Revealing the role of interfacial water and key intermediates at ruthenium surfaces in the alkaline hydrogen evolution reaction

Xing Chen, Xiao-Ting Wang, Jia-Bo Le, Shu-Min Li, Xue Wang, Yu-Jin Zhang, Petar Radjenovic, Yu Zhao, Yao-Hui Wang, Xiu-Mei Lin (), Jin-Chao Dong () and Jian-Feng Li ()
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Xing Chen: iChEM, Xiamen University
Xiao-Ting Wang: iChEM, Xiamen University
Jia-Bo Le: Ningbo Institute of Materials Technology and Engineering, Chinese Academy of Sciences
Shu-Min Li: iChEM, Xiamen University
Xue Wang: Ningbo Institute of Materials Technology and Engineering, Chinese Academy of Sciences
Yu-Jin Zhang: iChEM, Xiamen University
Petar Radjenovic: iChEM, Xiamen University
Yu Zhao: iChEM, Xiamen University
Yao-Hui Wang: iChEM, Xiamen University
Xiu-Mei Lin: iChEM, Xiamen University
Jin-Chao Dong: iChEM, Xiamen University
Jian-Feng Li: iChEM, Xiamen University

Nature Communications, 2023, vol. 14, issue 1, 1-11

Abstract: Abstract Ruthenium exhibits comparable or even better alkaline hydrogen evolution reaction activity than platinum, however, the mechanistic aspects are yet to be settled, which are elucidated by combining in situ Raman spectroscopy and theoretical calculations herein. We simultaneously capture dynamic spectral evidence of Ru surfaces, interfacial water, *H and *OH intermediates. Ru surfaces exist in different valence states in the reaction potential range, dissociating interfacial water differently and generating two distinct *H, resulting in different activities. The local cation tuning effect of hydrated Na+ ion water and the large work function of high-valence Ru(n+) surfaces promote interfacial water dissociation. Moreover, compared to low-valence Ru(0) surfaces, high-valence Ru(n+) surfaces have more moderate adsorption energies for interfacial water, *H, and *OH. They, therefore, facilitate the activity. Our findings demonstrate the regulation of valence state on interfacial water, intermediates, and finally the catalytic activity, which provide guidelines for the rational design of high-efficiency catalysts.

Date: 2023
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DOI: 10.1038/s41467-023-41030-1

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