Accelerating In Silico Discovery of Metal–Organic Frameworks for Ethane/Ethylene and Propane/Propylene Separation: A Synergistic Approach Integrating Molecular Simulation, Machine Learning, and Active Learning

Cryogenic distillation, a currently employed method for C₂H₄/C₂H₆ and C₃H₆/C₃H₈ mixture separation, is energy-intensive, prompting the research toward alternative technologies, including adsorbent-based separation. In this work, we combine machine learning (ML) technique with high-throughput screening to screen ∼23,000 hypothetical metal-organic frameworks (MOFs) for paraffin (C₂H₆ and C₃H₈) selective adsorbent separation. First, structure-based prescreening was employed to remove MOFs with undesired geometric properties. Further, a random forest model built upon the multicomponent grand canonical Monte Carlo (m-GCMC) simulation data of training set MOFs was found to be the most successful in learning the relationship between MOF features and olefin/paraffin mixture separation. Using this technique, the separation performance of the remaining (test set) MOFs was predicted, and the top-performing MOFs were identified. We also employed active learning (AL) to evaluate its effectiveness in improving the prediction of olefin/paraffin selectivity. AL was discovered to be ∼29 times more efficient than the best-supervised ML model, as it was able to identify the top materials in limited training data and at a fraction of computational cost and time as compared to ML techniques. Among the top selected materials, framework chemistry was found to be the most important parameter. Nickel and copper (as a metal node) in a tfzd and hms topological arrangement respectively, were discovered to be a prevalent attribute in high-performing MOFs, further demonstrating the prominent significance of framework chemistry. Additionally, the top MOFs discovered were studied in detail and further compared to the previously reported MOFs. These MOFs show the highest selectivity for C₂H₄/C₂H₆ and C₃H₆/C₃H₈ mixture separation, as reported until date. The hierarchical strategy devised in this study will facilitate the quick screening of MOFs across multiple databases toward industrially significant separation processes by leveraging molecular simulations and AL.