In Situ Implanting ZrW₂O₇(OH)₂(H₂O)₂ Nanorods into Hierarchical Functionalized Metal–Organic Framework via Solvent‐Free Approach for Upgrading Catalytic Performance

AbstractHost–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 ZrW2O7(OH)2(H2O)2 nanorods (ZrW‐NR) in nitro‐functionalized UiO‐66(Zr) (UiO‐66(Zr)‐NO2) 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)‐NO2 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)‐NO2, 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 H2O2 to WVI‐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.