Visible-light-driven anaerobic oxidative upgrading of biomass-derived HMF for co-production of DFF and H 2 over a 1D Cd 0.7 Zn 0.3 S/NiSe 2 Schottky junction

• Published in: Green chemistry : an international journal and green chemistry resource : GC Vol. 25; no. 7; pp. 2745 - 2756
• Main Authors: Shan, Tao, Luo, Luteng, Chen, Taoran, Deng, Lixun, Li, Mengqing, Yang, Xuhui, Shen, Lijuan, Yang, Min-Quan
• Format: Journal Article
• Language: English
• Published: 03.04.2023
• ISSN: 1463-9262; 1463-9270
• DOI: 10.1039/D3GC00026E

Visible-light-driven photocatalytic oxidation of renewable biomass into value-added chemicals is a prospective solar energy utilization strategy. However, the aerobic oxidation reactions commonly generate uncontrolled reactive oxygen species, which leads to the peroxidation of target products and results in low selectivity. Herein, we demonstrate a selective anaerobic oxidation of biomass-derived 5-hydroxymethylfurfural (HMF) to 2,5-diformylfuran (DFF) coupled with H 2 production over a hybrid Cd 0.7 Zn 0.3 S nanorod/NiSe 2 composite. Cd 0.7 Zn 0.3 S with a 1D structure serves as a light harvester that greatly promotes electron transportation over long distances, while NiSe 2 acts as an advanced cocatalyst that provides abundant active sites to accelerate H 2 reduction. Importantly, NiSe 2 with metal-like characteristics forms a Schottky contact with Cd 0.7 Zn 0.3 S, which captures the photoelectrons generated from the Cd 0.7 Zn 0.3 S nanorods, inhibits the back flow, and prolongs the lifetime of charge carriers. The optimal DFF and H 2 production rates of the Cd 0.7 Zn 0.3 S/NiSe 2 4% sample are 1728 and 1690 μmol h −1 g −1 , respectively, which are approximately 23 times greater than those of blank Cd 0.7 Zn 0.3 S. The DFF selectivity is close to 98%. It represents one of the best photocatalytic performances for the selective oxidation of HMF reported thus far. This research shows the great potential of constructing a transition metal sulfide/selenide Schottky junction for photocatalytic biomass conversion and provides insights into the green value-added utilization of biomass-derived alcohols via selective anaerobic oxidation.