Effective Ligand Functionalization of Zirconium-Based Metal Organic Frameworks for the Adsorption and Separation of Benzene and Toluene: A Multiscale Computational Study

The adsorption and separation properties of benzene and toluene on the zirconium-based frameworkS UiO-66, -67, -68, and their functional analogues UiO.Phe and UiO-Me2 were studied using grand canonical Monte Carlo simulations, density functional theory, and ideal adsorbed solution theory. Remarkable higher adsotption uptakes of benzene and toluene at low pressures on UiO-Phe and -Me2 were found compared to their parent framework UiO-67. It can be ascribed to the presence of functional groups (aromatic rings and methyl groups) that : significantly intensified the adsorption, majorly by reducing the effective pore size and increasing the interaction strength with the adsotbates. At high-pressures, the pore volumes and accessible surfaces of the frameworks turned out to be the dominant factors governing the adsorption. In the case Of toluene/benzene separation, toluene selectivities of UiOs showed a two-stage separation behavior at the measured pressure range, resulting from the greater interaction affinities of toluene at low pressures and setric hindrance effects at high pressures. Additionally, the counterbalancing factors of enhanced pi delocalization and suitable pore site of UiO-Phe gave rise to the highest toluene selectivity, suggesting the ligand functionalization Strategy could reach both high adsorption capacity and separation selectivity from aromatic mixtures at low concentrations.