Defect engineering of 1T'MX2(M= Mo, W andX= S, Se) transition metal dichalcogenide-based electrocatalyst for alkaline hydrogen evolution reaction.

The alkaline electrolyzer (AEL) is a promising device for green hydrogen production. However, their energy conversion efficiency is currently limited by the low performance of the electrocatalysts for the hydrogen evolution reaction (HER). As such, the electrocatalyst design for the high-performance HER becomes essential for the advancement of AELs. In this work, we used both hydrogen (H) and hydroxyl (OH) adsorption Gibbs free energy changes as the descriptors to investigate the catalytic HER performance of 1T' transition metal dichalcogenides (TMDs) in an alkaline solution. Our results reveal that the pristine sulfides showed better alkaline HER performance than their selenide counterparts. However, the activities of all pristine 1T' TMDs are too low to dissociate water. To improve the performance of these materials, defect engineering techniques were used to design TMD-based electrocatalysts for effective HER activity. Our density functional theory results demonstrate that introducing single S/Se vacancy defects can improve the reactivities of TMD materials. Yet, the desorption of OH becomes the rate-determining step. Doping defective MoS2with late 3d transition metal (TM) atoms, especially Cu, Ni, and Co, can regulate the reactivity of active sites for optimal OH desorption. As a result, the TM-doped defective 1T' MoS2can significantly enhance the alkaline HER performance. These findings highlight the potential of defect engineering technologies for the design of TMD-based alkaline HER electrocatalysts.

Vacancy impacts on electronic and mechanical properties of MX2 (M = Mo, W and X = S, Se) monolayers.

Monolayers of transition metal dichalcogenides (TMD) exhibit excellent mechanical and electrical characteristics. Previous studies have shown that vacancies are frequently created during the synthesis, which can alter the physicochemical characteristics of TMDs. Even though the properties of pristine TMD structures are well studied, the effects of vacancies on the electrical and mechanical properties have received far less attention. In this paper, we applied first-principles density functional theory (DFT) to comparatively investigate the properties of defective TMD monolayers including molybdenum disulfide (MoS2), molybdenum diselenide (MoSe2), tungsten disulfide (WS2), and tungsten diselenide (WSe2). The impacts of six types of anion or metal complex vacancies were studied. According to our findings, the electronic and mechanical properties are slightly impacted by anion vacancy defects. In contrast, vacancies in metal complexes considerably affect their electronic and mechanical properties. Additionally, the mechanical properties of TMDs are significantly influenced by both their structural phases and anions. Specifically, defective diselenides become more mechanically unstable due to the comparatively poor bonding strength between Se and metal based on the analysis of the crystal orbital Hamilton population (COHP). The outcomes of this study may provide the theoretical knowledge base to boost more applications of the TMD systems through defect engineering.