Urchin‐Like Structured MoO2/Mo3P/Mo2C Triple‐Interface Heterojunction Encapsulated within Nitrogen‐Doped Carbon for Enhanced Hydrogen Evolution Reaction

Abstract The development of highly efficient and cost‐effective hydrogen evolution reaction (HER) catalysts is highly desirable to efficiently promote the HER process, especially under alkaline condition. Herein, a polyoxometalates‐organic‐complex‐induced carbonization method is developed to construct MoO 2 /Mo 3 P/Mo 2 C triple‐interface heterojunction encapsulated into nitrogen‐doped carbon with urchin‐like structure using ammonium phosphomolybdate and dopamine. Furthermore, the mass ratio of dopamine and ammonium phosphomolybdate is found critical for the successful formation of such triple‐interface heterojunction. Theoretical calculation results demonstrate that such triple‐interface heterojunctions possess thermodynamically favorable water dissociation Gibbs free energy (ΔG H2O ) of ‐1.28 eV and hydrogen adsorption Gibbs free energy (ΔG H* ) of ‐0.41 eV due to the synergistic effect of Mo 2 C and Mo 3 P as water dissociation site and H* adsorption/desorption sites during the HER process in comparison to the corresponding single components. Notably, the optimal heterostructures exhibit the highest HER activity with the low overpotential of 69 mV at the current density of 10 mA cm −2 and a small Tafel slope of 60.4 mV dec −1 as well as good long‐term stability for 125 h. Such remarkable results have been theoretically and experimentally proven to be due to the synergistic effect between the unique heterostructures and the encapsulated nitrogen‐doped carbon.