Charge self-regulation in 1T'''-MoS<sub>2</sub> structure with rich S vacancies for enhanced hydrogen evolution activity.

Guo, Xiaowei; Song, Erhong; Zhao, Wei; Xu, Shumao; Zhao, Wenli; Lei, Yongjiu; Fang, Yuqiang; Liu, Jianjun et al. · Nat Commun · 2022

basic_science · Level V

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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-MoS<sub>2</sub> 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 MoS<sub>2</sub> (1T'''-MoS<sub>2</sub>) structure, which is favarable for the generation of active electronic states to boost the hydrogen evolution reaction activity. The optimal 1T'''-MoS<sub>2</sub> sample exhibits a low overpotential of 158 mV at 10 mA cm<sup>-2</sup> and a Tafel slope of 74.5 mV dec<sup>-1</sup> in acidic conditions, which are far exceeding the 2H-MoS<sub>2</sub> counterpart (369 mV and 137 mV dec<sup>-1</sup>). 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'''-MoS<sub>2</sub> with rich S vacancies.