Electronic Structure Regulation of Molybdenum Phosphide by Cerium and Nitrogen Dual‐Doping for Highly Durable and Efficient Hydrogen Evolution in Alkaline Media

Abstract Molybdenum phosphide (MoP) nanomaterials are of great promise as electrochemical hydrogen evolution reaction (HER) catalysts, but the catalytic performance suffers from insufficient active sites and poor material stability. To address these challenges, we employed cerium and nitrogen elements to regulate the electronic structure of MoP in this study, where Ce and N doped MoP (Ce, N‐MoP) was synthesized by one‐pot high‐temperature pyrolysis of the uniform mixture of (NH 4 ) 6 Mo 7 O 24 •4H 2 O, NH 4 H 2 PO 4 , Ce(Ac) 3 and melamine. Compared with the bare MoP and N‐doped MoP (N‐MoP), Ce, N‐MoP only requires 102.6 mV to obtain the current density of 10 mA cm −2 in alkaline electrolyte, and exhibits excellent electrochemical and material long‐term durability. From experimental results, Ce and N co‐doping effectively modulate electronic structure of MoP, alters binding strength of Mo‐P bonds and enriches Mo‐P active species, which not only promotes the HER performance but also prevent MoP oxidation and improve its material stability. Theoretical calculation results show that Ce and N co‐doping can effectively promote the desorption of *OH in alkaline HER, thus promoting the dissociation of water and improving overall HER efficiency. This work gives useful guidance for constructing advanced HER catalysts by rare‐earth metal and nonmetal co‐doped transition metal phosphides.