Preparation and catalysis of defected PVMo4W7@rht-MOF-1 for oxidation desulfurization under air

Aerobic oxidative desulfurization (AODS) is a promising deep desulfurization technique that can efficiently remove organosulfur compounds under mild conditions. In this study, a one-pot hydrothermal method was designed to encapsulate a quaternary heteropolyacid H 4 PVMo 4 W 7 O 40 (PVMo 4 W 7 ) into rht -MOF-1 { rht -MOF-1 = [Cu 6 O(TZI) 3 (H 2 O) 6 ] 4 ⋅nH 2 O}, and the single crystal structure of H 4 PVMo 4 W 7 O 40 @ rht -MOF-1 ( 1 ) indicated that PVMo 4 W 7 was effectively encapsulated within cage C of rht -MOF-1. Further, a similar one-pot hydrothermal reaction was employed to introduce acetic acid, resulting in the synthesis of defective H 4 PVMo 4 W 7 O 40 @ rht -MOF-1-De ( 1 - De ). 1 - De was characterized using various techniques such as FT-IR, XRD, TGA, XPS, and EPR. In comparison with 1, 1 - De exhibited numerous defect sites, high porosity, high surface area, high Mo 5+ ion content, well-dispersed PVMo 4 W 7 , and abundant oxygen vacancies, leading to efficient AODS capability. When applied as catalyst, 1 - De demonstrated high catalytic activity and good recyclability for the oxidation of dibenzothiophene (DBT) and 4,6-dimethyl dibenzothiophene (4,6-DMDBT) under air atmosphere. Strikingly, the removal rates of DBT and 4,6-DMDBT reached 99 % and 96 %, respectively under optimized conditions.