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Nanoporous Materials Can Tune the Critical Point of a Pure Substance.


Molecular simulations and NMR relaxometry experiments demonstrate that pure benzene or xylene confined in isoreticular metal-organic frameworks (IRMOFs) exhibit true vapor-liquid phase equilibria where the effective critical point may be reduced by tuning the structure of the MOF. Our results are consistent with vapor and liquid phases extending over many MOF unit cells. These results are counterintuitive since the MOF pore diameters are approximately the same length scale as the adsorbate molecules. As applications of these materials in catalysis, separations, and gas storage rely on the ability to tune the properties of adsorbed molecules, we anticipate that the ability to systematically control the critical point, thereby preparing spatially inhomogeneous local adsorbate densities, could add a new design tool for MOF applications.

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