Engineering the Reactive Oxygen Species Pathway via Electron Donor–Acceptor Microenvironment in Mo‐Doped FeCo Catalysts

Abstract This work presents a Mo‐doped FeCo catalyst (FeCoMo/NF) engineered to create an electron donor–acceptor microenvironment for regulating reactive oxygen species (ROS) during electrocatalysis. The catalyst exhibits exceptional hydrogen evolution reaction (HER) activity, achieving an overpotential of 62 mV at −10 mA cm −2 , and enables efficient glycerol oxidation reaction (GOR) in a coupled electrolyzer that requires only 1.381 V to reach 10 mA cm −2 . Through synergistic electronic modulation, the Fe–O–Mo bridges facilitate optimized adsorption of key intermediates, steering the glycerol conversion selectively toward formate and enhancing HER kinetics. Combined experimental and theoretical results reveal the critical role of Mo in controlling the ROS pathway via the donor–acceptor structure. This study offers a novel strategy for designing efficient electrocatalysts and sustainable biomass‐refining systems.