Mo2 C-Based Ceramic Electrode with High Stability and Catalytic Activity for Hydrogen Evolution Reaction at High Current Density.

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 Mo2 C-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 Mo2 C enabled the introduction of O in the Mo2 C crystal lattice and the formation of Mo2 C(O)/MoO2 heterostructures. The optimal Mo2 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 H2 SO4 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 Mo2 C(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.

Robust Porous WC-Based Self-Supported Ceramic Electrodes for High Current Density Hydrogen Evolution Reaction.

Developing an economical, durable, and efficient electrode that performs well at high current densities and is capable of satisfying large-scale electrochemical hydrogen production is highly demanded. A self-supported electrocatalytic "Pt-like" WC porous electrode with open finger-like holes is produced through industrial processes, and a tightly bonded nitrogen-doped WC/W (WC-N/W) heterostructure is formed in situ on the WC grains. The obtained WC-N/W electrode manifests excellent durability and stability under multi-step current density in the range of 30-1000 mA cm-2 for more than 220 h in both acidic and alkaline media. Although WC is three orders of magnitude cheaper than Pt, the produced electrode demonstrates comparable hydrogen evolution reaction performance to the Pt electrode at high current density. Density functional theory calculations attribute its superior performance to the electrode structure and the modulated electronic structure at the WC-N/W interface.