ABSTRACT Understanding the link between local electronic structure and water dissociation is important for making good working, pH‐universal electrocatalysts. Here, we describe phosphorus‐added vanadium‐containing metal‐organic framework (P@V‐MOF) nanosheets that show great hydrogen evolution activity in acid, neutral, and alkaline solutions. Using BOLS‐NEP theory, XPS, PRS, XAS, and DFT calculations, we show that P atoms create V─P─C bonding, make V─O bonds longer, and cause antibonding V δ + dipoles, which moves the V 3d‐band center closer to the Fermi level. The polarization of unpaired V 3d electrons help V δ + :O─H hydrogen bond formation to weaken the H─O bonds in water, which lowers the water dissociation and * H adsorption energy. P@V‐MOF electrocatalyst shows low overpotentials (94 mV in acid, 178 mV in neutral, and 77 mV in alkaline solutions) and good stability for overall water splitting (1.53 V at 10 mA cm −2 ). These findings show the importance of hetero‐coordination and dipolar coupling to activite water molecules and develop effective, non‐noble‐metal electrocatalysts.
Liu et al. (Tue,) studied this question.