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Abstract Engineering the electronic structure of transition metal catalysts is very important for regulating electrocatalytic reactions yet remains challenging, particularly in modulating the spin state for biomass valorization. Herein, a novel spin‐state engineering strategy is proposed to dramatically enhance the glycerol oxidation reaction (GOR) for selective formate production. It is demonstrated that vanadium (V) doping‐induced lattice distortion in Co 3 O 4 triggers a pivotal low‐spin to high‐spin (t 2g 4 e g 2 ) transition of Co 3+ ions. Through a combination of in situ spectroscopic techniques and theoretical calculations, it is revealed that this high‐spin state effectively tailors the interfacial microenvironment by reducing the population of strongly hydrogen‐bonded water molecules (≈30%) and concurrently strengthens the adsorption of glycerol and key intermediates (e.g., glyceric acid, glycolic acid), thereby optimizing the reaction pathway. As a result, the optimized high‐spin V‐Co 3 O 4 catalyst achieves an exceptionally low overpotential (reduced by 70–150 mV across the range of 10 – 300 mA cm −2 ) and a remarkable format selectivity of 93%, significantly outperforming its low‐spin counterpart (57%). This work not only provides profound atomic‐level insights into the spin‐state‐dependent reaction mechanism but also establishes spin‐state control as a fundamental and powerful paradigm for designing advanced electrocatalysts for sustainable energy conversion.
Ma et al. (Sun,) studied this question.