Does Mixed Linker-Induced Surface Heterogeneity Impact the Accuracy of IAST Predictions in UiO-66-NH₂?

To move toward more energy-efficient adsorption-based processes, there is a need for accurate multicomponent data under realistic conditions. While the Ideal Adsorbed Solution Theory (IAST) has been established as the preferred prediction method due to its simplicity, limitations and inaccuracies for less ideal adsorption systems have been reported. Here, we use amine-functionalized derivatives of the UiO-66 structure to change the extent of homogeneity of the internal surface toward the adsorption of the two probe molecules carbon dioxide and ethylene. Although it might seem plausible that more functional groups lead to more heterogeneity and, thus, less accurate predictions by IAST, we find a mixed-linker system with increased heterogeneity in terms of added adsorption sites where IAST predictions and experimental loadings agree exceptionally well. We show that incorporating uncertainty analysis into predictions with IAST is important for assessing the accuracy of these predictions. Energetic investigations combined with Grand Canonical Monte Carlo simulations reveal almost homogeneous carbon dioxide but heterogeneous ethylene adsorption in the mixed-linker material, resulting in local, almost pure phases of the individual components.