Tian‐Cai Yue, Xin-Fang Wang, Jian-Bo Huang, Lu−Lu Wang, Duo‐Zhi Wang
In this article, two new three-dimensional (3D) Fe II -MOFs ( 1 and 2 ) were successfully constructed, which can be employed as efficient heterogeneous photocatalysts in the product-selective oxidation of sulfides achieved by using hydrogen peroxide (H 2 O 2 ) as the green oxidant. The density functional theory (DFT) calculations proved that MOF 1 has higher catalytic activity than MOF 2 . As an efficient visible light-induced heterogeneous photocatalyst, MOF 1 displays superior photocatalytic activity in the product-selective oxidation of sulfides using H 2 O 2 . The oxidation products were sulfones when the reaction occurred in methanol (MeOH), and the oxidation products switched to sulfoxides when a small amount of water was added to the reaction system. Furthermore, the excellent catalytic activity of MOF 1 is well maintained even after 5 cycles and the plausible photocatalytic mechanism was investigated systematically. In the study of MOF photocatalytic, MOF 1 is the first MOF photocatalyst for efficient and selective transformation of sulfides into sulfones and sulfoxides using H 2 O 2 under mild conditions.