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

Abstract

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.I nt his contribution, we report ao ne-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 À1 at 30 8 8C, which is 109.0, 12.3 and 1.2 times higher than that of pristine UiO-66(Zr), WO 3 ,a nd WCl 6 (homogeneous catalyst). Theoretical and experimental studies showthat the anchored Ws ites can react with oxidant readily and generate W VI -peroxo intermediates that determine the reaction activity.O ur work not only manifests the application of SSCs in the field of desulfurization of fuel oil but also opens an ew solvent-free avenue for fabricating MOFs based SSCs.

Defective silicotungstic acid-loaded magnetic floral N-doped carbon microspheres for ultra-fast oxidative desulfurization of high sulfur liquid fuels

“…Additionally, by employing the W atom as the active site, the turnover frequency (TOF) of γ-Fe 2 O 3 @NC@SiW 12 -300 was determined to be 110.07 h −1 (see formula (3) of ESI†), which is higher compared to most earlier literature reports. 65,68,69 A good catalytic activity of γ-Fe 2 O 3 @NC@SiW 12 -300 in the presence of H 2 O 2 can thus easily be inferred from the comparatively high kinetic constant ( k = 0.235 min −1 ), low activation energy ( E a = 38.79 kJ mol −1 ), and high TOF (110.07 h −1 ).…”