Abstract

The isostructural mixed-ligand metal–organic frameworks (MOFs), LIFM-66, 66/67-mix, and 67, have been constructed via organic-linker modification and variation to introduce different portions of functional groups into the pore-nanospaces with tunable surface areas. Adsorption measurements of hydrofluorocarbon (HFC) and hydrochlorofluorocarbon (HCFC) with these MOFs reveal a record high uptake of R134a (1.09–1.14 g g–1) and an ultrahigh uptake of R22 (0.85–0.96 g g–1) under ordinary conditions of room temperature and atmospheric pressure. Noteworthily, the adsorption performance of greenhouse gases CO2, R134a, and R22 can be finely regulated by introduced methyl groups, which has been elucidated by molecular modeling and transient breakthrough simulations/experiments, demonstrating an effective protocol of pore-nanospace engineering through rational design of mixed-ligand MOFs for HFC and HCFC capture, sequestration, and reclamation.

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