H2/CO2 separations in multicomponent metal-adeninate MOFs with multiple chemically distinct pore environments

Metal-organic frameworks constructed from multiple (>= 3) components often exhibit dramatically increased structural complexity compared to their 2 component (1 metal, 1 linker) counterparts, such as multiple chemically unique pore environments and a plurality of diverse molecular diffusion pathways. This inherent complexity can be advantageous for gas separation applications. Here, we report two isoreticular multicomponent MOFs, bMOF-200 (4 components; Cu, Zn, adeninate, pyrazolate) and bMOF-201 (3 components; Zn, adeninate, pyrazolate). We describe their structures, which contain 3 unique interconnected pore environments, and we use Kohn-Sham density functional theory (DFT) along with the climbing image nudged elastic band (CI-NEB) method to predict potential H-2/CO2 separation ability of bMOF-200. We examine the H-2/CO2 separation performance using both column breakthrough and membrane permeation studies. bMOF-200 membranes exhibit a H-2/CO2 separation factor of 7.9. The pore space of bMOF-201 is significantly different than bMOF-200, and one molecular diffusion pathway is occluded by coordinating charge-balancing formate and acetate anions. A consequence of this structural difference is reduced permeability to both H-2 and CO2 and a significantly improved H-2/CO2 separation factor of 22.2 compared to bMOF-200, which makes bMOF-201 membranes competitive with some of the best performing MOF membranes in terms of H-2/CO2 separations.