Full Composition Tuning of W 1- x Nb x Se 2 Alloy Nanosheets to Promote the Electrocatalytic Hydrogen Evolution Reaction.

Composition modulation of transition metal dichalcogenides is an effective way to engineer their crystal/electronic structures for expanded applications. Here, fully composition-tuned W 1- x Nb x Se 2 alloy nanosheets were produced via colloidal synthesis. These nanosheets ultimately exhibited a notable transition between WSe 2 and NbSe 2 hexagonal phases at x = 0.6. As x approaches 0.6, point doping is converted into cluster doping and eventually separated domains of WSe 2 and NbSe 2 . Extensive density functional theory calculations predicted the composition-dependent crystal structures and phase transitions, consistently with the experiments. The electrocatalytic activity for the hydrogen evolution reaction (HER) in acidic electrolyte was significantly enhanced at x = 0.2, which was linked with the d - band center. The Gibbs free energy for the H adsorption at various basal and edge sites supported the enhanced HER performance of the metallic alloy nanosheets. We suggested that the dispersed doping structures of Nb atoms resulted in the best HER performance. Our findings highlight the significance of composition tuning in enhancing the catalytic activity of alloys.