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 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 ± 6MPa) 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 212mV at 70°C under a high current intensity of 1500 mAcm-2 in 0.5m H2SO4 and 1.0m 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 mAcm-2 range, confirmed its excellent long-term stability in acidic and alkaline media for more than 260h. 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.