Molybdenum‐Enhanced Conductivity and Nickel Electron Density Synergizing With Phosphorus‐Induced Oxygen Vacancies in NiMo‐Based Heterostructures for Efficient Electrooxidation of 5‐Hydroxymethylfurfural

ABSTRACT 5‐Hydroxymethylfurfural (HMF) can be electrocatalytically oxidized to 2,5‐furandicarboxylic acid (FDCA) with concurrent hydrogen evolution, providing a sustainable route for biomass valorization and clean energy generation. In this study, we synthesized a three‐dimensional nanorod heterostructured catalyst composed of NiMoO 4 and NiMoP 2 directly on nickel foam (NiMoP@NF) via a one‐step hydrothermal method. Mo doping effectively enhanced the material's electrical conductivity and increased the electron cloud density around Ni active sites, while P doping introduced abundant oxygen vacancies and modulated the catalyst's electronic structure, thereby strengthening interfacial electronic coupling and optimizing the adsorption energies of reaction intermediates. Electrochemical testing shows that NiMoP@NF exhibits outstanding HMF oxidation activity: at 1.50 V vs. RHE, HMF conversion approaches 100%, FDCA yield reaches 97%, and the Faradaic efficiency is 96.8%. Mechanistic analysis indicates that the Ni 3+ /Ni 2+ redox couple serves as the active center, while phosphorus doping improves adsorption energies and lowers the activation barrier of the rate‐determining step. This work presents a high‐performance, non‐precious electrocatalyst for biomass upgrading and offers design principles for heterostructured catalysts in integrated energy systems.