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Nanoporous solids are ubiquitous in chemical, energy, and environmental processes, where controlled transport of molecules through the pores plays a crucial role. They are used as sorbents, chromatographic or membrane materials for separations, and as catalysts and catalyst supports. Defined as materials where confinement effects lead to substantial deviations from bulk diffusion, nanoporous materials include crystalline microporous zeotypes and metal–organic frameworks (MOFs), and a number of semi-crystalline and amorphous mesoporous solids, as well as hierarchically structured materials, containing both nanopores and wider meso- or macropores to facilitate transport over macroscopic distances. The ranges of pore sizes, shapes, and topologies spanned by these materials represent a considerable challenge for predicting molecular diffusivities, but fundamental understanding also provides an opportunity to guide the design of new nanoporous materials to increase the performance of transport limited processes. Remarkable progress in synthesis increasingly allows these designs to be put into practice. Molecular simulation techniques have been used in conjunction with experimental measurements to examine in detail the fundamental diffusion processes within nanoporous solids, to provide insight into the free energy landscape navigated by adsorbates, and to better understand nano-confinement effects. Pore network models, discrete particle models and synthesis-mimicking atomistic models allow to tackle diffusion in mesoporous and hierarchically structured porous materials, where multiscale approaches benefit from ever cheaper parallel computing and higher resolution imaging. Here, we discuss synergistic combinations of simulation and experiment to showcase theoretical progress and computational techniques that have been successful in predicting guest diffusion and providing insights. We also outline where new fundamental developments and experimental techniques are needed to enable more accurate predictions for complex systems. [ABSTRACT FROM AUTHOR]

We investigated eight representative metal–organic frameworks for methane storage using molecular simulation. Validated force fields were used to calculate the amount adsorbed for pure methane and its mixtures with CO2 and H2O at 5.8 and 65 bar at 298 K within the composition limits specified for natural gas. Within the analyzed concentrations, the MOFs without open metal sites were minimally influenced by the presence of CO2 and H2O. However, for the MOFs with open metal sites, the presence of these species proved to be harmful. We found that concentrations as low as 25 ppm of water can reduce the delivered volume of methane by more than 20%. A detailed analysis of the adsorption mechanisms leading to this poisoning is presented. These results highlight the possible limitations of MOFs with open metal sites for use in natural gas storage. [ABSTRACT FROM AUTHOR]