Computational Characterization of Zr-Oxide MOFs for Adsorption Applications

Abstract

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 CO2 adsorption in selected Zr-oxide MOFs, we demonstrate the sensitivity of CO2 adsorption predictions at the Henry’s regime to the choice of the DFT method for partial charge calculations. We characterized Zr-MOFs for their CO2 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 CO2 uptake predictions. We found that the maximum CO2 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.

High-Throughput Computational Screening of Experimental Zr-Based MOFs for Elemental Mercury Capture

“…Simulation Details. Oktavian et al 42 created 102 Zroxide MOF structures from the Cambridge Structural Database (CSD) and manually corrected the topology of OH and water groups on the Zr-oxides. To assess the impact of various functional groups, the computation-ready, experimental metal−organic frameworks (CoRE-MOFs) were selected as the MOF database.…”

Optimal Surrogate Models for Predicting the Elastic Moduli of Metal–Organic Frameworks via Multiscale Features

“…21 However, existing topological analysis tools (for example, TOPOS 53 ) require manual input and user involvement, making it challenging to extract topological information automatically. 54,55…”

DigiMOF: A Database of Metal–Organic Framework Synthesis Information Generated via Text Mining

“…Metal–organic frameworks (MOFs) are a class of crystalline materials consisting of a lattice of metal ions co-ordinately bonded by organic linkers. MOFs are well known for their high surface areas and exceptionally tunable properties, which enable their potential application in areas including gas storage, − sensing, − separations, − drug delivery, − and catalysis. − Since the first MOFs were synthesized in the 1990s, thousands of MOFs have been produced at a laboratory scale. As of 2023, more than 100,000 MOF structures have been reported in the Cambridge Structural Database (CSD). , The sheer volume of distinct real MOF materials poses significant challenges for screening and isolating the best candidates for a given application: a typical problem of finding a needle in a haystack.…”