Modulating the Electronic Structure of Cobalt‐Vanadium Bimetal Catalysts for High‐Stable Anion Exchange Membrane Water Electrolyzer

Abstract Modulating the electronic structure of catalysts to effectively couple the hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) is essential for developing high‐efficiency anion exchange membrane water electrolyzer (AEMWE). Herein, a coral‐like nanoarray composed of nanosheets through the synergistic layering effect of cobalt and the 1D guiding of vanadium is synthesized, which promotes extensive contact between the active sites and electrolyte. The HER and OER activities can be enhanced by modulating the electronic structure through nitridation and phosphorization, respectively, enhancing the strength of metal‐H bond to optimize hydrogen adsorption and facilitating the proton transfer to improve the transformation of oxygen‐containing intermediates. Resultantly, the AEMWE achieves a current density of 500 mA cm –2 at 1.76 V for 1000 h in 1.0 M KOH at 70 °C. The energy consumption is 4.21 kWh Nm –3 with the producing hydrogen cost of $0.93 per kg H 2 . Operando synchrotron radiation and Bode phase angle analyses reveal that during the high‐energy consumed OER, the dissolution of vanadium species transforms distorted Co−O octahedral into regular octahedral structures, accompanied by a shortening of the Co−Co bond length. This structural evolution facilitates the formation of oxygen intermediates, thus accelerating the reaction kinetics.