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Direct observation of the dealloying process of a platinum–yttrium nanoparticle fuel cell cathode and its oxygenated species during the oxygen reduction reaction

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Malacrida, Paolo
Casalongue, Hernan G. Sanchez
Masini, Federico
Hernandez-Fernandez, Patricia
Deiana, Davide
Ogasawara, Hirohito
Stephens, Ifan E. L.
Nilsson, Anders
Chorkendorff, Ib

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Size-selected 9 nm PtxY nanoparticles have recently shown an outstanding catalytic activity for the oxygen reduction reaction, representing a promising cathode catalyst for proton exchange membrane fuel cells (PEMFCs). Studying their electrochemical dealloying is a fundamental step towards the understanding of both their activity and stability. Herein, size-selected 9 nm PtxY nanoparticles have been deposited on the cathode side of a PEMFC specifically designed for in situ ambient pressure X-ray photoelectron spectroscopy (APXPS). The dealloying mechanism was followed in situ for the first time. It proceeds through the progressive oxidation of alloyed Y atoms, soon leading to the accumulation of Y3+ cations at the cathode. Acid leaching with sulfuric acid is capable of accelerating the dealloying process and removing these Y3+ cations which might cause long term degradation of the membrane. The use of APXPS under near operating conditions allowed observing the population of oxygenated surface species as a function of the electrochemical potential. Similar to the case of pure Pt nanoparticles, non-hydrated hydroxide plays a key role in the ORR catalytic process.

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Royal Society of Chemistry (RSC)

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Physical chemistry, Physics

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Physical Chemistry Chemical Physics

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10.1039/c5cp00283d

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