Two POM-based compounds containing Zn-capped Keggin anions as decent heterogeneous catalysts for sulfur oxidation and CO 2 cycloaddition reactions.

Carbon dioxide (CO 2 ) and the combustion of sulfide in gasoline are the main causes of air pollution. A great deal of attention has been paid to solving the problem and the catalytic reaction seems to be a decent choice. Due to the high-density of Lewis acidic active sites, polyoxometalates are undoubtedly an ideal choice for the sulfur oxidation reaction. With the reasons foregoing, two novel Zn-capped polyoxometalate-based organic-inorganic hybrids, {[α-PMoV2MoVI10O 39 (OH)Zn 2 ][bbbm] 3 }·0.5C 2 H 5 OH (1) and TBA 2 {[ε-PMoV8MoVI4O 37 (OH) 3 Zn 4 ][phim] 3 } (2) ((where bbbm = 1-(4-imidazol-1-ylbutyl) imidazole) and phim = 2-phenylimidazole) were successfully obtained by hydrothermal synthesis. In the two compounds, the N-donor ligands in a monodentate or bidentate coordination mode are directly connected to the Keggin anions by Zn-capped atoms, forming an extended one-dimensional chain. It is noteworthy that compound 2 ends up with an interesting spiral infinite chain possibly thanks to the TBA + cations residing in gaps as structure-directing agents. Simultaneously, the catalytic properties indicate that compounds 1 and2 as efficient heterogeneous catalysts display a decent catalytic activity in the sulfur removal process. Especially, 2 enabled satisfying catalytic oxidation of dibenzothiophene (DBT) to produce more valuable dibenzothiophene sulfone (DBTO 2 ) at 55 °C, and the conversion almost reached 99%. Besides, compound 2 also shows satisfactory catalytic effectiveness in the oxidation of various epoxides in the CO 2 cycloaddition reaction, which suggests that compound 2 has the potential to function as a dual functional material with tremendous prospects in sulfur oxidation and carbon dioxide cycloaddition for the first time.