Li Xiao-Xin, Zhang Lei, Liu Jiang, Yuan Lin, Wang Tong, Wang Jun-Yi, Dong Long-Zhang, Huang Kai, Lan Ya-Qian
School of Chemistry, South China Normal University, Guangzhou 510006, P. R. China.
School of Chemistry and Chemical Engineering, Southeast University, Nanjing 211189, P. R. China.
JACS Au. 2021 Jul 8;1(8):1288-1295. doi: 10.1021/jacsau.1c00186. eCollection 2021 Aug 23.
Metal cluster-based compounds have difficulty finishing the photocatalytic carbon dioxide reduction reaction (CORR) 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 () cluster-based catalysts connecting reductive { } (M = Zn, Co, and Ni for , , respectively) cluster and oxidative {PMoVO} cluster through a single oxygen atom bridge to achieve artificial photosynthesis successfully. These clusters can all photocatalyze CO-to-CO and HO-to-O reactions simultaneously, of which the CO yield of 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 CORR and WOR, respectively) and the effective electron transfer between the sites in these photocatalysts are the key factors to complete the overall photosynthesis.
基于金属簇的化合物难以同时完成光催化二氧化碳还原反应（CORR）和水氧化反应（WOR），因为要在一种化合物中实现独立且协同的还原和氧化活性位点共存面临巨大挑战。在此，我们精心设计并合成了一种基于氧化还原（）簇的晶体催化剂，该催化剂通过单个氧原子桥连接还原型{}（对于、、，M分别为Zn、Co和Ni）簇和氧化型{PMoVO}簇，从而成功实现人工光合作用。这些簇均能同时光催化CO到CO和HO到O的反应，其中的CO产率为13.8 μmol/g·h，选择性接近100%。密度泛函理论计算表明，这些光催化剂中伴随存在的催化还原和氧化活性位点（分别用于CORR和WOR）以及位点之间有效的电子转移是完成整体光合作用的关键因素。
