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Research Article | Open Access

Performance evaluation of homogeneous dual-atom site M2-N6-graphene catalysts for hydrogen evolution reaction

Jing Meng1,§, Letong Feng1,§, Zhaoyang Zhang1,2, Liang Zhang2, Xiangwen Liu3 (), Zhenwei Zhang4 (), Wenming Sun1 ()
Department of Chemistry, Capital Normal University, Beijing 100048, China
Dassault Systemes (Shanghai) Information Technology Co., Ltd., Shanghai 200120, China
Institute of Analysis and Testing, Beijing Academy of Science and Technology, Beijing 100094, China
Linyi Vocational University of Science and Technology (Linyi Branch of Steinbeis Intelligent Manufacturing Technology Transfer Center), Linyi 276000, China

§ Jing Meng and Letong Feng contributed equally to this work.

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We constructed a workflow containing both thermodynamic and kinetic descriptors and revealed that the shared nitrogen atoms between dual metal atoms can serve as crucial adsorption sites for hydrogen. This study provides valuable insights for the rational design of efficient hydrogen evolution reaction (HER) catalysts.

Abstract

Using first-principles calculations, we systematically investigated the hydrogen evolution reaction (HER) potential of 27 types of homogeneous dual-atom M2-N6-graphene catalysts. Shared nitrogen atoms between dual metal atoms were identified as crucial adsorption sites for hydrogen atoms. Notably, we found that relying solely on the free energy of hydrogen adsorption (ΔGH∗) could exclude the extremely unfavorable substrates, but may lead to misleading assessments of HER activation for substrates with modest ΔGH∗. Thermodynamic activity evaluation reveals that M2-N6-graphene (M = Cr, Co, Ni, Cu, Os, Pt) models exhibit promising HER activities. Kinetic analysis, based on the Volmer–Tafel mechanism, determined that the hydrogen coverage and relative distance between the adsorbed hydrogen atoms in the Tafel step affect the reaction energy barrier significantly. The coverage limits depend on the reaction free energy of the non-spontaneous third hydrogen adsorption step. By integrating the kinetic metric with thermodynamic assessments, we propose that the Co2-N6-graphene model displays superior HER activity. We further recommend selecting one of the metal positions in MaMb-N6-graphene to be Cr and excluding Cu and Ni elements during the selection of the second metal atom when designing heterogeneous MaMb-N6-graphene for alkaline HER catalyst. This study establishes a convenient workflow and provides valuable insights for the rational design of efficient HER catalysts.

Keywords

shared nitrogen sitehydrogen evolution reaction (HER)dual-atom site catalystM2-N6-graphene

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Nano Research
Volume 18 Issue 1,
January 2025
Article number: 94907004
DOI: 10.26599/NR.2025.94907004
Cite this article:
Meng J, Feng L, Zhang Z, et al. Performance evaluation of homogeneous dual-atom site M2-N6-graphene catalysts for hydrogen evolution reaction. Nano Research, 2025, 18(1): 94907004. https://doi.org/10.26599/NR.2025.94907004
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