Adapted thermodynamical model for the prediction of adsorption in nanoporous materials

In this paper, we introduce a novel, adapted approach for computing gas adsorption properties in porous materials. Our methodology is based on the Dubinin-Polanyi's adsorption model, and we investigate various frameworks to estimate its required essential components and prediction capabilities. The required components are linked to the physicochemical properties of the adsorbates, such as the vapor saturation pressure and density in the adsorbed phase. To conduct this analysis, we obtain adsorption isotherms for several metal–organic frameworks encompassing a range of pore sizes, shapes, and chemical compositions. We then apply and evaluate multiple combinations of models for saturation pressure and density. After the evaluation of the methods, we propose a working thermodynamic model for computing adsorption isotherms, which entails using the critical isochore as an approximation of the saturation pressure above the critical point and applying Hauer's method with a universal thermal expansion coefficient for density in the adsorbed state. This framework is applicable not only to simulated isotherms but also to experimental data from the literature for various molecules and structures of different natures, demonstrating robust predictive capabilities and high transferability. Our method showcases superior performance in terms of accuracy, generalizability, and simplicity compared to existing methods currently in use. In light of our results, this method, starting from a single adsorption curve and based on physically interpretable parameters, can predict adsorption properties across a wide range of operating conditions.