Ambient γ‐Rays‐Mediated Noble‐Metal Deposition on Defect‐Rich Manganese Oxide for Glycerol‐Assisted H₂ Evolution at Industrial‐Level Current Density

Abstract

Developing novel synthesis technologies is crucial to expanding bifunctional electrocatalysts for energy‐saving hydrogen production. Herein, we report an ambient and controllable γ‐ray radiation reduction to synthesize a series of noble metal nanoparticles anchored on defect‐rich manganese oxides (M@MnO2‐x, M=Ru, Pt, Pd, Ir) for glycerol‐assisted H2 evolution. Benefiting from the strong penetrability of γ‐rays, nanoparticles and defect supports are formed simultaneously and bridged by metal‐oxygen bonds, guaranteeing structural stability and active site exposure. The special Ru−O−Mn bonds activate the Ru and Mn sites in Ru@MnO2‐x through strong interfacial coordination, driving glycerol electrolysis at low overpotential. Furthermore, only a low cell voltage of 1.68 V is required to achieve 0.5 A cm−2 in a continuous‐flow electrolyzer system along with excellent stability. In situ spectroscopic analysis reveals that the strong interfacial coordination in Ru@MnO2‐x balances the competitive adsorption of glycerol and OH* on the catalyst surface. Theoretical calculations further demonstrate that the defect‐rich MnO2 support promotes the dissociation of H2O, while the defect‐regulated Ru sites promote deprotonation and hydrogen desorption, synergistically enhancing glycerol‐assisted hydrogen production.