Efficient Models for Predicting Temperature-Dependent Henry’s Constants and Adsorption Selectivities for Diverse Collections of Molecules in Metal–Organic Frameworks

Adsorption-based separations using metal–organic frameworks (MOFs) are a promising alternative to traditional energy-intensive separation process. Machine learning (ML) methods have been applied to predict large collections of adsorption isotherms in MOFs. Previous ML models, however, focus only on predicting single-component adsorption isotherms of a small number of molecules at a single temperature and lack accuracy in the dilute limit. Here we describe a useful strategy for predicting Henry’s constants and heats of adsorption for a diverse set of molecules in large collections of MOFs. To achieve this, a data set containing 21,195 MOF–molecule pairs with 45 adsorbates in 471 MOFs is generated, and a set of 135 descriptors combining energy and chemical information is developed. Robust ML models are developed to predict Henry’s constants and heats of adsorption after removing physically unfavorable adsorption pairs. The adsorption selectivity of near-azeotropic mixtures at two temperatures (300 and 373 K) is predicted with acceptable accuracy by using the predicted Henry’s constants and heats of adsorption. The ability to make temperature-dependent predictions is important for many practical separation applications. Our work sheds light on important challenges and opportunities for developing accurate models predicting adsorption properties for diverse collection of adsorbates and adsorbents.