Molecular Design of Zirconium Tetrazolate Metal–Organic Frameworks for CO2 Capture

Zirconium (Zr) metal–organic frameworks (MOFs) have received considerable interest due to their superior hydrolytic, thermal, and chemical stability. On the basis of 40 topological nets, 120 Zr-MOFs with 8-, 10-, and 12-coordination are designed in this study with nitrogen-rich CO2-philic tetrazolate toward CO2 capture. The Zr-tetrazolate MOFs are revealed to exhibit substantially stronger CO2 adsorption than their carboxylate counterparts of identical topologies. By synergizing multiscale modeling from molecular simulation to breakthrough prediction, MOF-eft-P is identified among the 120 Zr-MOFs to possess the largest isosteric heat at infinite dilution and uptake at 1 bar for CO2, as well as the highest CO2/N2 selectivity; it outperforms many typical MOFs and other adsorbents reported in the literature. The breakthrough time of CO2 in MOF-eft-P is predicted to be 25 min and significantly longer than that of N2, indicating excellent CO2/N2 separation. This study demonstrates the bottom-up strategy to design Zr-MOFs and suggests MOF-eft-P to be an interesting candidate for CO2 capture.