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

Abstract

Photocatalytic selective oxidation of 5‐hydroxymethylfurfural (HMF) coupled H2 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 H2 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 µmol h−1 g−1 and the selectivity of >97%, simultaneously with the H2 evolution rate of 1522 µmol 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)2O*) 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.

Hydrogen‐Bond‐Enhanced Photoreforming of Biomass Furans over a Urea‐Incorporated Cu(II) Porphyrin Framework

“…Active oxygen species might be assigned to the peak at 1170 cm −1 [26] . Moreover, the formation of (CH 2 OH)C 4 H 2 O(CO)* intermediate were observed at 1600 cm −1 rather than (CH 2 O)C 4 H 2 O(CHO)* at 1084 cm −1 as reported before [7b] . Therefore, it is suggested that TBUPP−Cu adsorbs HMF via the hydrogen bonds, and oxidise it upon light irradiation to generated HMFCA via the (CH 2 OH)C 4 H 2 O(CO)* intermediate.…”

Sunlight-driven photocatalytic conversion of furfural and its derivatives

“…97 Such surface vacancies were beneficial for electron accumulation and substrate adsorption, thus the H 2 evolution rate was eight times higher than that of CdS-P. Zhu et al treated ZnIn 2 S 4 nanowires with oxygen plasma for 2 min and obtained a hierarchical porous O-ZIS-120 photocatalyst. 31 It showed the highest H 2 evolution rate of 1522 μmol h −1 g −1 in the current literature.…”

“…30 Moreover, owing to the unique redox ability of photogenerated electrons (e − ) and holes (h + ) in the photocatalytic system, selective oxidation and reduction can simultaneously occur over the same catalyst. In such a context, H 2 evolution 31,32 or CO 2 reduction 33 can be simultaneously performed with photoconversion of FAL and HMF. Besides, the tandem photoreduction and oxidation of FAL can yield tetrahydrofurfuryl alcohol (THFA) and γ-butyrolactone (GBL).…”

Regulating the Transfer of Photogenerated Carriers for Photocatalytic Hydrogen Evolution Coupled with Furfural Synthesis

“…Artificial photosynthesis represents the most viable and promising strategy for achieving carbon neutrality . Among its various forms, photocatalyst-based hydrogen (H 2 ) evolution from overall water splitting has garnered significant research attention, which offers a potential option to replacing conventional fossil fuels with clean and renewable energy sources. − However, the H 2 evolution performance is constrained by unfavorable thermodynamics, sluggish kinetics, and rapid inverse reactions. , The solution of incorporating hole sacrificial agents also results in wasting the oxidation ability of photogenerated holes and exacerbating product separation challenges due to the emergence of undesirable byproducts. − Impressively, photocatalytic H 2 evolution coupled with value-added chemicals synthesis via the effective utilization of photogenerated electrons and holes is a win-win strategy for sustainable development. − …”