Molecular-Scale Structure of Electrode–Electrolyte Interfaces: The Case of Platinum in Aqueous Sulfuric Acid

Wu, Cheng Hao; Pascal, Tod A.; Baskin, Artem; Wang, Huixin; Fang, Hai-Tao; Liu, Yi-Sheng; Lu, Yi-Hsien; Guo, Jinghua; Prendergast, David; Salmeron, Miquel B.

doi:10.1021/jacs.8b09743

Title: Molecular-Scale Structure of Electrode–Electrolyte Interfaces: The Case of Platinum in Aqueous Sulfuric Acid

Journal Article · 28 October 2018 · Journal of the American Chemical Society

DOI: https://doi.org/10.1021/jacs.8b09743 · OSTI ID:1604655

^[1];

^[2]; Baskin, Artem ^[2]; Wang, Huixin ^[3]; Fang, Hai-Tao ^[3]; Liu, Yi-Sheng ^[2]; Lu, Yi-Hsien ^[4];

^[5]; Prendergast, David ^[2];

^[6]

Univ. of California, Berkeley, CA (United States); Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States); Harbin Inst. of Technology (China)
Materials Science Division, Lawrence Berkeley National Laboratory, Berkeley, California 94720, United States
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States); Univ. of California, Santa Cruz, CA (United States)
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States); Univ. of California, Berkeley, CA (United States)

Knowledge of the molecular composition and electronic structure of electrified solid-liquid interfaces is key to understanding elemental processes in heterogeneous reactions. Using X-ray absorption spectroscopy in the interface-sensitive electron yield mode (EY-XAS), first-principles electronic structure calculations, and multiscale simulations, we determined the chemical composition of the interfacial region of a polycrystalline platinum electrode in contact with aqueous sulfuric acid solution at potentials between the hydrogen and oxygen evolution reactions. We found that between 0.7 and 1.3 V vs Ag/AgCl the electrical double layer (EDL) region comprises adsorbed sulfate ions with hydrated hydronium ions in the next layer. No evidence was found for bisulfate or Pt-O/Pt-OH species, which have very distinctive spectral signatures. In addition to resolving the long-standing issue of the EDL structure, our work establishes interface- and element-sensitive EY-XAS as a powerful spectroscopic tool for studying condensed phase, buried solid-liquid interfaces relevant to various electrochemical processes and devices.

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Research Organization:: Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22). Materials Sciences & Engineering Division

Grant/Contract Number:: AC02-05CH11231

OSTI ID:: 1604655

Journal Information:: Journal of the American Chemical Society, Journal Name: Journal of the American Chemical Society Journal Issue: 47 Vol. 140; ISSN 0002-7863

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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Cited By (3)

The hydrogen evolution reaction: from material to interfacial descriptors Dubouis, Nicolas; Grimaud, Alexis Chemical Science, Vol. 10, Issue 40 https://doi.org/10.1039/c9sc03831k	journal	January 2019
DFT Calculations of the Electrochemical Adsorption of Sulfuric Acid Anions on the Pt(110) and Pt(100) Surfaces Santana, Juan A.; Ishikawa, Yasuyuki Electrocatalysis, Vol. 11, Issue 1 https://doi.org/10.1007/s12678-019-00574-x	journal	December 2019
The hydrogen evolution reaction: from material to interfacial descriptors Dubouis, Nicolas; Grimaud, Alexis Chemical Science, Vol. 10, Issue 40 https://doi.org/10.1039/c9sc03831k	journal	January 2019

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