Atomically dispersed bismuth on ZnIn2S4 Dual-Functional photocatalyst for photocatalytic hydrogen production coupled with oxidation of aromatic alcohols to aldehydes

Bi/ZnIn 2 S 4 is first excited by visible light and generates photoexcited electron-hole pairs. Due to the existence of the Schottky junction, electrons were transferred from the conduction band of ZnIn 2 S 4 to the atomically dispersed Bi, leaving holes in the valence band of ZnIn 2 S 4 . During the oxidation of R-PhCH 2 OH, hydroxyl (–OH) and C α -H bonds may be preferentially activated to produce corresponding carbon center radicals. • Non-noble Bi single atom on hierarchical structure ZnIn 2 S 4 was first synthesized through a one-pot strategy, forming a -S-Bi-S- coordination structure with surrounding S atoms. • Experiments and DFT calculations show that the light response range of Bi/ZnIn 2 S 4 was extended to the near-infrared region after the introduction of Bi atoms. • Without a wasteful sacrificial agent, Bi/ZnIn 2 S 4 exhibited an excellent hydrogen evolution rate of 3658.75 µmol g -1 h −1 . • A series of aromatic alcohols with different substituents (RPhCH 2 OH, R = Me, OH and Cl) were tested to prove the general applicability of the Bi/ZnIn 2 S 4 . It is of great significance to develop a simple method of non-noble metal atomical dispersion to establish a dual-function photocatalysis system for the oxidation of aromatic alcohols to aldehydes, and to couple it with the photocatalytic hydrogen production, so as to fully utilize the photogenerated carriers. Herein, we report a noble metal-free photocatalyst decorated with atomic dispersed Bi atoms in ZnIn 2 S 4 hierarchical structures by a one-pot method, for selective oxidation of R-PhCH 2 OH (R = H, Me, OH, Cl) coupled with high H 2 evolution. Aberration corrected transmission electron microscopy and theoretical calculations demonstrated that Bi atoms are atomically dispersed and bridged with two S atoms. Atomically dispersed Bi provides the maximum atom efficiency and promotes light absorption to the near-infrared region. By excluding all wasteful sacrificial agents, Bi/ZnIn 2 S 4 exhibits a high hydrogen evolution rate of 3658.8 µmol g -1 h −1 , which is approximately 14 times of that of bare ZnIn 2 S 4 (256 µmol g -1 h −1 ). This work provides insights into the effective utilization of photogenerated carriers in one system and the designing of promising photocatalysts with atomic precision.