Defective Metal‐Organic Frameworks with Tunable Porosity and Metal Active Sites for Significantly Improved Performance in Styrene Oxidation

Metal active sites and sufficient porosity in metal‐organic frameworks (MOFs) are crucial parameters determining the performances of catalysis, guest molecule adsorption, etc. Herein, through in situ introduction of Ru sites with different levels to Cu‐BTC structure together with post‐synthetic activation at 180 °C, a series of hierarchically porous CuRu‐BTC (HP‐CuRu‐BTC) MOFs were obtained. Besides, selective thermal decomposition (STD) treatment was carried out at 240 °C to further tune the hierarchical pores and metal sites, yielding rare case of metal nanoparticles (NPs)@HP‐CuRu‐BTC composites. After full characterization by XRD, N2 physisorption, SEM, ICP and XPS, these HP‐CuRu‐BTC and NPs@HP‐CuRu‐BTC samples possess high surface area (682–1199 m2 g−1), hierarchical pores and highly distributed metal sites with reduced oxidation states (Cu+ and Ru2+), indicating regulation of both metal sites and hierarchical pores. The HP‐CuRu‐BTC and NPs@HP‐CuRu‐BTC were further employed as catalysts for the heterogeneous styrene oxidation reaction under mild condition. Compared to microporous Cu‐BTC with unary metal component, HP‐CuRu‐BTC‐3 and NPs@HP‐CuRu‐BTC‐3 exhibited more than 2 times higher styrene conversion after 7 hours reaction under same condition. Through in situ introduction of Ru sites to Cu‐BTC and post‐synthetic selective thermal decomposition (STD) strategy, novel case of hierarchically porous (HP) CuRu‐BTC and metal nanoparticles@HP‐CuRu‐BTC composites were reported, which exhibited much better performance for styrene oxidation than parent Cu‐BTC.