Merging open metal sites and Lewis basic sites in a NbO-type metal-organic framework for improved C2H2/CH4 and CO2/CH4 separation

摘要

A new three-dimensional NbO-type porous metal-organic framework ZJNU-47 was synthesized via a solvothermal reaction of Cu(NO3)(2)center dot 3H(2)O and a Lewis basic nitrogen donor site-rich tetracarboxylate, namely, 5,5'-(pyridazine-3,6-diyl)-diisophthalate, and the structure was characterized by single-crystal X-ray diffraction to be isostructural with NOTT-101. With the synergistic effect of open metal sites, Lewis basic sites and a suitable pore space, the MOF material ZJNU-47a after activation can take up a large amount of C2H2 and CO2. The gravimetric C2H2 uptake of 214 cm(3) (STP) g(-1) at room temperature and 1 atm is the highest among all reported MOFs to date, and the gravimetric CO2 uptake of 108 cm(3) (STP) g(-1) is also among the highest reported for MOFs. Compared to the isostructural MOF NOTT-101a, ZJNU-47a exhibits a significant increase in C2H2 and CO2 uptake and thus improved C2H2/CH4 and CO2/CH4 separations. Significantly, comprehensive DFT studies of C2H2 and CO2 adsorption have revealed that the open nitrogen donor sites are comparable and even superior to open metal sites regarding the adsorption sites. This work demonstrated that the simultaneous introduction of Lewis basic nitrogen donor sites and Lewis acidic metal sites into the framework is a promising approach to improve the gas sorption toward CO2 and C2H2 and thus to produce materials possessing enhanced C2H2/CH4 and CO2/CH4 separation performance.