Unveiling the Regulatory Factors for Phase Transitions in Zeolitic Imidazolate Frameworks: A High-Throughout Calculations and Data Mining

TL;DR

This study uses high-throughput calculations and data mining on over 20,000 MOFs to identify structural parameters that predict glass-forming ability and thermal stability, advancing understanding of MOF phase transitions.

Contribution

It introduces specific structural order parameters as structural genes for predicting MOF glass formation and validates their effectiveness through molecular dynamics simulations.

Findings

Identified TBOD and LCD as key predictors of GFA.

Validated order parameters via molecular dynamics simulations.

Predicted external pressure and electric fields influence TBOD.

Abstract

Recently, there have been significant advancements in the study of Metal-Organic Frameworks (MOFs), particularly in the discovery of glassy states in zeolitic imidazolate frameworks (ZIFs), a subset of MOFs. However, the correlation between the glass-forming ability (GFA) of MOFs and their structural characteristics remains poorly understood. To address this gap, we analyze over 20,000 MOFs from the QMOF database, comparing geometric and electronic order parameters between ZIFs and other MOFs. Our findings reveal a set of order parameters that effectively capture the thermal stability and GFA of MOFs, acting as structural genes to predict glass formation. Through molecular dynamics simulations on representative ZIF structures, we validate the reliability of these order parameters, particularly the total bond-order density (TBOD) and the largest cavity diameter (LCD), for screening potential melt-quenched MOFs. Furthermore, we predict that external pressure and electric fields can control the TBOD of MOFs, expanding our understanding of their thermal stability. This work identifies structural genes associated with the melt stability of MOFs,and contributes valuable insights into the prediction and understanding of MOF glass-forming ability.