Enhanced selectivity of CO(2) over CH(4) in sulphonate-, carboxylate- and iodo-functionalized UiO-66 frameworks.

Three new functionalized UiO-66-X (X = -SO(3)H, 1; -CO(2)H, 2; -I; 3) frameworks incorporating BDC-X (BDC: 1,4-benzenedicarboxylate) linkers have been synthesized by a solvothermal method using conventional electric heating. The as-synthesized (AS) as well as the thermally activated compounds were characterized by X-ray powder diffraction (XRPD), diffuse reflectance infrared Fourier transform (DRIFT) spectroscopy, thermogravimetric (TG), and elemental analysis. The occluded H(2)BDC-X molecules can be removed by exchange with polar solvent molecules followed by thermal treatment under vacuum leading to the empty-pore forms of the title compounds. Thermogravimetric analysis (TGA) and temperature-dependent XRPD (TDXRPD) experiments indicate that 1, 2 and 3 are stable up to 260, 340 and 360 °C, respectively. The compounds maintain their structural integrity in water, acetic acid and 1 M HCl, as verified by XRPD analysis of the samples recovered after suspending them in the respective liquids. As confirmed by N(2), CO(2) and CH(4) sorption analyses, all of the thermally activated compounds exhibit significant microporosity (S(Langmuir): 769-842 m(2) g(-1)), which are comparable to that of the parent UiO-66 compound. Compared to the unfunctionalized UiO-66 compound, all the three functionalized solids possess higher ideal selectivity in adsorption of CO(2) over CH(4) at 33 °C.