Abstract MoS2, as a low-cost catalyst for hydrogen evolution reaction (HER), suffers from poor catalytic performance on the basal plane. Herein, by doping 19 main-group elements on the S-defective MoS2 nanosheet, the most promising MoS2-based catalysts for the HER are screened with high-throughput density functional theory (DFT) calculations. Remarkably, the doping of main-group elements except chalcogens can improve the activity of the MoS2 basal plane to a certain extent. The S-defective MoS2 monolayer doped with In/Ge atom (In3@MoS2 and Ge3@MoS2) show excellent HER performance, and their reaction barrier is even lower than that of commercial Pt/C catalyst. In In3@MoS2 and Ge3@MoS2, the In/Ge atoms act as electron donors to increase the unoccupied anti-bonding orbital, which enhances the interaction of In/Ge-H bonding. On the other hand, the unique co-existence of electron-depletion and electron-accumulation regions near In/Ge atoms enables the adsorption of free radical H to be moderate. Moreover, the In/Ge atoms also increase the conductivity of MoS2, especially the In atom brings a new impurity state near the Fermi level. This work presents a promising strategy for exploiting high-performance MoS2-based catalysts for HER, and would stimulate more researchers to optimize other two-dimensional materials by doping main-group elements for HER.

中文翻译：

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IIIA-VIIA族元素掺杂促进MoS2基面析氢的理论筛选

摘要 二硫化钼作为析氢反应（HER）的低成本催化剂，其基面催化性能较差。在此，通过在 S 缺陷型 MoS2 纳米片上掺杂 19 种主族元素，通过高通量密度泛函理论 (DFT) 计算筛选出最有前途的用于 HER 的 MoS2 基催化剂。值得注意的是，掺杂除硫属元素以外的主族元素可以在一定程度上提高MoS2基面的活性。掺杂有 In/Ge 原子的 S 缺陷 MoS2 单层（In3@MoS2 和 Ge3@MoS2）表现出优异的 HER 性能，其反应势垒甚至低于商业 Pt/C 催化剂。在 In3@MoS2 和 Ge3@MoS2 中，In/Ge 原子作为电子供体增加了未占据的反键轨道，从而增强了 In/Ge-H 键的相互作用。另一方面，In/Ge 原子附近电子耗尽区和电子积累区的独特共存使自由基 H 的吸附适度。此外，In/Ge 原子还增加了 MoS2 的电导率，尤其是 In 原子带来了接近费米能级的新杂质态。这项工作为开发用于 HER 的高性能 MoS2 基催化剂提供了一种有前景的策略，并将刺激更多的研究人员通过掺杂主族元素来优化其他二维材料以用于 HER。