It is highly demanded to steer the charge flow in photocatalysts for efficient photocatalytic hydrogen reactions (PHRs). In this study, we developed a smart strategy to position MoS quantum dots (QDs) at the S vacancies on a Zn facet in monolayered ZnInS (Vs-M-ZnInS) to craft a two-dimensional (2D) atomic-level heterostructure (MoSQDs@Vs-M-ZnInS). The electronic structure calculations indicated that the positive charge density of the Zn atom around the sulfur vacancy (Vs) was more intensive than other Zn atoms. The Vs confined in monolayered ZnInS established an important link between the electronic manipulation and activities of ZnInS. The Vs acted as electron traps, prevented vertical transmission of electrons, and enriched electrons onto the Zn facet. The Vs-induced atomic-level heterostructure sewed up vacancy structures of Vs-M-ZnInS, resulting in a highly efficient interface with low edge contact resistance. Photogenerated electrons could quickly migrate to MoSQDs through the intimate Zn-S bond interfaces. As a result, MoSQDs@Vs-M-ZnInS showed a high PHR activity of 6.884 mmol g h, which was 11 times higher than 0.623 mmol g h for bulk ZnInS, and the apparent quantum efficiency reached as high as 63.87% (420 nm). This work provides a prototype material for looking into the role of vacancies between electronic structures and activities in 2D photocatalytic materials and gives insights into PHR systems at the atomic level.

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The metallic 1T-MoS has attracted considerable attention as an effective catalyst for hydrogen evolution reactions (HERs). However, the fundamental mechanism about the catalytic activity of 1T-MoS and the associated phase evolution remain elusive and controversial. Herein, we prepared the most stable 1T-MoS by hydrothermal exfoliation of MoS nanosheets vertically rooted into rigid one-dimensional TiO nanofibers. The 1T-MoS can keep highly stable over one year, presenting an ideal model system for investigating the HER catalytic activities as a function of the phase evolution. Both experimental studies and theoretical calculations suggest that 1T phase can be irreversibly transformed into a more active 1T' phase as true active sites in photocatalytic HERs, resulting in a "catalytic site self-optimization". Hydrogen atom adsorption is the major driving force for this phase transition.

Monolayer MoS2nanosheets with activated basal planes have been prepared using a simple hydrothermal method.

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