Electrocatalytic Activation in ReSe₂‐VSe₂ Alloy Nanosheets to Boost Water‐Splitting Hydrogen Evolution Reaction

Abstract It is challenging to control the electronic structure of 2D transition metal dichalcogenides (TMD) for extended applications in renewable energy devices. Here, ReSe₂‐VSe₂ (Re_1−xV_xSe₂) alloy nanosheets over the whole composition range via a colloidal reaction is synthesized. Increasing x makes the nanosheets more metallic and induces a 1T″‐to‐1T phase transition at x = 0.5–0.6. Compared to the MoSe₂‐VSe₂ and WSe₂‐VSe₂ alloy nanosheets, ReSe₂ and VSe₂ are mixed more homogeneously at the atomic scale. The alloy nanosheets at x = 0.1–0.7 exhibit an enhanced electrocatalytic activity toward acidic hydrogen evolution reaction (HER). In situ X‐ray absorption fine structure measurements reveal that alloying caused the Re and V atoms to be synergically more active in the HER. Gibbs free energy (ΔG_H*) and density of state calculations confirm that alloying and Se vacancies effectively activate the metal sites toward HER. The composition dependence of HER performance is explained by homogenous atomic mixing with the increased Se vacancies. The study provides a strategy for designing new TMD alloy nanosheets with enhanced catalytic activity.