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

Abstract

In this work, we propose a computational system withtwo metalcatecholates that can potentially cause synergistic effects in thebinding energy of the gas molecules. Specifically, large-scale screeningwas conducted on 2880 Zr metal-organic frameworks, and we haveidentified a couple of materials that possessed the optimal configurationbetween the neighboring linkers to induce synergetic binding in theCO(2) molecule. Periodic DFT simulations on these candidatematerials indicate that while the binding energy values of CO andCO(2) are comparable for the single metal-catecholate case,the presence of the second metal-catecholate leads to a significantenhancement in the CO2 binding energy but not in CO. Thiscan be explained by the difference between CO2, which canbind cooperatively, and CO, which only binds on one side of the Catom. We expect that our study can be applied to diverse applicationsthat require both strong binding and high selectivity.