Concurrent Vacancy and Adatom Defects of Mo1–xNbxSe₂ Alloy Nanosheets Enhance Electrochemical Performance of Hydrogen Evolution Reaction

Earth-abundant transition metal dichalcogenide nanosheets have emerged as an excellent catalyst for electrochemical water splitting to generate H₂. Alloying the nanosheets with heteroatoms is a promising strategy to enhance their catalytic performance. Herein, we synthesized hexagonal (2H) phase Mo1-xNbxSe₂ nanosheets over the whole composition range using a solvothermal reaction. Alloying results in a variety of atomic-scale crystal defects such as Se vacancies, metal vacancies, and adatoms. The defect content is maximized when x approaches 0.5. Detailed structure analysis revealed that the NbSe₂ bonding structures in the alloy phase are more disordered than the MoSe₂ ones. Compared to MoSe₂ and NbSe₂, Mo0.5Nb0.5Se₂ exhibits much higher electrocatalytic performance for hydrogen evolution reaction. First-principles calculation was performed for the formation energy in the models for vacancies and adatoms, supporting that the alloy phase has more defects than either NbSe₂ or MoSe₂. The calculation predicted that the separated NbSe₂ domain at x = 0.5 favors the concurrent formation of Nb/Se vacancies and adatoms in a highly cooperative way. Moreover, the Gibbs free energy along the reaction path suggests that the enhanced HER performance of alloy nanosheets originates from the higher concentration of defects that favor H atom adsorption.