Abstract
Metal–organic frameworks are known to contain defects within their crystalline structures. Successful engineering of these defects can lead to modifications in material properties that can potentially improve the performance of many existing frameworks. Herein, we report the high-throughput computational screening of a large experimental metal–organic framework database to identify 13 frameworks that show significantly improved methane storage capacities with linker vacancy defects. The candidates are first identified by focusing on structures with methane-inaccessible pores blocked away from the main adsorption channels. Then, organic linkers of the candidate structures are judiciously replaced with appropriate modulators to emulate the presence of linker vacancies, resulting in the integration and utilization of the previously inaccessible pores. Grand canonical Monte Carlo simulations of defective candidate frameworks show significant enhancements in methane storage capacities, highlighting that rational defect engineering can be an effective method to significantly improve the performance of the existing metal–organic frameworks.
Highlights
Metal–organic frameworks are known to contain defects within their crystalline structures
A large number of Metal–organic frameworks (MOFs) have been experimentally synthesized to date, researchers are generally interested in a select few MOFs (e.g., HKUST-1, MOF-74, MIL-53, UiO-66, and ZIF8) renowned for exhibiting exceptional attributes well suited for the development of important, industrial applications
A large-scale computational screening was conducted on an extended version of computation-ready experimental (CoRE) MOF data set[1] prior to application of the porosity filter, and the DFT-minimized MOF data set[34], for a total of 11,558 structures with a unique Cambridge Structural Database (CSD) reference codes
Summary
Metal–organic frameworks are known to contain defects within their crystalline structures Successful engineering of these defects can lead to modifications in material properties that can potentially improve the performance of many existing frameworks. Given thousands of experimentally synthesized MOFs, we hypothesize that many of them will exhibit inaccessible pores whose presence has been neglected for the most part These inaccessible pores can be viewed as potential interaction sites yet to be exploited, and as such, the goal of this work is to develop a methodology in which these sites can be freshly excavated to significantly improve the adsorption properties of MOFs. One possible way to achieve this is via defect engineering. Several different types of defects can be present within MOFs21–25, this study primarily focuses on zerodimensional linker vacancy defects that are more controlled
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