Nanoporous {Co3}-Organic framework for efficiently seperating gases and catalyzing cycloaddition of epoxides with CO2 and Knoevenagel condensation

Enhancing the catalysis of metal-organic frameworks (MOFs) by regulating inherent Lewis acid-base sites to realize the efficient seperation and chemical fixation of inert carbon dioxide (CO2) is crucial but challenging. Herein, the solvothermal self-assembly of Co2+, 5 '-(4-carboxy-2-nitrophenyl)-2,2 ',2 '',4 ',6 '-pentanitro-[1,1 ':3 ',1 ''terphenyl]-4,4 ''-dicarboxylic acid (H3TNBTB) and 4 '-phenyl-4,2 ':6 ',4 ''-terpyridine (PTP) generated a highly robust cobalt-organic framework of {[Co3(TNBTB)2(PTP)]center dot 7DMF center dot 6H2O}n (NUC-82). In NUC-82, the tri-core clusters of {Co3} with linear shape are bridged by TNBTB3- to form two-dimensional structure in ac plane, which is further linked by PTP to generate a three-dimensional framework with two kinds of solvent-accessible channels: rhombic-like (ca. 11.57 x 10.76 angstrom) along a axis and rectangular-like (ca. 7.32 x 11.56 angstrom) along b axis. Furthermore, it is worth emphasizing that the confined pore environments are characterized by plentiful Lewis acid-base sites of tricobalt clusters, grafted nitro groups and free pyridinyl, high specific surface area and solventfree nano-caged windows. Activated NUC-82a owns the ultra-high ethylene (C2H2) separation performance over the mixture of C2H2/CH4 and CO2/CH4 with the selectivity of 223.1 and 44.7. Thanks to the great Lewis-acid sites as well as the large pore volume, activated NUC-82a displays the high catalytic performace on the cycloaddition of CO2 with epoxides under wield condtions such as amibient pressure. Furthermore, because of the rich Lewis base sites, NUC-82a can efficiently catalyze Knoevenagel condensation of aldehydes and malononitrile. In the above organic reactions, NUC-82a not only shows the high catalytic activity, but also exhibits the high selectivity, satifactory recyclability and easy-to-separate heterogeneity, confirming that NUC-82a is a promising catalyst. Hence, this work provides in-depth insight into the construction of multifunctional MOFs by modifying the traditional ligands with as many Lewis acid-base active sites as possible.