Simultaneous phase and electronic structure regulation of MoC via B,N-doping and bimetallic synergy for efficient hydrogen evolution

Abstract

To address the challenges of poor H adsorption, agglomeration, and acidic instability in Mo_xC for HER, we synthesized Co,Ni-modified MoC nanocrystals embedded in a B,N-doped carbon matrix (Co,Ni–MoC@BNC) via molten-salt pyrolysis of POM@ZIF precursors. The catalyst achieves a low overpotential of 127 mV at 10 mA cm⁻² and 30-h stability in 0.5 M H₂SO₄, outperforming commercial Pt/C at high current densities. Density functional theory calculations reveal that Co d-orbital and C p-orbital hybridization, modulated by B-doping, optimizes the hydrogen adsorption free energy (ΔG_H* = 0.21 eV), approaching the ideal value.