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Research Article

Key role of electron accessibility at the noble metal-free catalytic interface in hydrogen evolution reaction

Dongchen Han1,2,3,4, Nanxing Gao1,2,3,4, Yuyi Chu1,2,3,4, Zhaoping Shi1,2,3,4, Ying Wang5( ), Junjie Ge2( ), Meiling Xiao1,2,3,4( ), Changpeng Liu1,2,3,4( ), Wei Xing1,2,3,4( )
State Key Laboratory of Electroanalytical Chemistry, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, Changchun 130022, China
School of Applied Chemistry and Engineering, University of Science and Technology of China, Hefei 230026, China
Laboratory of Advanced Power Sources, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, Changchun 130022, China
Jilin Province Key Laboratory of Low Carbon Chemical Power Sources, Changchun 130022, China
State Key Laboratory of Rare Earth Resource Utilization, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, Changchun 130022, China
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Graphical Abstract

We demonstrate the interrelation of conductivity and hydrogen evolution reaction (HER) apparent activity of catalysts, and elucidate the key role of conductivity of catalyst towards water electrolysis. We propose a mechanism to evaluate overall catalytic activity based on electron accessibility and ΔGH from the view of dynamics and thermodynamics.

Abstract

The reactant concentration at the catalytic interface holds the key to the activity of electrocatalytic hydrogen evolution reaction (HER), mainly referring to the capacity of adsorbing hydrogen and electron accessibility. With hydrogen adsorption free energy (ΔGH) as a reactivity descriptor, the volcano curve based on Sabatier principle is established to evaluate the hydrogen evolution activity of catalysts. However, the role of electron as reactant received insufficient attention, especially for noble metal-free compound catalysts with poor conductivity, leading to cognitive gap between electronic conductivity and apparent catalytic activity. Herein we successfully construct a series of catalyst models with gradient conductivities by regulating molybdenum disulfide (MoS2) electronic bandgap via a simple solvothermal method. We demonstrate that the conductivity of catalysts greatly affects the overall catalytic activity. We further elucidate the key role of intrinsic conductivity of catalyst towards water electrolysis, mainly concentrating on the electron transport from electrode to catalyst, the electron accumulation process at the catalyst layer, and the charge transfer progress from catalyst to reactant. Theoretical and experimental evidence demonstrates that, with the enhancement in electron accessibility at the catalytic interface, the dominant parameter governing overall HER activity gradually converts from electron accessibility to combination of electron accessibility and hydrogen adsorbing energy. Our results provide the insight from various perspective for developing noble metal-free catalysts in electrocatalysis beyond HER.

Keywords

conductivitymolybdenum disulfidecatalytic interfaceelectron accessibilityhydrogen evolutioncharge transfer.

Electronic Supplementary Material

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Nano Research
Volume 17 Issue 4,
April 2024
Pages 2538-2545
DOI: 10.1007/s12274-023-6229-2
Cite this article:
Han D, Gao N, Chu Y, et al. Key role of electron accessibility at the noble metal-free catalytic interface in hydrogen evolution reaction. Nano Research, 2024, 17(4): 2538-2545. https://doi.org/10.1007/s12274-023-6229-2
Topics:
Hydrogen evolution reaction

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Received: 28 July 2023
Revised: 18 September 2023
Accepted: 24 September 2023
Published: 17 November 2023
© Tsinghua University Press 2023
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