Partial oxidation of step-bound water leads to anomalous pH effects on metal electrode step-edges

Schwarz, Kathleen; Xu, Bingjun; Yan, Yushan; Sundararaman, Ravishankar

doi:10.1039/c6cp01652a

Title: Partial oxidation of step-bound water leads to anomalous pH effects on metal electrode step-edges

Journal Article · Thu May 26 00:00:00 EDT 2016 · Physical Chemistry Chemical Physics. PCCP

DOI:https://doi.org/10.1039/c6cp01652a· OSTI ID:1435805

Schwarz, Kathleen ^[1]; Xu, Bingjun ^[2]; Yan, Yushan ^[2];

^[3]

National Inst. of Standards and Technology (NIST), Gaithersburg, MD (United States). Materials Measurement Lab.
Univ. of Delaware, Newark, DE (United States). Dept. of Chemical and Biomolecular Engineering
California Inst. of Technology (CalTech), Pasadena, CA (United States). Joint Center for Artificial Photosynthesis (JCAP)

The design of better heterogeneous catalysts for applications such as fuel cells and electrolyzers requires a mechanistic understanding of electrocatalytic reactions and the dependence of their activity on operating conditions such as pH. A satisfactory explanation for the unexpected pH dependence of electrochemical properties of platinum surfaces has so far remained elusive, with previous explanations resorting to complex co-adsorption of multiple species and resulting in limited predictive power. This knowledge gap suggests that the fundamental properties of these catalysts are not yet understood, limiting systematic improvement. In this paper, we analyze the change in charge and free energies upon adsorption using density-functional theory (DFT) to establish that water adsorbs on platinum step edges across a wide voltage range, including the double-layer region, with a loss of approximately 0.2 electrons upon adsorption. We show how this as-yet unreported change in net surface charge due to this water explains the anomalous pH variations of the hydrogen underpotential deposition (H_upd) and the potentials of zero total charge (PZTC) observed in published experimental data. This partial oxidation of water is not limited to platinum metal step edges, and we report the charge of the water on metal step edges of commonly used catalytic metals, including copper, silver, iridium, and palladium, illustrating that this partial oxidation of water broadly influences the reactivity of metal electrodes.

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Research Organization:: California Institute of Technology (CalTech), Pasadena, CA (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: SC0004993

OSTI ID:: 1435805

Journal Information:: Physical Chemistry Chemical Physics. PCCP, Vol. 18, Issue 24; ISSN 1463-9076

Publisher:: Royal Society of ChemistryCopyright Statement

Country of Publication:: United States

Language:: English

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Cited by: 35 works

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