Octahedral–Tetrahedral Site Synergism in Spinel Oxides Enables 1700 h‐Stable Electrosynthesis of 2,5‐Furandicarboxylic Acid in Near‐Neutral Media

Abstract

ABSTRACT The electrosynthesis of 2,5‐furandicarboxylic acid (FDCA) from 5‐hydroxymethylfurfural (HMF) in near‐neutral media offers a sustainable alternative to alkaline routes by suppressing HMF degradation and thus mitigating carbon loss. However, it remains challenging to achieve both enhanced activity and long‐term durability for the deep oxidation of HMF intermediates into FDCA in a neutral medium. Herein, we report a Ru/Ni─co‐modified spinel cobalt oxide catalyst, Ru─CoNiOx, prepared through a scalable strategy. Structural analyses reveal that atomically dispersed Ru species preferentially incorporated into distorted octahedral Co coordination environment, while Ni species are mainly stabilized at tetrahedral Co sites, forming asymmetric [Ru oct ─O 6 ] and [Ni tet ─O 4 ] coordination motifs within the Co 3 O 4 lattice. This tailored coordination environment promotes surface hydroxylation and the transformation of Co(Ni)─OH ads /Co(Ni)─OOH, while strengthening the interfacial interaction with HMF. In near‐neutral KHCO 3 electrolyte, Ru─CoNiOx achieves approximately 91.0% FDCA Faradaic efficiency and 88.2% FDCA yield at 60°C, while showing a high carbon balance of 99.4%. Furthermore, a continuously HMFOR || HER membrane electrode assembly sustains FDCA production at 200 mA cm −2 for over 1700 h at approximately 1.9 V. This work demonstrates an effective strategy for asymmetric coordination regulation in spinel oxides and highlights the promise of near‐neutral electrocatalysis for coupled FDCA and H 2 production.