Perylene imide supermolecule promote oxygen to superoxide radical for ultrafast photo-oxidation of 5-hydroxymethylfurfural

The Photocatalytic preparation of 2, 5-diformylfuran (DFF) from biomass 5-hydroxymethylfurfural (HMF), is subjected to a low conversion efficiency. In view of superoxide radical is a crucial reactive oxygen species, we suggest an ultra-fast selective oxidation reaction achieved by modulating the photocatalytic oxygen reduction processes. Herein, we developed a novel photocatalytic system by anchoring perylene imide supramolecular as an oxygen reduction co-catalyst on ZnIn2S4. The functionalized perylene imide supramolecular as an active site greatly accelerates the generation of superoxide radical by absorbing oxygen while concentrating the photogenerated electrons of ZnIn2S4. Compared with pure ZnIn2S4, SA-PDI/ZnIn2S4 showed a more excellent photocatalytic performance under mild conditions (30-fold increase in photo-oxidation kinetics). Notably, the HMF transformation frequency is 1952 μmol·g−1·h−1, nearly one order of magnitude higher than previously reported techniques for photocatalytic HMF aerobic oxidation. This work open up a perspective for the design of photocatalytic systems for high added-value compounds production. Over Perylene imide supermolecule/ZnIn2S4 photocatalysts, the ultra-fast synthesis of the high value-added product 2,5-dimethylfuran from biomass-derived 5-hydroxymethylfurfural was developed. By controlling the adsorption and reduction of oxygen, the strategy significantly accelerates the proliferation of superoxide radicals and greatly enhances the conversion efficiency. Within only 30 min, a 90 % yield of 2,5-dimethylfuran was obtained, which is much higher than the 1–2 orders of magnitude in the previously reported photocatalysis 5-hydroxymethylfurfural oxidation. [Display omitted] •The SA-PDI are first applied to the photocatalytic value-added conversion of HMF.•Excellent TOF (1952 μmol h-1·g-1) was prepared by SA-PDI /ZnIn2S4 photocatalyst.•The oxygen adsorption and reduction processes can be effectively controlled by the SA-PDI co-catalyst.•The environment is rich in ·O2- was provided by SA-PDI /ZnIn2S4 for the selective oxidation of HMF to DFF.