Boosting Alkaline Hydrogen Evolution on Stoichiometric Molybdenum Carbonitride via an Interstitial Vacancy‐Elimination Strategy

Abstract

AbstractAn interstitial vacancy on molybdenum nitride has been determined as a negative factor towards the alkaline hydrogen evolution reaction (HER) by reason of upraising the d orbitals of Mo. Nevertheless, investigations aiming to eliminate the vacancies are rarely reported. Here, an interstitial reconfiguration method for the design of stoichiometric molybdenum carbonitride (Mo2CN) is proposed, in which the vacancies are fulfilled by lattice carbon. Multiple fine structural analyses alongside with the theoretical calculations indicate that beyond lower the d orbitals of Mo by the hybridization of additive p‐d orbitals, lattice carbon also behaves as the extra active center with exceptional H adsorption/desorption energy. Mo2CN reveals an adorable overpotential of −84 mV at a current density of 10 mA cm−2 with a long‐term electrochemical stability by accompanying the nitrogen‐doped carbon substrate. It is anticipated that the vacancy‐eliminating concept will provide a constructive entry point for the rational design of electro‐catalysts and beyond.