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

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.