Efficient Generation of Large Collections of Metal–Organic Framework Structures Containing Well-Defined Point Defects

High-throughput molecular simulations of metal–organic frameworks (MOFs) are a useful complement to experiments to identify candidates for chemical separation and storage. All previous efforts of this kind have used simulations in which MOFs are approximated as defect-free. We introduce a tool to readily generate missing-linker defects in MOFs and demonstrate this tool with a collection of 507 defective MOFs. We introduce the concept of the maximum possible defect concentration; at higher defect concentrations, deviations from the defect-free crystal structure would be readily evident experimentally. We studied the impact of defects on molecular adsorption as a function of defect concentrations. Defects have a slightly negative or negligible influence on adsorption at low pressures for ethene, ethane, and CO2 but a strong positive influence for methanol due to hydrogen bonding with defects. Defective structures tend to have loadings slightly higher than those of defect-free structures for all adsorbates at elevated pressures.