In Silico Design of Metal–Organic Frameworks Using Cooperative Binding of Two Metal Catecholates

Abstract

In this work, we propose a computational system with two metal catecholates that can potentially cause synergistic effects in the binding energy of the gas molecules. Specifically, large-scale screening was conducted on 2880 Zr metal–organic frameworks, and we have identified a couple of materials that possessed the optimal configuration between the neighboring linkers to induce synergetic binding in the CO2 molecule. Periodic DFT simulations on these candidate materials indicate that while the binding energy values of CO and CO2 are comparable for the single metal-catecholate case, the presence of the second metal-catecholate leads to a significant enhancement in the CO2 binding energy but not in CO. This can be explained by the difference between CO2, which can bind cooperatively, and CO, which only binds on one side of the C atom. We expect that our study can be applied to diverse applications that require both strong binding and high selectivity.