The Role of Phosphate Group in Doped Cobalt Molybdate: Improved Electrocatalytic Hydrogen Evolution Performance

The hydrogen evolution reaction (HER) is a critical process in the electrolysis of water. Recently, much effort has been dedicated to developing low‐cost, highly efficient, and stable electrocatalysts. Transition metal phosphides are investigated intensively due to their high electronic conductivity and optimized absorption energy of intermediates in acid electrolytes. However, the low stability of metal phosphide materials in air and during electrocatalytic processes causes a decay of performance and hinders the discovery of specific active sites. The HER in alkaline media is more intricate, which requires further delicate design due to the Volmer steps. In this work, phosphorus‐modified monoclinic β‐CoMoO_{4} is developed as a low‐cost, efficient, and stable HER electrocatalyst for the electrolysis of water in alkaline media. The optimized catalyst shows a small overpotential of 94 mV to reach a current density of 10 mA cm^{-2} for the HER with high stability in KOH electrolyte, and an overpotential of 197 mV to reach a current density of 100 mA cm^{−2}. Combined computational and in situ spectroscopic techniques show P is present as a surface phosphate ion; that electron holes localize on the surface ions and both (P-O^{-1}) and Co^{3+}-OH^{-} are prospective surface active sites for the HER.