In Situ Topochemical Transformation of ZnIn₂S₄ for Efficient Photocatalytic Oxidation of 5-Hydroxymethylfurfural to 2,5-Diformylfuran

Photocatalytic selective oxidation of 5-hydroxymethylfurfural (HMF) coupled H-2 production offers a promising approach to producing valuable chemicals. Herein, an efficient in situ topological transformation tactic is developed for producing porous O-doped ZnIn2S4 nanosheets for HMF oxidation cooperative with H-2 evolution. Aberration-corrected high-angle annular dark-field scanning TEM images show that the hierarchical porous O-ZIS-120 possesses abundant atomic scale edge steps and lattice defects, which is beneficial for electron accumulation and molecule adsorption. The optimal catalyst (O-ZIS-120) exhibits remarkable performance with 2,5-diformylfuran (DFF) yields of 1624 & mu;mol h(-1) g(-1) and the selectivity of >97%, simultaneously with the H-2 evolution rate of 1522 & mu;mol h(-1) g(-1). Mechanistic investigations through theoretical calculations show that O in the O-ZIS-120 lattice can reduce the oxidation energy barrier of hydroxyl groups of HMF. In situ attenuated total reflection surface-enhanced infrared absorption spectroscopy (ATR-SEIRAS) results reveal that DFF* (C4H2(CHO)(2)O*) intermediate has a weak interaction with O-ZIS-120 and desorb as the final product. This study elucidates the topotactic structural transitions of 2D materials simultaneously with electronic structure modulation for efficient photocatalytic DFF production.