Tailoring Lewis Acidity of Nanoporous V‐Doped Co 2 P for Self‐Powered Hydrazine‐Water Splitting

ABSTRACT The hydrazine oxidation‐assisted hydrogen generation provides a promising alternative for low‐energy hydrogen production. Regulating the atomic structure of the catalyst and optimizing the reaction microenvironment is essential for overcoming the sluggish kinetics of alkaline hydrogen evolution reaction (HER) and hydrazine oxidation reaction (HzOR), yet remains a great challenge. Herein, nanoporous V‐doped Co 2 P (V‐Co 2 P) is introduced as a bifunctional catalyst for HER and HzOR through the regulation of Lewis acidity. The optimized Lewis acidity by V doping facilitates the formation of an ordered hydrogen bond network, accelerating water dissociation and active hydrogen species generation for HER. In addition, the nanoporous V‐Co 2 P can enhance the HzOR catalytic activity by creating a reactant‐enriched local environment, and reduce the energy barrier for converting *N 2 H 3 to *N 2 H 2 . As a result, the nanoporous V‐Co 2 P based electrolyser achieves a current density of 100 mA cm −2 at a low cell potential of 0.13 V. In addition, a self‐powered zinc hydrazine battery and an integrated overall hydrazine splitting system deliver a hydrogen generation rate of 1.12 mmol h −1 cm −2 . The proposed Lewis acidity regulation strategy opens new avenues for designing highly efficient sustainable energy conversion systems.