In Situ Implanting of Single Tungsten Sites into Defective UiO‐66(Zr) by Solvent‐Free Route for Efficient Oxidative Desulfurization at Room Temperature. (19th July 2021)

• Record Type: Journal Article
• Authors: Ye, Gan; Wang, Hanlu; Chen, Wenxing; Chu, Hongqi; Wei, Jinshan; Wang, Dagang; Wang, Jin; Li, Yadong
• Is Part Of: Angewandte Chemie. Volume 133:Number 37(2021)
• Page Start: 20481
• Page End: 20487
• Publication Date: 2021-07-19
• Subjects: oxidative desulfurization -- single site -- solvent-free -- tungsten -- UiO-66(Zr); Chemistry -- Periodicals; 540
• DOI: 10.1002/ange.202107018
• Languages: English
• ISSNs: 0044-8249

Abstract

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. 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 °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. Abstract : 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 conditions is reported. The W/UiO‐66(Zr) SSCs display extraordinary ODS activity under very mild condition, achieving complete oxidation of sulfur compounds (1000 ppm S) at room temperature within 30 min by using diluted H2 O2 as oxidant.