Boosting Catalytic Performance of MOF-808(Zr) by Direct Generation of Rich Defective Zr Nodes via a Solvent-Free Approach.

Creation of rich open metal sites (defect) on the nodes of metal-organic frameworks (MOFs) is an efficient approach to enhance their catalytic performance in heterogeneous reactions; however, direct generation of such defects remains challenging. In this contribution, we developed an in situ green route for rapid fabrication of defective MOF-808(Zr) with rich Zr-OH/OH sites (occupying 25% Zr coordination sites) and hierarchical porosity without the assistance of formic acid and solvent. The optimal MOF-808(Zr) not only displayed superior activity in oxidative desulfurization (ODS) for removing 1000 ppm sulfur at ambient temperature within 20 min but also could convert 3.8 mmol of benzaldehyde to (dimethoxymethyl)benzene within 90 s at 30 °C. The turnover frequencies reached 45.4 h for ODS and 3451 h for acetalization, outperforming the most reported MOF-based catalysts. Theoretical calculation and experimental results show that the formed Zr-OH/OH can react with HO to generate peroxo-zirconium species, which readily oxidize the sulfur compound. Our work provides a new approach to the synthesis of defect-rich MOF-808(Zr) with the accessibility of active sites for target reactions.