Well-Defined Mo2C Nanoparticles Embedded in Porous N-Doped Carbon Matrix for Highly Efficient Electrocatalytic Hydrogen Evolution.

On the design of efficient and affordable electrocatalysts for water reduction half reaction, this paper fabricates molybdenum carbide nanoparticles uniformly loaded in highly porous N-doped carbon matrix derived from polyaniline-molybdate monolith with the use of graphitic carbon nitride (g-C3N4) as template. The obtained molybdenum carbide-carbon hybrid catalysts (MoC@NCS) exhibit extraordinarily electrochemical hydrogen evolution activity with a small overpotential of 89 and 81 mV to deliver a current density of 10 mA cm-2 in alkaline (1.0 M KOH) and acidic (0.5 M H2SO4) medium, respectively, even comparable to noble-metal Pt/C benchmark. Specially, MoC@NCS also shows excellent long-term durability in alkaline or acidic electrolyte. Furthermore, the obtained carbon matrix (NCS) featuring high content of N dopants and hierarchically porous architecture exhibits high catalytic efficiency for oxygen evolution reaction in alkaline electrolyte. For a further step, the obtained NCS coupled with the MoC@NCS, working as anodic and cathodic electrodes, in a two-electrode alkaline electrolyzer for overall water splitting, which can obtain a current density of 10 mA cm-2 at 1.69 V, along with robust operation durability. The synergistic effect of the porous carbon matrix of high nitrogen content and the molybdenum carbide nanoparticles of uniform distribution, together with hierarchically porous structure, should be responsible for the outstanding electrocatalytic HER performance. This work presents an easy and cost-effective strategy to prepare molybdenum-based materials with controlled size for electrocatalytic hydrogen evolution.