Zinc Single Atom Confinement Effects on Catalysis in 1T-Phase Molybdenum Disulfide

Active sites are atomic sites within catalysts that drive reactions and are essential for catalysis. Spatially confining guest metals within active site microenvironments has been predicted to improve catalytic activity by altering the electronic states of active sites. Using the hydrogen evolution reaction (HER) as a model reaction, we show that intercalating zinc single atoms between layers of 1T-MoS₂ (Zn SAs/1T-MoS₂) enhances HER performance by decreasing the overpotential, charge transfer resistance, and kinetic barrier. The confined Zn atoms tetrahedrally coordinate to basal sulfur (S) atoms and expand the interlayer spacing of 1T-MoS₂ by ∼3.4%. Under confinement, the Zn SAs donate electrons to coordinated S atoms, which lowers the free energy barrier of H* adsorption-desorption and enhances HER kinetics. In this work, which is applicable to all types of catalytic reactions and layered materials, HER performance is enhanced by controlling the coordination geometry and electronic states of transition metals confined within active-site microenvironments.