Zr-Based Metal-Organic Framework with Wall-Shared Dual Ultramicroporous Channels for Effective CH4/N2 Separation

Theadsorptive separation of methane (CH4) and nitrogen(N-2) is a challenging yet crucial process in the purificationof unconventional natural gas. In this work, we report a robust Zr-basedmetal-organic framework, termed as MIP-203-F, for the selectiveadsorption of CH4 from CH4/N-2 mixtureswith varied concentrations. The framework possesses a rhombic one-dimensional(1D) micropore structure that is effectively divided into two symmetricwall-shared triangular pores by the presence of pendent -OHgroups, which endow the material with an optimal pore size and a plethoraof synergistic polar sites, facilitating the efficient adsorptionof CH4 with a high polarizability and overcoming the trade-offbetween CH4 capacity and CH4/N-2 selectivity.The exceptional separation performance of MIP-203-F was validatedthrough comprehensive experimental investigations encompassing thermodynamicanalyses, breakthrough experiments, and theoretical calculations.These findings underscore the immense potential of MIP-203-F as apromising candidate for the adsorptive separation of CH4/N-2.