Activating Co 2+ /Co 3+ Redox Couple Mediated‐Electrooxidation of 5‐Hydroxymethyl Furfuryl Under Low Potentials

作者：Jingwei Cui, Bing Du, Xiuqi Jin, Zhenghui Huang, Xiaosong Peng, W Li, Wei Li, Wei Li, Ying‐Rui Lu, Yucheng Huang, Ying‐Rui Lu, Chaoji Chen, Hongbing Deng · 发表于：Angewandte Chemie International Edition · 年份：2025 · DOI：10.1002/anie.202513396 · 被引用次数：20 · 研究领域：Electrocatalysts for Energy Conversion、Catalysis for Biomass Conversion、Polyoxometalates: Synthesis and Applications

Abstract Cobalt‐based electrocatalysts are promising candidates for electrochemical 5‐hydroxymethylfurfural oxidation reaction (eHMFOR). However, the activity origin for eHMFOR on most cobalt‐based electrocatalysts is the Co 3+ /Co 4+ redox couple at the high‐potential window, instead of the Co 2+ /Co 3+ redox couple at the low‐potential window, thus leading to a high onset potential above 1.3 V. Herein, we developed F‐V O ‐CoMoO 4 catalyst containing abound oxygen vacancies and lattice fluorine (F) heteroatom, which activates the Co 2+ /Co 3+ redox couple for eHMFOR at the low‐potential window, e.g., 1.15 V. Oxygen vacancies prompt the electrochemical generation of Co 3+ ‐OH ads at low potentials, and meanwhile, lattice F heteroatoms enhance the electrophilicity of Co 3+ ‐OH ads . Benefiting by those unique structure, F‐V O ‐CoMoO 4 catalyst effectively electro‐synthesizes 2,5‐furandicarboxylic acid from 5‐hydroxymethylfurfural, with a high yield (95.3%) and Faradaic efficiency (96.1%). This work provides an intelligent strategy for achieving the low‐potential eHMFOR mediated by the Co 2+ /Co 3+ redox couple, unlocking significant potential for reducing the energy consumption in biomass conversion.