Metal-organic frameworks (MOFs) or porous coordination polymers (PCPs) are under intense investigation not only because of their intriguing structural architectures and topologies, but also for their novel properties. Designing reversible redox- or photo-active MOFs will reduce the energy cost required for sorption/desorption of CO2 by applying voltage or UV irradiation. Three new porous MOFs based on trinuclear copper-pyrazolato structural building units (SBUs) connected by photo-active 1,2-bis(4-pyridyl) ethylene (bpe) or 4,4’-azobipyridine (abp) linkers have been synthesized and studied. FIU-1 demonstrated the usefulness of a hexanuclear CuII -pyrazolate moiety as an SBU for generating 3-fold interpenetrated 3D polymeric network. FIU-2 has a 3D, three-fold interpenetrated structure with 46.7% pore volume, composed of 4-connected trinuclear SBUs. The related FIU-3, with 42.5% pore volume, contains the same trinuclear SBU as FIU-2 and differs from it only in the SBU/linker ratio and connectivity. The gas adsorption properties of the three MOFs have been determined experimentally in the 0-7 atm pressure range. All MOFs sorb CO2 selectively over N2, CH4. FIU-1 and FIU-3 also exhibit hysteretic sorption-desorption profiles indicating the flexibility of the MOFs upon adsorption. FIU-1 shows slight selectivity toward N2 over CH4. FIU-2 has the largest CO2 adsorption capacity among the MOFs studied in our group.

Selective CO2 adsorption on Cu-pyrazolato MOFs

255th National Meeting (2018)

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