Visible-Light-Driven Highly Selective 5-Hydroxymethylfurfural Upgrading and H2 Generation via Atomically Dispersed Ni Sites on ZnIn2S4 Nanosheets

Solar-driven biomass upgrading coupled with H2 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 ZnIn2S4 nanosheets (Ni1/ZIS), we decipher the reactive active sites that enable high-performance photocatalytic 5-hydroxymethylfurfural (HMF) oxidation coupled with H2 evolution. Under visible-light irradiation, Ni1/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 H2 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 ZnIn2S4 are favored for H2 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.