The novel Zr^IV-based perfluorinated metal-organic framework (PF-MOF) [Zr₆O₄(OH)₄(TFS)₆] (ZrTFS) was prepared under solvent-free conditions using the commercially available tetrafluorosuccinic acid (H₂TFS) as a bridging ditopic linker. Since H₂TFS can be seen as the fully aliphatic and perfluorinated C₄ analogue of fumaric acid, ZrTFS was found to be isoreticular to zirconium fumarate (MOF-801). The structure of ZrTFS was solved and refined from X-ray powder diffraction data. Despite this analogy, the gas adsorption capacity of ZrTFS is much lower than that of MOF-801; in the former, the presence of bulky fluorine atoms causes a considerable window size reduction. To have PF-MOFs with more accessible porosity, postsynthetic exchange (PSE) reactions on (defective) MOF-801 suspended in H₂TFS aqueous solutions were carried out. Despite the different H₂TFS concentrations used in the PSE process, the exchanges yielded two mixed-linker materials of similar minimal formulae [Zr₆O₄(μ₃-OH)₄(μ₁-OH)_2.08(H₂O)_2.08(FUM)_4.04(HTFS)_1.84] (PF-MOF1) and [Zr₆O₄(μ₃-OH)₄(μ₁-OH)_1.83(H₂O)_1.83(FUM)_4.04(HTFS)_2.09] (PF-MOF2) (FUM^2- = fumarate), where the perfluorinated linker was found to fully replace the capping acetate in the defective sites of pristine MOF-801. CO₂ and N₂ adsorption isotherms collected on all samples reveal that both CO₂ thermodynamic affinity (isosteric heat of adsorption at zero coverage, Q_st) and CO₂/N₂ adsorption selectivity increase with the amount of incorporated TFS^2-, reaching the maximum values of 30 kJ mol^-1 and 41 (IAST), respectively, in PF-MOF2. This confirms the beneficial effect coming from the introduction of fluorinated linkers in MOFs on their CO₂ adsorption ability. Finally, solid-state density functional theory calculations were carried out to cast light on the structural features and on the thermodynamics of CO₂ adsorption in MOF-801 and ZrTFS. Due to the difficulties in modeling a defective MOF, an intermediate structure containing both linkers in the framework was also designed. In this structure, the preferential CO₂ adsorption site is the tetrahedral pore in the "UiO-66-like" structure. The extra energy stabilization stems from a hydrogen bond interaction between CO₂ and a hydroxyl group on the inorganic cluster.

Maria Sole Notari

Publications