Exploiting Large‐Pore Metal–Organic Frameworks for Separations through Entropic Molecular Mechanisms

We review the molecular mechanisms behind adsorption and the separations of mixtures in metal–organic frameworks and zeolites. Separation mechanisms can be based on differences in the affinity of the adsorbate with the framework and on entropic effects. To develop next‐generation adsorbents, the separation efficiency of the materials needs to be improved. The performance under industrially relevant conditions largely depends on two factors: 1) the separation selectivity and 2) the pore volume capacity of the material. Enthalpic mechanisms can lead to increased selectivities, but these are mostly restricted to the low loading regime, and hence these mechanisms are unable to make use of all of the large‐pore volume that a metal–organic framework can provide. Industrial processes routinely operate in the pore saturation regime. In this Review, we focus on entropic molecular separation mechanisms that are effective under these conditions and, in particular, on a recent methodology to obtain high selectivities at high pore loading.