深圳大学王进团队利用无溶剂法在缺陷UiO-66(Zr)中原位注入单一W位点用于室温下高效氧化脱硫硫。相关研究成果发表在2021年6月13日出版的《德国应用化学》。

设计具有原子级催化中心和高原子利用率的单中心催化剂，为靶向反应提供了获得优异催化性能的新机会。

在该文中，研究人员报道了一种一锅绿色方法，通过在无溶剂条件下形成Zr-O-W键，在缺陷UiO-66（Zr）结构的节点上原位注入单个钨位（高达12.7 wt.%）。催化剂在室温下30min内表现出优异的氧化脱硫活性（1000ppm S），在30℃时转化频率（TOF）可达44.0h-1°C、 比纯UiO-66（Zr）、WO3和WCl6（均相催化剂）分别高109.0、12.3和1.2倍。理论和实验研究表明，锚定的W位点很容易与氧化剂发生反应，生成决定反应活性的W（VI）-过氧中间体。

该研究工作不仅展示了SSCs在燃油脱硫领域的应用，而且为制备SSCs基MOFs开辟了一条新的无溶剂途径。

附：英文原文

Title: In situ implanting single tungsten site into defective UiO-66(Zr) by solvent-free route for efficient oxidative desulfurization at room temperature

Author: Jin Wang, Gan Ye, Hanlu Wang, Wenxin Chen, Hongqi Chu, Jinshan Wei, Dagang Wang, Yadong Li

Issue&Volume: 2021-06-13

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 single tungsten site (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), WO  3  , and WCl  6  (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.

DOI: 10.1002/anie.202107018

Source: https://onlinelibrary.wiley.com/doi/10.1002/anie.202107018