Modulation of hydroxymethyl/aldehyde groups activation on V2O3 decorated CuCo for 5-hydroxymethylfurfural electrooxidation

5-Hydroxymethylfurfural electrooxidation reaction (HMFOR) has attracted increasing attention due to energy conservation and value-added production. It is crucial to design highly active catalysts with fast kinetics and reveal the catalytic mechanism. Herein, the activation of hydroxymethyl/aldehyde groups is tuned on V2O3-modificated CuCo for efficient HMFOR. Experimental and theoretical results reveal that strong electron transfer occurs on the heterointerface between V2O3 and CuCo, endowing its unique electronic structure and conductivity. Meanwhile, CuCo-V2O3 heterostructure facilitates the modulation of local electron density, charge transfer, and adsorption behavior to promote the activation of hydroxymethyl/aldehyde groups. The higher activation of hydroxymethyl groups than that of aldehyde groups over CuCo-V2O3 induces an altered rate-determining step for HMFOR. Consequently, CuCo-V2O3 presents enhanced HMFOR activity (E10, 1.27 VRHE), reaction kinetics (38 mV dec−1), 2,5-furandicarboxylic acid selectivity (99.1%), and stability (40 successive cycles). This work provides a strategy for designing highly active catalysts for synthesizing value-added products.