B,N‐Codoping Modulating Electron Redistribution for Efficient Electrocatalytic Oxidation of 5‐Hydroxymethylfurfural

ABSTRACT Replacing the oxygen evolution reaction (OER) with electrocatalytic 5‐hydroxymethylfurfural oxidation reaction (HMFOR) upgrades the energy‐intensive anodic process into a value‐generating reaction. Herein, an efficient electrocatalyst (Ni ₉ S ₈ /BNC) with Ni ₉ S ₈ nanoparticles on porous B, N‐codoped carbon was synthesized for HMFOR. The electron‐withdrawing B–N pair within the carbon matrix enhanced electron transfer from Ni ₉ S ₈ to the BNC support through the Ni─S─C linkage, thereby increasing the proportion of Ni ³⁺ species active for HMFOR. In addition, the electron‐deficient Ni ₉ S ₈ surface facilitated adsorption of the aldehyde group in HMF, while the electron‐enriched BNC framework preferentially interacted with the furan ring. This dual adsorption behavior strengthened HMF binding at the Ni ₉ S ₈ /BNC interface and accelerated the reaction kinetics. As a result, the Ni ₉ S ₈ /BNC catalyst achieved high electrocatalytic performance, with an HMF conversion of >99%, an FDCA yield of 92.7%, and a Faradaic efficiency of 93.3%. Overall, this work provided a detailed analysis of electron redistribution induced by B, N‐codoping and its effect on HMFOR activity, offering valuable insights for designing efficient, durable, and economical nonprecious metal catalysts for HMFOR.