4.6 Article

Nanoporous Pd-Cu thin films as highly active and durable catalysts for oxygen reduction in alkaline media

Journal

ELECTROCHIMICA ACTA
Volume 385, Issue -, Pages -

Publisher

PERGAMON-ELSEVIER SCIENCE LTD
DOI: 10.1016/j.electacta.2021.138306

Keywords

Nanoporous metals; PdCu alloy; Alkaline media; Oxygen reduction reaction; De-alloying

Funding

  1. Center for AlkalineBased Energy Solutions, an Energy Frontier Research Center program - US Department of Energy [DE-SC00194 45]
  2. Shimadzu Summer Fellowship at the Department of Chemistry
  3. National Science Foundation [DMR 1808383]
  4. S3IP, State University of New York at Binghamton

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A facile electrochemical etching approach was developed to enhance the electrocatalytic performance of Pd-Cu films for ORR in alkaline media. The nanoporous Pd-Cu catalyst showed excellent ORR activity and durability, attributed to its unique porous structure and modified electronic structure with residual Cu.
A facile electrochemical etching approach was developed and implemented to enhance the electrocatalytic performance of Pd-Cu films for oxygen reduction reaction (ORR) in alkaline media. The nanoporous (np) Pd-Cu was synthesized through electrochemical de-alloying of pre-deposited Pd-Cu films. Scanning electron microscopy (SEM) with energy dispersive spectroscopy was employed to confirm the residual amount of Cu in the np structure. The accordingly prepared np catalysts showed excellent ORR activity up to 1.11 A/mg Pd at a potential of 0.9 V vs. RHE which is around 22-times and 6.2-times higher than that of a plain Pd film and commercial Pd/C catalyst, respectively. The ORR activity enhancement is attributed to the unique porous structure, large Pd surface area, and modified electronic structure of Pd with residual Cu as confirmed by the SEM, hydrogen underpotential deposition, and CO stripping characterizations. The np Pd-Cu catalyst also showed excellent durability which is manifested by a negligible decrease in the half-wave potential (4 mV negative shift) after 10,0 00 potential cycles in alkaline media. These findings provide insights into the rational design of an electrocatalyst's structure utilizing an electrochemical de-alloying method to achieve high atomic utilization and improved catalytic performance. (C) 2021 Elsevier Ltd. All rights reserved.

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