Orbital Symmetry Matching in Tailored Bimetal Oxides: Steering 5‐Hydroxymethylfurfural Electrooxidation via Concurrent Activation of sp ³ /sp ² Dual‐Oxygen Species

ABSTRACT The electrooxidation of 5‐hydroxymethylfurfural (HMF) to 2,5‐furandicarboxylic acid (FDCA), a sustainable polymer monomer, holds significant potential for biomass upgrading. Nevertheless, challenges arise in achieving the concurrent activation of sp ³ /sp ² dual‐oxygen species within a HMF molecule, which is crucial for a selective and efficient reaction pathway. Here, we propose an orbital‐symmetry‐matching strategy to simultaneously optimize the electronic structure of sp ³ /sp ² dual‐oxygen species and boost the efficiency of the HMF oxidation reaction (HMFOR) over the tailored M ₃ O ₄ spinel oxide. In the typical (V‐Co) ₃ O ₄ system, Co ³⁺ (t _2g ⁶ e _g ⁰ ) enables the “locking” of O (sp ² ) for aldehyde by the strong σ bonds and π feedback, which facilitates the C═O polarization and the nucleophilic attack; V ³⁺ (t _2g ² e _g ⁰ ) can couple O (sp ³ ) of hydroxymethyl to form a moderate σ bond, promoting the cleavage of the O─H bond. This design drives the concurrent activation of dual‐oxygen species and endows (V‐Co) ₃ O ₄ @NF with exceptional HMFOR performance of nearly 100% yield and selectivity toward FDCA. Our work provides a fundamental understanding of d‐p orbital hybridization, opening a new avenue for developing advanced electrocatalysts for diverse oxygen‐related reactions.