Insights into the sacrificial structure-activity relationship of a Ti-based metal-organic framework in an oxidative desulfurization reaction.

Abstract

Insights into the relationship between the crystal structure and activity of metal-organic frameworks (MOFs) are meaningful to investigate the potential properties of pristine MOFs for targeted catalytic reactions. Herein, we develop a high-efficiency method for boosting the oxidative desulfurization (ODS) activity of Ti-MOF in the presence of H+. The ODS activity of pristine Ti-MOF prepared via a solvothermal approach is very poor at a low reaction temperature but can be enhanced in the presence of H+. Ti-MOF in the presence of H+ shows ultrahigh ODS activity that can eliminate 1000 ppm sulfur after 7 min at 30 °C with no catalytic activity loss after recycling 11 times. The turnover frequency value reaches 12.4 h-1 at 30 °C, surpassing all the previously reported Ti-MOFs as ODS catalysts even at high temperatures. Characterization and quenching experimental results indicate that more uncoordinated Ti sites can be formed from slight damage to the structure of Ti-MOF during the catalytic reaction, and such exposed Ti sites can easily react with H+ and H2O2 to form Ti-hydroperoxo active species that determine the upgradation of ODS activity. This work provides a significant way to upgrade the catalytic activity of pristine Ti-MOFs for future application.