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. 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 WVI‐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.

Preparation of Zr-Based Phosphotungstic Acid Catalyst, ZrPTAX-BTC, and Its Application in Ultradeep and Fast Oxidative Desulfurization of Fuels

“…In order to further reveal the synergistic catalytic effect between Zr IV and PTA in the process of ODS, a series of radical trapping experiments were carried out. Here, we first used benzoquinone (BQ) as a superoxide radical (O 2 ·) scavenger, − and isopropanol (IPA) as a hydroxyl radical (·OH) scavenger. − Here, we added 0.5 g of radical scavenger into the oxidative desulfurization reaction system, and this is excessive relative to the free radicals decomposed by H 2 O 2 in the system. Thus, the free radicals in the system can be quickly and fully captured.…”

Advances in Oxidative Desulfurization of Fuel Oils over MOFs-Based Heterogeneous Catalysts

“…On the basis of UiO-66(Zr), various types of active species including MnO 2 [104], MoO 3 [105], WO x [106] and 1-methylimidazolium-3-propylsulfonate hydrosulfate (abbreviated as PSMIMHSO 4 ) [107] were introduced into the pore channels or grafted on the framework of UiO-66(Zr). Therefore, W/UiO-66(Zr) prepared by in-situ injection of a single W site on the node of the defective UiO-66(Zr) structure by forming a Zr-O-W bond under solvent-free conditions exhibited excellent catalytic performance in the ODS reactions of DBT and 4,6-DMDBT.…”

“…Therefore, W/UiO-66(Zr) prepared by in-situ injection of a single W site on the node of the defective UiO-66(Zr) structure by forming a Zr-O-W bond under solvent-free conditions exhibited excellent catalytic performance in the ODS reactions of DBT and 4,6-DMDBT. Such performance was attributed to the presence of single-atom W sites [106].…”

Rational Design of Caprolactam-Based Deep Eutectic Solvents for Extractive Desulfurization of Diesel Fuel and Mechanism Study

“…Petroleum fuel has played an extremely important role since the industrial revolution . Although petroleum fuel promotes the development of social economy and production technology, the sulfur oxides (SO x ) produced by its combustion seriously endanger the natural environment and human health. , Therefore, minimizing the sulfur content in fuel oil (<10 mg kg –1 ) and realizing ultradeep desulfurization have become worldwide problems that need to be solved urgently. , …”