Platinum Surface Water Orientation Dictates Hydrogen Evolution Reaction Kinetics in Alkaline Media

Shah, Aamir Hassan; Zhang, Zisheng; Wan, Chengzhang; Wang, Sibo; Zhang, Ao; Wang, Laiyuan; Alexandrova, Anastassia N.; Huang, Yu; Duan, Xiangfeng

doi:10.1021/jacs.3c12934

Title: Platinum Surface Water Orientation Dictates Hydrogen Evolution Reaction Kinetics in Alkaline Media

Journal Article · 26 March 2024 · Journal of the American Chemical Society

DOI: https://doi.org/10.1021/jacs.3c12934 · OSTI ID:2337929

^[1];

^[2]; Wan, Chengzhang ^[2]; Wang, Sibo ^[2]; Zhang, Ao ^[2]; Wang, Laiyuan ^[2];

^[3];

^[3]

Univ. of California, Los Angeles, CA (United States); UCLA
Univ. of California, Los Angeles, CA (United States)
Univ. of California, Los Angeles, CA (United States); California NanoSystems Institute, Los Angeles, CA (United States)

The fundamental understanding of sluggish hydrogen evolution reaction (HER) kinetics on a platinum (Pt) surface in alkaline media is a topic of considerable debate. Herein, we combine cyclic voltammetry (CV) and electrical transport spectroscopy (ETS) approaches to probe the Pt surface at different pH values and develop molecular-level insights into the pH-dependent HER kinetics in alkaline media. The change in HER Tafel slope from ~110 mV/decade in pH 7–10 to ~53 mV/decade in pH 11–13 suggests considerably enhanced kinetics at higher pH. The ETS studies reveal a similar pH-dependent switch in the ETS conductance signal at around pH 10, suggesting a notable change of surface adsorbates. Fixed-potential calculations and chemical bonding analysis suggest that this switch is attributed to a change in interfacial water orientation, shifting from primarily an O-down configuration below pH 10 to a H-down configuration above pH 10. This reorientation weakens the O–H bond in the interfacial water molecules and modifies the reaction pathway, leading to considerably accelerated HER kinetics at higher pH. Finally, our integrated studies provide an unprecedented molecular-level understanding of the nontrivial pH-dependent HER kinetics in alkaline media.

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Research Organization:: Univ. of California, Los Angeles, CA (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES); US Department of the Navy, Office of Naval Research (ONR)

Grant/Contract Number:: SC0019152; AC02-06CH11357

OSTI ID:: 2337929

Journal Information:: Journal of the American Chemical Society, Journal Name: Journal of the American Chemical Society Journal Issue: 14 Vol. 146; ISSN 0002-7863

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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