American Chemical Society
au1c00186_si_004.cif (484.66 kB)

Design of Crystalline Reduction–Oxidation Cluster-Based Catalysts for Artificial Photosynthesis

Download (484.66 kB)
posted on 2021-07-08, 10:04 authored by Xiao-Xin Li, Lei Zhang, Jiang Liu, Lin Yuan, Tong Wang, Jun-Yi Wang, Long-Zhang Dong, Kai Huang, Ya-Qian Lan
Metal cluster-based compounds have difficulty finishing the photocatalytic carbon dioxide reduction reaction (CO2RR) and water oxidation reaction (WOR) simultaneously because of the big challenge in realizing the coexistence of independently and synergistically reductive and oxidative active sites in one compound. Herein, we elaborately designed and synthesized one kind of crystalline reduction–oxidation (RO) cluster-based catalysts connecting reductive {M3L8(H2O)2} (M = Zn, Co, and Ni for RO-1, 2, 3 respectively) cluster and oxidative {PMo9V7O44} cluster through a single oxygen atom bridge to achieve artificial photosynthesis successfully. These clusters can all photocatalyze CO2-to-CO and H2O-to-O2 reactions simultaneously, of which the CO yield of RO-1 is 13.8 μmol/g·h, and the selectivity is nearly 100%. Density functional theory calculations reveal that the concomitantly catalytically reductive and oxidative active sites (for CO2RR and WOR, respectively) and the effective electron transfer between the sites in these RO photocatalysts are the key factors to complete the overall photosynthesis.