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 CO 2 -philic tetrazolate toward CO 2 capture. The Zr-tetrazolate MOFs are revealed to exhibit substantially stronger CO 2 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 CO 2, as well as the highest CO 2 /N 2 selectivity; it outperforms many typical MOFs and other adsorbents reported in the literature. The breakthrough time of CO 2 in MOF-eft-P is predicted to be 25 min and significantly longer than that of N 2, indicating excellent CO 2 /N 2 separation. This study demonstrates the bottom-up strategy to design Zr-MOFs and suggests MOF-eft-P to be an interesting candidate for CO 2 capture.