Atomically Dispersed Mo Sites Anchored on Multichannel Carbon Nanofibers toward Superior Electrocatalytic Hydrogen Evolution

Developing affordable and efficient electrocatalysts as precious metal alternatives toward the hydrogen evolution reaction (HER) is crucially essential for the substantial progress of sustainable H₂ energy-related technologies. The dual manipulation of coordination chemistry and geometric configuration for single-atom catalysts (SACs) has emerged as a powerful strategy to surmount the thermodynamic and kinetic dilemmas for high-efficiency electrocatalysis. We herein rationally designed N-doped multichannel carbon nanofibers supporting atomically dispersed Mo sites coordinated with C, N, and O triple components (labeled as Mo@NMCNFs hereafter) as a superior HER electrocatalyst. Systematic characterizations revealed that the local coordination microenvironment of Mo is determined to be a Mo-O₁N₁C₂ moiety, which was theoretically probed to be the energetically favorable configuration for H intermediate adsorption by density functional theory calculations. Structurally, the multichannel porous carbon nanofibers with open ends could effectively enlarge the exposure of active sites, facilitate mass diffusion/charge transfer, and accelerate H₂ release, leading to promoted reaction kinetics. Consequently, the optimized Mo@NMCNFs exhibited superior Pt-like HER performance in 0.5 M H₂SO₄ electrolyte with an overpotential of 66 mV at 10 mA cm^-2, a Tafel slope of 48.9 mV dec^-1, and excellent stability, outperforming a vast majority of the previously reported nonprecious HER electrocatalysts. The concept of both geometric and electronic engineering of SACs in this work may provide guidance for the design of high-efficiency molecule-like heterogeneous catalysts for a myriad of energy technologies.