In Silico Design\nof Metal–Organic Frameworks\nUsing Cooperative Binding of Two Metal Catecholates

Abstract

In this work, we propose a computational system with\ntwo metal\ncatecholates that can potentially cause synergistic effects in the\nbinding energy of the gas molecules. Specifically, large-scale screening\nwas conducted on 2880 Zr metal–organic frameworks, and we have\nidentified a couple of materials that possessed the optimal configuration\nbetween the neighboring linkers to induce synergetic binding in the\nCO₂ molecule. Periodic DFT simulations on these candidate\nmaterials indicate that while the binding energy values of CO and\nCO₂ are comparable for the single metal-catecholate case,\nthe presence of the second metal-catecholate leads to a significant\nenhancement in the CO₂ binding energy but not in CO. This\ncan be explained by the difference between CO₂, which can\nbind cooperatively, and CO, which only binds on one side of the C\natom. We expect that our study can be applied to diverse applications\nthat require both strong binding and high selectivity.