Achieving Excess Hydrogen Output via Concurrent Electrochemical and Chemical Redox Reactions on P‐Doped Co‐Based Catalysts with Electron Manipulation and Kinetic Regulation

Electrolytic hydrogen production is of great significance in energy conversion and sustainable development. Traditional electrolytic water splitting confronts high anode voltage with oxygen generation and the amount of hydrogen produced at cathode depends entirely on the quantity of electric charge input. Herein, excess hydrogen output can be achieved by constructing a spontaneous hydrazine oxidation reaction (HzOR) coupled hydrogen evolution reaction (HER) system. For the hydrazine oxidation-assisted electrolyzer in this work, both the external input electrons and the electrons produced by spontaneous chemical redox reaction can reduce water, producing more hydrogen than traditional electrolytic water splitting system. The ultrafast kinetics of bifunctional P-doped Co-based catalysts plays a key role in the spontaneous feature of HzOR/HER redox reaction and low working voltage of hydrazine oxidation-assisted electrolyzer (12 mV@100 mA cm^-2). Theoretical calculation results and ex situ/in situ spectra demonstrate that doped P could optimize electronic structure, regulate adsorption energy of intermediates, and thus endows catalysts with ultrafast kinetics. This work provides a new pathway for the development of spontaneous oxidation-assisted hydrogen production, to achieve excess hydrogen output via concurrent electrochemical and chemical redox reactions.