Coupling Structural and Adsorption Properties of Metal-Organic Frameworks: From Pore Size Distribution to Pore Type Distribution.

Metal-organic frameworks (MOFs) attract a rapidly growing attention across the disciplines due to their multifarious pore structures and unique ability to selectively adsorb, store, and release various guest molecules. Pore structure characterization and coupling of adsorption and structural properties are imperative for rational design of advanced MOF materials and their applications. The pore structure of MOFs represents a three-dimensional network comprised of several types of pore compartments: interconnected cages and channels distinguished by their size, shape, and chemistry. Here, we propose a novel methodology for pore structure characterization of MOF materials based on matching of the experimental adsorption isotherms to in silico-generated fingerprint isotherms of adsorption in individual pore compartments of the ideal crystal. The proposed approach couples structural and adsorption properties, determines the contributions of different types of pores into the total adsorption, and estimates to what extent the pore structure of the sample under investigation is different from the ideal crystal. The MOF pore structure is characterized by the pore type distribution (PTD), which is more informative than the traditional pore size distribution that is based on oversimplistic pore models. The method is illustrated on the example of Ar adsorption at 87 K on hydrated and dehydrated structures of Cu-BTC, one of the most well-known MOF materials. The PTD determined from the experimental isotherm provides an estimate of the crystal fraction in the sample and the accessibility and degree of hydration of different types of pore compartments. In addition, the PTD determined from the experimental adsorption isotherm is used to predict the isosteric heat of adsorption that provides important information on the specifics of adsorption interactions. The results are found to be in excellent agreement with experimental data. Such detailed information about the pore structure and adsorption properties of practical MOF samples cannot be obtained with currently available methods of adsorption characterization.