Charge self-regulation in 1T'''-MoS2 structure with rich S vacancies for enhanced hydrogen evolution activity

Xiaowei Guo; Erhong Song; Wei Zhao; Shumao Xu; Wenli Zhao; Yongjiu Lei; Yuqiang Fang; Jianjun Liu; Fuqiang Huang

doi:10.1038/s41467-022-33636-8

Charge self-regulation in 1T'''-MoS₂ structure with rich S vacancies for enhanced hydrogen evolution activity

Nat Commun. 2022 Oct 10;13(1):5954. doi: 10.1038/s41467-022-33636-8.

Authors

Xiaowei Guo^#^{1

2}, Erhong Song^#^{1

2}, Wei Zhao^#^{1

2}, Shumao Xu¹, Wenli Zhao³, Yongjiu Lei⁴, Yuqiang Fang^{1

2}, Jianjun Liu^{5

6

7}, Fuqiang Huang^{8

9

10}

Affiliations

¹ State Key Laboratory of High Performance Ceramics and Superfine Microstructure, Shanghai Institute of Ceramics, Chinese Academy of Sciences, 200050, Shanghai, China.
² Center of Materials Science and Optoelectronics Engineering, University of Chinese Academy of Science, 100049, Beijing, China.
³ School of Physical and Mathematical Sciences, Nanjing Tech University, 211800, Nanjing, China.
⁴ Materials Science and Engineering, King Abdullah University of Science and Technology (KAUST), Thuwal, 23955-6900, Saudi Arabia.
⁵ State Key Laboratory of High Performance Ceramics and Superfine Microstructure, Shanghai Institute of Ceramics, Chinese Academy of Sciences, 200050, Shanghai, China. jliu@mail.sic.ac.cn.
⁶ Center of Materials Science and Optoelectronics Engineering, University of Chinese Academy of Science, 100049, Beijing, China. jliu@mail.sic.ac.cn.
⁷ Shanghai Institute of Materials Genome, 99 Shangda road, 200444, Shanghai, China. jliu@mail.sic.ac.cn.
⁸ State Key Laboratory of High Performance Ceramics and Superfine Microstructure, Shanghai Institute of Ceramics, Chinese Academy of Sciences, 200050, Shanghai, China. huangfq@mail.sic.ac.cn.
⁹ Center of Materials Science and Optoelectronics Engineering, University of Chinese Academy of Science, 100049, Beijing, China. huangfq@mail.sic.ac.cn.
¹⁰ State Key Laboratory of Rare Earth Materials Chemistry and Applications, College of Chemistry and Molecular Engineering, Peking University, 100871, Beijing, China. huangfq@mail.sic.ac.cn.

^# Contributed equally.

Abstract

Active electronic states in transition metal dichalcogenides are able to prompt hydrogen evolution by improving hydrogen absorption. However, the development of thermodynamically stable hexagonal 2H-MoS₂ as hydrogen evolution catalyst is likely to be shadowed by its limited active electronic state. Herein, the charge self-regulation effect mediated by tuning Mo-Mo bonds and S vacancies is revealed in metastable trigonal MoS₂ (1T'''-MoS₂) structure, which is favarable for the generation of active electronic states to boost the hydrogen evolution reaction activity. The optimal 1T'''-MoS₂ sample exhibits a low overpotential of 158 mV at 10 mA cm^-2 and a Tafel slope of 74.5 mV dec^-1 in acidic conditions, which are far exceeding the 2H-MoS₂ counterpart (369 mV and 137 mV dec^-1). Theoretical modeling indicates that the boosted performance is attributed to the formation of massive active electronic states induced by the charge self-regulation effect of Mo-Mo bonds in defective 1T'''-MoS₂ with rich S vacancies.

Grants and funding

21871008, 21801247, 21872166, 21973107 and 51702345/National Natural Science Foundation of China (National Science Foundation of China)