In Situ Implanting of Single Tungsten Sites into Defective UiO-66(Zr) by Solvent-Free Route for Efficient Oxidative Desulfurization at Room Temperature

Design of single-site catalysts with catalytic sites at atomic-scale and high atom utilization, provides new opportunities to gain superior catalytic performance for targeted reactions. In this contribution, we report a one-pot green approach for in situ implanting of single tungsten sites (up to 12.7 wt.%) onto the nodes of defective UiO-66(Zr) structure via forming Zr-O-W bonds under solvent-free condition. The catalysts displayed extraordinary activity for the oxidative removal of sulfur compounds (1000 ppm S) at room temperature within 30 min. The turnover frequency (TOF) value can reach 44.0 h(-1) at 30 degrees C, which is 109.0, 12.3 and 1.2 times higher than that of pristine UiO-66(Zr), WO3, and WCl6 (homogeneous catalyst). Theoretical and experimental studies show that the anchored W sites can react with oxidant readily and generate W-VI-peroxo intermediates that determine the reaction activity. Our work not only manifests the application of SSCs in the field of desulfurization of fuel oil but also opens a new solvent-free avenue for fabricating MOFs based SSCs.

Automated summary

The study presents a green one-pot method for in situ implanting single tungsten sites into the nodes of defective UiO-66(Zr) structure, achieving high catalytic activity for the oxidative removal of sulfur compounds at room temperature. Anchored tungsten sites react readily with oxidants to generate intermediates that determine the reaction activity.