Regulating Local Atomic Environment around Vacancies for Efficient Hydrogen Evolution

Defect engineering is essential for the development of efficient electrocatalysts at the atomic level. While most work has focused on various vacancies as effective catalytic modulators, little attention has been paid to the relation between the local atomic environment of vacancies and catalytic activities. To face this challenge, we report a facile synthetic approach to manipulate the local atomic environments of vacancies in MoS₂ with tunable Mo-to-S ratios. Our studies indicate that the MoS₂ with more Mo terminated vacancies exhibits better hydrogen evolution reaction (HER) performance than MoS₂ with S terminated vacancies and defect-free MoS₂. The improved performance originates from the adjustable orbital orientation and distribution, which is beneficial for regulating H adsorption and eventually boosting the intrinsic per-site activity. This work uncovers the underlying essence of the local atomic environment of vacancies on catalysis and provides a significant extension of defect engineering for the rational design of transition metal dichalcogenides (TMDs) catalysts and beyond.