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 Mo2C-based ceramics with oriented finger-like holes directly used as self-supported HER electrodes. Due to the suitable MoO3 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 MoO3 and Mo2C enabled the introduction of O in the Mo2C crystal lattice and the formation of Mo2C(O)/MoO2 heterostructures. The optimal Mo2C-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 H2SO4 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 Mo2C(O)/MoO2 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.
Keywords: Mo2C(O)/MoO2 heterostructure; high current density; hydrogen evolution reaction (HER); open hole structure; self‐supported electrode.
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