Transferable force fields for adsorption of small gases in zeolites.

We provide transferable force fields for oxygen, nitrogen, and carbon monoxide that are able to reproduce experimental adsorption in both pure silica and alumino-substituted zeolites at cryogenic and high temperatures. The force field parameters can be combined with those previously reported for carbon dioxide, methane, and argon, opening the possibility for studying mixtures of interest containing the six components. Using these force field parameters we obtained some adsorption isotherms at cryogenic temperatures that at first sight were in discrepancies with experimental values for certain molecules and structures. We attribute these discrepancies to the sensitiveness of the equipment and to kinetic impedimenta that can lead to erratic results. Additional problems can be found during simulations when extra-framework cations are present in the system as their lack of mobility at low temperatures could lead to kinetic effects that hinder experimental adsorption.

Zeolites for the selective adsorption of sulfur hexafluoride.

Molecular simulations have been used to investigate at the molecular level the suitability of zeolites with different topology on the adsorption, diffusion and separation of a nitrogen-sulfur hexafluoride mixture containing the latter at low concentration. This mixture represents the best alternative for the sulfur hexafluoride in industry since it reduces the use of this powerful greenhouse gas. A variety of zeolites are tested with the aim to identify the best structure for the recycling of sulfur hexafluoride in order to avoid its emission to the atmosphere and to overcome the experimental difficulties of its handling. Even though all zeolites show preferential adsorption of sulfur hexafluoride, we identified local structural features that reduce the affinity for sulfur hexafluoride in zeolites such as MOR and EON, providing exclusive adsorption sites for nitrogen. Structures such as ASV and FER were initially considered as good candidates based on their adsorption features. However, they were further discarded based on their diffusion properties. Regarding operation conditions for separation, the range of pressure that spans from 3 × 10(2) to 3 × 10(3) kPa was identified as the optimal to obtain the highest adsorption loading and the largest SF6/N2 selectivity. Based on these findings, zeolites BEC, ITR, IWW, and SFG were selected as the most promising materials for this particular separation.

Zeolite screening for the separation of gas mixtures containing SO2, CO2 and CO.

We used a combination of experiments and molecular simulations to investigate at the molecular level the effects of zeolite structure on the adsorption and diffusion of sulfur dioxide, carbon dioxide and carbon monoxide as well as separation processes of their mixtures. Our study involved different zeolite topologies and revealed numerous structure-property trends depending on the temperature and pressure conditions. Sulfur dioxide, which has the strongest interactions with zeolites due to its size and polarity, showed the largest adsorption across investigated temperatures and pressures. Our results indicate that structures with channel-type pore topology and low pore volume are the most promising for selective adsorption of sulfur dioxide over carbon dioxide and carbon monoxide under room conditions, while structures with higher pore volume exhibit better storage capacity at higher pressure. Our results emphasize the need for considering both adsorption and diffusion processes in the selection of the optimal structure for a given separation process. Our findings help to identify the best materials for effective separation processes under realistic operating conditions.

Understanding Gas-Induced Structural Deformation of ZIF-8.

ZIF-8 is a zeolitic imidazolate framework with very good thermal and chemical stability that opens up many applications that are not feasible by other metal-organic frameowrks (MOFs) and zeolites. Several works report the adsorption properties of ZIF-8 for strategic gases. However, despite the vast experimental corpus of data reported, there seems yet to be a dearth in the understanding of the gas adsorption properties. In this work we provide insights at a molecular level on the mechanisms governing the ZIF-8 structural deformation during molecular adsorption. We demonstrate that the ZIF-8 structural deformation during the adsorption of different molecules at cryogenic temperature goes beyond the gas-induced rotation of the imidazolate linkers. We combine experimental and simulation studies to demonstrate that this deformation is governed by the polarizability and molecular size and shape of the gases, and that the stepped adsorption behavior is defined by the packing arrangement of the guest inside the host.