High Oxidation State V‐O‐Co Structure Promotes the Role of V‐ ^* O Intermediates in Efficient HMF Oxidation

Abstract Designing heterometallic oxygen‐bridge structure (M1‐O‐M2) to achieve the efficient and stable electrochemical conversion of 5‐hydroxymethylfurfural (HMF) to 2,5‐furandicarboxylic acid (FDCA) has become an important approach to address the rapid consumption of fossil fuels and mitigate white pollution. However, designing effective M1‐O‐M2 structures and elucidating their catalytic mechanisms remains a key challenge in this field. In this study, a high oxidation state V‐O‐Co structure is constructed by doping V into reconstructed CoOOH, which promotes the formation of the active intermediate V‐ ^* O. The catalyst achieves a low HMF oxidation onset potential of 1.13 V vs. RHE, the HMF conversion rate reaches 99.6%, the FDCA selectivity reaches 97.8%, and the Faradaic efficiency reaches 97.0% at an applied potential of 1.30 V vs. RHE. Based on this novel design strategy, V‐doped Ni ₂ P/NF is further constructed, which also forms the active intermediate V‐ ^* O, validating the effectiveness of this strategy. Notably, the oxidation state‐controlled V‐O‐Co structure demonstrates excellent catalytic performance in promoting the efficient conversion of various organic compounds (such as glycerol, glucose, methanol, etc.) into high‐value chemicals, providing a precedent for the development of single hetero‐oxygen‐bridge structures for the effective conversion of various high‐value compounds.