Visible-Light-Driven Highly Selective 5-Hydroxymethylfurfural Upgrading and H<sub>2</sub> Generation via Atomically Dispersed Ni Sites on ZnIn<sub>2</sub>S<sub>4</sub> Nanosheets
Shenghe Si, Piyu Gong, Xiaolei Bao, Xinying Tan, Yuyin Mao, Honggang Zhang, Difei Xiao, Kepeng Song, Zeyan Wang, Peng Wang, Yuanyuan Liu, Zhaoke Zheng, Ying Dai, Baibiao Huang, Hefeng Cheng
Abstract
Solar-driven biomass upgrading coupled with H 2 generation is promising for achieving carbon neutrality. However, identification of the active sites for the simultaneous photocatalytic redox reactions remains elusive at the atomic level. Herein, through the rational construction of atomically dispersed Ni on ZnIn 2 S 4 nanosheets (Ni 1 /ZIS), we decipher the reactive active sites that enable high-performance photocatalytic 5-hydroxymethylfurfural (HMF) oxidation coupled with H 2 evolution. Under visible-light irradiation, Ni 1 /ZIS greatly outperforms its pristine ZIS counterpart and can deliver high selectivity (>97%) for 2,5-diformylfuran (DFF), along with high-activity DFF production (394 μmol g –1 h –1 ) and H 2 evolution (342.2 μmol g –1 h –1 ) in a near stoichiometric ratio. Combined detailed experiments and theoretical calculations uncover that atomically dispersed Ni species act as active sites for HMF oxidation, while S sites on ZnIn 2 S 4 are favored for H 2 evolution. This work provides new insights into the development of artificial photosynthesis for value-added chemicals from biomass upgrading via the rational construction of atomically dispersed active sites.