Surface selectivity of Ni3S2 toward hydrogen evolution reaction: a first-principles study

Bo Zhang; Xiuli Fu; Li Song; Xiaojun Wu

doi:10.1039/D0CP03845H

Surface selectivity of Ni₃S₂ toward hydrogen evolution reaction: a first-principles study†

Bo Zhang,

^a Xiuli Fu,

*^a Li Song

^b and Xiaojun Wu

*^c

Author affiliations

* Corresponding authors

^a State Key Laboratory of Information Photonics and Optical Communications, and School of Science, Beijing University of Posts and Telecommunications, Beijing 100876, P. R. China
E-mail: xiulifu@bupt.edu.cn
Fax: +86-10-62282242
Tel: +86-10-62282242

^b University of Science and Technology of China, National Synchrotron Radiation Laboratory, CAS Center for Excellence in Nanoscience, CAS Key Laboratory of Strongly-Coupled Quantum Matter Physics, Hefei 230029, Anhui, P. R. China

^c Hefei National Laboratory for Physical Sciences at the Microscale, School of Chemistry and Materials Sciences, CAS Key Laboratory of Materials for Energy Conversion, CAS Center for Excellence in Nanoscience, University of Science and Technology of China, Hefei 230026, P. R. China
E-mail: xjwu@ustc.edu.cn

Abstract

Exploring materials with high catalytic performance toward hydrogen evolution reaction (HER) is of importance for the development of clean hydrogen energy, and their surface structure is essential for this function. In this study, using density functional theory (DFT), we reported a comprehensive study on the phase stability, surface structures, electronic properties and HER catalytic properties of the low-index surfaces of Ni₃S₂, including the (0001), (10 [1 with combining macron] 0), (101), (11 [2 with combining macron] 0) and (111) planes with different terminations. Our calculated results demonstrate that S-rich surfaces and several stoichiometric surfaces of Ni₃S₂ are thermodynamically stable, including (0001)A, (100)A, (110)C, (100)C, (100)B and (111)A surfaces. Among the six stable surface structures, the (0001)A, (10 [1 with combining macron] 0)B and (100)C surfaces of Ni₃S₂ are indispensable for high HER performance because of their high catalytic activity, suitable potential and high thermodynamic stability. The calculated changes of Gibbs free energy (ΔG_H*) of the Top S2 site on (0001)A, Hollow Ni₂S₃S₄ site on (10 [1 with combining macron] 0)C, and Bridge Ni₁Ni₃ site and Hollow Ni₂S₁S₂ site on (100)B are −0.143, 0.122, 0.012, and −0.112 eV, respectively, comparable with or even better than those of Pt(111) (−0.07 eV). In addition, the possible Volmer–Heyrovsky and Volmer–Tafel processes on the considered surfaces are also investigated. When the overpotential is in the range of 0 to 300 mV, the density of active sites on the (10 [1 with combining macron] 0)B surface of Ni₃S₂ is found to be the highest. This work provides significant insights on the surface selectivity of Ni₃S₂ toward HER and provides a route to optimize the performance of Ni₃S₂ with exposed surfaces.

Physical Chemistry Chemical Physics

Surface selectivity of Ni₃S₂ toward hydrogen evolution reaction: a first-principles study†

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Surface selectivity of Ni₃S₂ toward hydrogen evolution reaction: a first-principles study

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Physical Chemistry Chemical Physics