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 V 2 O 3 -modificated CuCo for efficient HMFOR. Experimental and theoretical results reveal that strong electron transfer occurs on the heterointerface between V 2 O 3 and CuCo, endowing its unique electronic structure and conductivity. Meanwhile, CuCo-V 2 O 3 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-V 2 O 3 induces an altered rate-determining step for HMFOR. Consequently, CuCo-V 2 O 3 presents enhanced HMFOR activity (E 10 , 1.27 V RHE ), 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.