Identifying the Active Sites in MoSi 2 @MoO 3 Heterojunctions for Enhanced Hydrogen Evolution

Developing Two‐dimensional (2D) Mo‐based heterogeneous nanomaterials is of great significance for energy conversion, especially in alkaline hydrogen evolution reaction (HER), however, it remains a challenge to identify the active sites at the interface due to the structure complexity. Herein, the real active sites are systematically explored during the HER process in varied Mo‐based 2D materials by theoretical computational and magnetron sputtering approaches first to filtrate the candidates, then successfully combined the MoSi 2 and MoO 3 together through Oxygen doping to construct heterojunctions. Benefiting from the synergistic effects between the MoSi 2 and MoO 3 , the obtained MoSi 2 @MoO 3 exhibits an unprecedented overpotential of 72 mV at a current density of 10 mA cm −2 . Density functional theory calculations uncover the different Gibbs free energy of hydrogen adsorption (Δ G H* ) values achieved at the interfaces with different sites as adsorption sites. The results can facilitate the optimization of heterojunction electrocatalyst design principles for the Mo‐based 2D materials.