Molecular Probing in a Metal–Organic Framework for Selective Gas Adsorption and Separation

Metal-organic frameworks (MOFs) hold significant potential for selective gas adsorption and separation. However, it remains challenging to experimentally reveal collective host-guest interactions and cooperative binding sites at the atomic level in nanosized MOFs and thereby rationalize their separation preferences. Here, we report a molecular probing strategy combined with cryo-3D ED for guiding the selective gas adsorption and separation in MOFs. Molecular probes were purposefully selected to map the binding domains of gas adsorbates in the candidate MOF via atomic-level structural analysis by cryo-3D ED, thereby rationalizing which separation scenario the MOF is most likely to favor. As an example, CO