Highly Robust Tetranuclear Cobalt-Based 3d Framework For Efficient C2h2/Co2 And C2h2/C(2)H(4)Separations

A novel noninterpenetrated tetranuclear cobalt(II)-based metal-organic framework, (NH4)(2).[Co-4(mu(3)-OH)(2)(ina)(2)(pip)(3)].4EtOH.H2O (simplified as NbU-10.S), constructed by mix linkers was synthesized by a hydrothermal method. Interestingly, the presence of a hydrophobic benzene ring in the organic linker makes NbU-10.S exhibit high stability in high temperature and even in aqueous solution over a wide pH range of about 4-13. Magnetic studies showed that the tetranuclear cobalt(II) units in NbU-10.S show dominant antiferromangetic properties. However, in the absence of Lewis basic functional sites and open metal sites in the material, NbU-10 still displays high C2H2/CO2 and C2H2/C2H4 selectivity in ideal adsorbed solution theory calculations and dynamic breakthrough experiments. Moreover, density functional theory calculations were performed to identify the adsorption characteristics of different gas molecules.