Mo2C‐Based Ceramic Electrode with High Stability and Catalytic Activity for Hydrogen Evolution Reaction at High Current Density

Abstract Developing robust electrodes with high catalytic performance is a key step for expanding practical HER (hydrogen evolution reaction) applications. This paper reports on novel porous Mo 2 C‐based ceramics with oriented finger‐like holes directly used as self‐supported HER electrodes. Due to the suitable MoO 3 sintering additive, high‐strength (55 ± 6 MPa) ceramic substrates and a highly active catalytic layer are produced in one step. The in situ reaction between MoO 3 and Mo 2 C enabled the introduction of O in the Mo 2 C crystal lattice and the formation of Mo 2 C(O)/MoO 2 heterostructures. The optimal Mo 2 C‐based electrode displayed an overpotential of 333 and 212 mV at 70 °C under a high current intensity of 1500 mA cm −2 in 0.5 m H 2 SO 4 and 1.0 m KOH, respectively, which are markedly better than the performance of Pt wire electrode; furthermore, its price is three orders of magnitude lower than Pt. The chronopotentiometric curves recorded in the 50 – 1500 mA cm −2 range, confirmed its excellent long‐term stability in acidic and alkaline media for more than 260 h. Density functional theory (DFT) calculations showed that the Mo 2 C(O)/MoO 2 heterostructures has an optimum electronic structure with appropriate *H adsorption‐free energy in an acidic medium and minimum water dissociation energy barrier in an alkaline medium.