Crystalline Phase Engineering to Modulate the Interfacial Interaction of the Ruthenium/Molybdenum Carbide for Acidic Hydrogen Evolution.

Ruthenium (Ru) is an ideal substitute to commercial Pt/C for the acidic hydrogen evolution reaction (HER), but it still suffers from undesirable activity due to the strong adsorption free energy of H* (ΔGH*). Herein, we propose crystalline phase engineering by loading Ru clusters on precisely prepared cubic and hexagonal molybdenum carbide (α-MoC/β-Mo2C) supports to modulate the interfacial interactions and achieve high HER activity. Advanced spectroscopies demonstrate that Ru on β-Mo2C shows a lower valence state and withdraws more electrons from the support than that of Ru on α-MoC, indicative of a strong interfacial interaction. Density functional theory reveals that the ΔGH* of Ru/β-Mo2C approaches 0 eV, illuminating an enhancement mechanism at the Ru/β-Mo2C interface. The resultant Ru/β-Mo2C exhibits an encouraging performance in a proton exchange membrane water electrolyzer with a low cell voltage (1.58 V@ 1.0 A cm-2) and long stability (500 h@ 1.0 A cm-2).