Xu, Y.; Zhang, B. Facile synthesis of 3D Pd–P nanoparticle networks with enhanced electrocatalytic performance towards formic acid electrooxidation. Chem. Commun. 2014, 50, 13451–13453.
45
Ma, J. W.; Wang, J.; Zhang, G. H.; Fan, X. B.; Zhang, G. L.; Zhang, F. B.; Li, Y. Deoxyribonucleic acid-directed growth of well dispersed nickel-palladium-platinum nanoclusters on graphene as an efficient catalyst for ethanol electrooxidation. J. Power Sources 2015, 278, 43–49.
46
Delpeuch, A. B.; Asset, T.; Chatenet, M.; Cremers, C. Influence of the temperature for the ethanol oxidation reaction (EOR) on Pt/C, Pt-Rh/C and Pt-Rh-SnO2/C. Fuel Cells 2015, 15, 352–360.
Pages 3324-3332
Cite this article:
Liu H, Li J, Wang L, et al. Trimetallic PtRhNi alloy nanoassemblies as highly active electrocatalyst for ethanol electrooxidation. Nano Research, 2017, 10(10): 3324-3332. https://doi.org/10.1007/s12274-017-1545-z
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