The role of alkali metal cations and platinum-surface hydroxyl in the alkaline hydrogen evolution reaction

Shah, Aamir Hassan; Zhang, Zisheng; Huang, Zhihong; Wang, Sibo; Zhong, Guangyan; Wan, Chengzhang; Alexandrova, Anastassia N.; Huang, Yu; Duan, Xiangfeng

doi:10.1038/s41929-022-00851-x

Title: The role of alkali metal cations and platinum-surface hydroxyl in the alkaline hydrogen evolution reaction

Journal Article · Wed Oct 19 00:00:00 EDT 2022 · Nature Catalysis

DOI:https://doi.org/10.1038/s41929-022-00851-x· OSTI ID:1968774

^[1]; Zhang, Zisheng ^[1]; Huang, Zhihong ^[1];

^[1]; Zhong, Guangyan ^[1]; Wan, Chengzhang ^[1];

^[1];

^[1]

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

The platinum-catalysed hydrogen evolution reaction (HER) generally shows poorer kinetics in alkaline electrolyte and represents a key challenge for alkaline water electrolysis. In the presence of alkali metal cations and hydroxyl anions, the electrode–electrolyte (platinum–water) interface in an alkaline electrolyte is far more complex than that in an acidic electrolyte. Here we combine electrochemical impedance spectroscopy and an electrical transport spectroscopy approach to probe and understand the fundamental role of different cations (Li⁺, Na⁺ and K⁺) in HER kinetics. Our integrated studies suggest that the alkali metal cations play an indirect role in modifying the HER kinetics, with the smaller cations being less destabilizing to the hydroxyl adsorbate (OH_ad) species in the HER potential window, which favours a higher coverage of OH_ad on the platinum surface. Here, the surface OH_ad species are highly polar and act as both electronically favoured proton acceptors and geometrically favoured proton donors to promote water dissociation in alkaline media, thus boosting the Volmer-step kinetics and the HER activity.

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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). Chemical Sciences, Geosciences & Biosciences Division; USDOE Office of Science (SC), Basic Energy Sciences (BES). Scientific User Facilities Division

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

OSTI ID:: 1968774

Alternate ID(s):: OSTI ID: 2001182

Journal Information:: Nature Catalysis, Vol. 5, Issue 10; ISSN 2520-1158

Publisher:: Springer NatureCopyright Statement

Country of Publication:: United States

Language:: English

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