Cooperative Boron and Vanadium Doping of Nickel Phosphides for Hydrogen Evolution in Alkaline and Anion Exchange Membrane Water/Seawater Electrolyzers

Abstract Developing low‐cost and high‐performance transition metal‐based electrocatalysts is crucial for realizing sustainable hydrogen evolution reaction (HER) in alkaline media. Here, a cooperative boron and vanadium co‐doped nickel phosphide electrode (B, V‐Ni 2 P) is developed to regulate the intrinsic electronic configuration of Ni 2 P and promote HER processes. Experimental and theoretical results reveal that V dopants in B, V‐Ni 2 P greatly facilitate the dissociation of water, and the synergistic effect of B and V dopants promotes the subsequent desorption of the adsorbed hydrogen intermediates. Benefiting from the cooperativity of both dopants, the B, V‐Ni 2 P electrocatalyst requires a low overpotential of 148 mV to attain a current density of −100 mA cm −2 with excellent durability. The B, V‐Ni 2 P is applied as the cathode in both alkaline water electrolyzers (AWEs) and anion exchange membrane water electrolyzers (AEMWEs). Remarkably, the AEMWE delivers a stable performance to achieve 500 and 1000 mA cm −2 current densities at a cell voltage of 1.78 and 1.92 V, respectively. Furthermore, the developed AWEs and AEMWEs also demonstrate excellent performance for overall seawater electrolysis.