Activity and Durability of PEFCs Alloy Core-Shell Catalysts: Role of Surface Oxidation

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Low temperature fuel cells are one of the most promising systems for the transformation of fuels into electricity in an efficient, silent, and environmentally friendly manner. In this paper we show the advances accomplished in the synthesis and a theoretical-experimental analysis of the changes induced by the Ni@Pt structure and the presence of the almost unavoidable NiO species. The synthesis of core-shell nanoparticles is described and then physical and electrochemical characterizations confirm the presence of core-shell nanoparticles with a high electrochemical activity towards the Oxygen Reduction Reaction. Periodic density functional theory calculations are used to analyze the shift in the oxidation potential for Pt, Ni@Pt and NiO@Pt with different number of layers in the shell. The changes in the electrochemical activity towards oxygen reduction are evaluated by allowing oxygen to adsorb on the surface of the nanoparticle and alloys. It is found that only the first and second layers of Pt are being affected by the presence of the Ni or NiO core.

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31-40

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October 2014

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© 2014 Trans Tech Publications Ltd. All Rights Reserved

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[1] Song, C.S., Global challenges and strategies for control, conversion and utilization of CO2 for sustainable development involving energy, catalysis, adsorption and chemical processing. Catalysis Today, 2006. 115(1-4): pp.2-32.

DOI: 10.1016/j.cattod.2006.02.029

Google Scholar

[2] Specht, M., et al., Comparison of the renewable transportation fuels, liquid hydrogen and methanol, with gasoline-energetic and economic aspects. International Journal of Hydrogen Energy, 1998. 23(5): pp.387-396.

DOI: 10.1016/s0360-3199(97)00077-3

Google Scholar

[3] Zhang, J., et al., Mixed-Metal Pt Monolayer Electrocatalysts for Enhanced Oxygen Reduction Kinetics. Journal of the American Chemical Society, 2005. 127(36): pp.12480-12481.

DOI: 10.1021/ja053695i

Google Scholar

[4] Guo, S., S. Zhang, and S. Sun, Tuning Nanoparticle Catalysis for the Oxygen Reduction Reaction. Angewandte Chemie International Edition, 2013. 52(33): pp.8526-8544.

DOI: 10.1002/anie.201207186

Google Scholar

[5] Cui, C., et al., Compositional segregation in shaped Pt alloy nanoparticles and their structural behaviour during electrocatalysis. Nature Materials, 2013. 12(8): pp.765-771.

DOI: 10.1038/nmat3668

Google Scholar

[6] Godinez-Salomon, F., M. Hallen-Lopez, and O. Solorza-Feria, Enhanced electroactivity for the oxygen reduction on Ni@Pt core-shell nanocatalysts. International Journal of Hydrogen Energy, 2012. 37(19): pp.14902-14910.

DOI: 10.1016/j.ijhydene.2012.01.157

Google Scholar

[7] Garsany, Y., et al., Experimental Methods for Quantifying the Activity of Platinum Electrocatalysts for the Oxygen Reduction Reaction. Analytical Chemistry, 2010. 82(15): pp.6321-6328.

DOI: 10.1021/ac100306c

Google Scholar

[8] Kresse, G. and J. Hafner, Ab initio molecular dynamics of liquid metals. Physical Review B: Condensed Matter and Materials Physics, 1993. 47(1): pp.558-61.

DOI: 10.1103/physrevb.47.558

Google Scholar

[9] Kresse, G. and J. Furthmueller, Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set. Physical Review B: Condensed Matter, 1996. 54(16): pp.11169-11186.

DOI: 10.1103/physrevb.54.11169

Google Scholar

[10] Perdew, J.P. and Y. Wang, Accurate and simple analytic representation of the electron-gas correlation energy. Physical Review B, 1992. 45(23): p.13244.

DOI: 10.1103/physrevb.45.13244

Google Scholar

[11] Blochl, P.E., Projector Augmented-Wave Method. Phys. Rev. B, 1994. 50(24): pp.17953-17979.

DOI: 10.1103/physrevb.50.17953

Google Scholar

[12] Kresse, G. and D. Joubert, From ultrasoft pseudopotentials to the projector augmented-wave method. Phys. Rev. B, 1999. 59(3): pp.1758-1775.

DOI: 10.1103/physrevb.59.1758

Google Scholar

[13] Dudarev, S.L., et al., Electron-energy-loss spectra and the structural stability of nickel oxide: An LSDA+U study. Physical Review B, 1998. 57(3): pp.1505-1509.

DOI: 10.1103/physrevb.57.1505

Google Scholar

[14] Heyd, J. and G.E. Scuseria, Efficient hybrid density functional calculations in solids: Assessment of the Heyd-Scuseria-Ernzerhof screened Coulomb hybrid functional. Journal of Chemical Physics, 2004. 121(3): pp.1187-1192.

DOI: 10.1063/1.1760074

Google Scholar

[15] Heyd, J., G.E. Scuseria, and M. Ernzerhof, Hybrid functionals based on a screened Coulomb potential (vol 118, pg 8207, 2003). Journal of Chemical Physics, 2006. 124(21).

DOI: 10.1063/1.2204597

Google Scholar

[16] Chen, S.L. and A. Kucernak, Electrocatalysis under conditions of high mass transport rate: Oxygen reduction on single submicrometer-sized Pt particles supported on carbon. Journal of Physical Chemistry B, 2004. 108(10): pp.3262-3276.

DOI: 10.1021/jp036831j

Google Scholar

[17] Stamenkovic, V., et al., Changing the activity of electrocatalysts for oxygen reduction by tuning the surface electronic structure. Angewandte Chemie, International Edition, 2006. 45(18): pp.2897-2901.

DOI: 10.1002/anie.200504386

Google Scholar

[18] Balbuena, P.B., et al., Evolution of Pt and Pt-Alloy Catalytic Surfaces Under Oxygen Reduction Reaction in Acid Medium. Topics in Catalysis, 2012. 55(5-6): pp.322-335.

DOI: 10.1007/s11244-012-9800-8

Google Scholar