Computational Characterization of Zr-Oxide MOFs for Adsorption Applications

[Image: see text] Zr-oxide secondary building units construct metal–organic framework (MOF) materials with excellent gas adsorption properties and high mechanical, thermal, and chemical stability. These attributes have led Zr-oxide MOFs to be well-recognized for a wide range of applications, including gas storage and separation, catalysis, as well as healthcare domain. Here, we report structure search methods within the Cambridge Structural Database (CSD) to create a curated subset of 102 Zr-oxide MOFs synthesized to date, bringing a unique record for all researchers working in this area. For the identified structures, we manually corrected the proton topology of hydroxyl and water molecules on the Zr-oxide nodes and characterized their textural properties, Brunauer–Emmett–Teller (BET) area, and topology. Importantly, we performed systematic periodic density functional theory (DFT) calculations comparing 25 different combinations of basis sets and functionals to calculate framework partial atomic charges for use in gas adsorption simulations. Through experimental verification of CO(2) adsorption in selected Zr-oxide MOFs, we demonstrate the sensitivity of CO(2) adsorption predictions at the Henry’s regime to the choice of the DFT method for partial charge calculations. We characterized Zr-MOFs for their CO(2) adsorption performance via high-throughput grand canonical Monte Carlo (GCMC) simulations and revealed how the chemistry of the Zr-oxide node could have a significant impact on CO(2) uptake predictions. We found that the maximum CO(2) uptake is obtained for structures with the heat of adsorption values >25 kJ/mol and the largest cavity diameters of ca. 6–7 Å. Finally, we introduced augmented reality (AR) visualizations as a means to bring adsorption phenomena alive in porous adsorbents and to dynamically explore gas adsorption sites in MOFs.