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

Carbon dioxide (CO) 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(OH)Zn][bbbm]}·0.5CHOH (1) and TBA{[ε-PMoV8MoVI4O(OH)Zn][phim]} (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) 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 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.