Enhanced selectivity of CO2 over CH4 in sulphonate-, carboxylate- and iodo-functionalized UiO-66 frameworks

Abstract

Three new functionalized UiO-66-X (X = –SO₃H, 1; –CO₂H, 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 H₂BDC-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 N₂, CO₂ and CH₄ sorption analyses, all of the thermally activated compounds exhibit significant microporosity (S_Langmuir: 769–842 m² 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 CO₂ over CH₄ at 33 °C.