Carbon Dioxide Adsorption in Amine-Functionalized Mixed-Ligand Metal-Organic Frameworks of UiO-66 Topology

A series of mixed-ligand [1,4-benzenedicarboxylic acid (BDC)/2-amino-1,4-benzenedicarboxylic acid (ABDC)] UiO-66 metal-organic frameworks (MOFs) synthesized through two different methods (low (LT) and high temperature (HT)) have been investigated for their carbon dioxide adsorption properties from 0 to 1 bar to clarify the role of amino loading on carbon dioxide uptake. Volumetric CO2 isotherms show that the CO2 capacity (normalized to the Langmuir surface area) increases with a degree of functionalization of about 46 %; for similar NH2 contents, the same values are found for both synthetic procedures. Microcalorimetric isotherms reveal that amino-functionalized materials have a larger differential heat of adsorption (q(diff)) towards CO2; reaching 27(25) and 20(22) kJmol(-1) on HT(LT)-UiO-66-NH2 and UiO-66, respectively, at the lowest equilibrium pressures used in this study. All experimental results are supported by values obtained through quantum mechanical calculations.