In Situ Implanting ZrW<sub>2</sub>O<sub>7</sub>(OH)<sub>2</sub>(H<sub>2</sub>O)<sub>2</sub> Nanorods into Hierarchical Functionalized Metal–Organic Framework via Solvent‐Free Approach for Upgrading Catalytic Performance
Gan Ye, Guangming Shi, Hanlu Wang, Xingye Zeng, Lei Wu, Jun Zhou, Qiuli Zhang, Jinshan Wei, Zhiming Li, Long Nie, Jin Wang
Abstract
Abstract Host–guest catalyst provides new opportunities for targeted applications and the development of new strategies for preparing host–guest catalysts is highly desired. Herein, an in situ solvent‐free approach is developed for implanting ZrW 2 O 7 (OH) 2 (H 2 O) 2 nanorods (ZrW‐NR) in nitro‐functionalized UiO‐66(Zr) (UiO‐66(Zr)‐NO 2 ) with hierarchical porosity, and the encapsulation of ZrW‐NR enables the as‐prepared host–guest catalyst remarkably enhanced catalytic performance for both for oxidative desulfurization (ODS) and acetalization reactions. ZrW‐NR@UiO‐66(Zr)‐NO 2 can eliminate 500 ppm sulfur within 9 min at 40 °C in ODS, and can transform 5.6 mmol benzaldehyde after 3 min at room temperature in acetalization reaction. Its turnover frequencies reach 72.3 h −1 at 40 °C for ODS which is 33.4 times higher than UiO‐66(Zr)‐NO 2 , and 28140 h −1 for acetalization which is the highest among previous reports. Density functional theory calculation result indicates that the W sites in ZrW‐NR can decompose H 2 O 2 to W VI ‐peroxo intermediates that contribute to catalytic activity for the ODS reaction. This work opens a new solvent‐free approach for preparing MOFs‐based host–guest catalysts to upgrade their redox and acid performance.