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

Gan Ye; Hanlu Wang; Wenxing Chen; Hongqi Chu; Jinshan Wei; Dagang Wang; Jin Wang; Yadong Li

doi:10.1002/anie.202107018

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

Angew Chem Int Ed Engl. 2021 Sep 6;60(37):20318-20324. doi: 10.1002/anie.202107018. Epub 2021 Jul 19.

Authors

Gan Ye^{1

2}, Hanlu Wang³, Wenxing Chen⁴, Hongqi Chu⁵, Jinshan Wei^{1

2}, Dagang Wang¹, Jin Wang¹, Yadong Li⁶

Affiliations

¹ College of Materials Science and Engineering, Shenzhen University, Shenzhen, 518060, China.
² Key Laboratory of Optoelectronic Devices and Systems of Ministry of Education and Guangdong Province, College of Optoelectronic Engineering, Shenzhen University, Shenzhen, 518060, China.
³ College of Chemical Engineering, Guangdong University of, Petrochemical Technology, Maoming, 525000, China.
⁴ Beijing Key Laboratory of Construction Tailorable Advanced, Functional Materials and Green Applications, School of Materials Science and Engineering, Beijing Institute of Technology, Beijing, 100081, China.
⁵ School of Chemistry and Chemical Engineering, Harbin Institute of Technology, Harbin, 150001, China.
⁶ Department of Chemistry, Tsinghua University, Beijing, 100084, China.

PMID: 34121275
DOI: 10.1002/anie.202107018

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.

Keywords: UiO-66(Zr); oxidative desulfurization; single site; solvent-free; tungsten.

Abstract

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