Alcohol (methanol, ethanol, 1-propanol, 2-propanol and 1-butanol) and water vapor adsorption in zeolitic imidazolate frameworks (ZIF-8, ZIF-71 and ZIF-90) with similar crystal sizes was systematically studied. The feasibility of applying these ZIF materials to the recovery of bio-alcohols is evaluated by estimating the vapor-phase alcohol-water sorption selectivity.

We examine the adsorption and diffusion of small alcohols in ZIF-8 and ZIF-90 with a combined experimental and modeling approach. Our Grand Canonical Monte Carlo (GCMC) simulations predict that both ZIFs exhibit a slight adsorption selectivity for ethanol over methanol, in good agreement with previous experimental data. The adsorption uptake of the alcohols at low pressures is found to be significantly higher in ZIF-90 than ZIF-8. Our simulations indicate that this is due to hydrogen bonding between the alcohols and the carbonyl group of ZIF-90 but that this effect is not strong enough to cause appreciable flexibility of the ZIF-90 framework during adsorption. We also report alcohol self-diffusivities and Arrhenius parameters measured using pulsed field gradient NMR (PFG-NMR) and molecular dynamics (MD) simulations. The diffusivities measured using PFG-NMR indicate that the diffusion selectivity of methanol over ethanol is significantly higher in ZIF-8 (S = 229) than in ZIF-90 (S = 6) at T = 25 °C. Qualitative agreement is obtained between experimental and simulated diffusivities using the generalized AMBER (GAFF) force field including framework flexibility.

Macromolecules that exhibit both electron transport and ionic mass transport (i.e., mixed conducting polymers) are ascendant with respect to both emerging application spaces and the elucidation of their fundamental physical principles. The unique coupling between the two modes of conduction puts these materials at the center of many next-generation organic electronic applications. The molecular details of this coupling are also at the epicenter of outstanding questions about how these materials function; how monomer and macromolecular chemistry dictates observable properties; and ultimately, how these macromolecular materials can be rationally designed, processed, and implemented into high-performance devices. Here, we focus on what is currently known about coupled ionic-electronic transport in these polymers and where there are open opportunities in the field. These opportunities include the syntheses of designer macromolecules, the need for significant simulation efforts that provide molecular-level insights into the mixed conduction mechanism, and the need for advanced characterization techniques for real-time monitoring of polymer morphology, as this is critical to coupled ion-charge transport processes. Considering the early stage of this important subfield of polymer science, we also present our view of how the development of mixed conductors can benefit from the lessons learned from previous polymerbased electronic devices.

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