The permeation of solutes through hydrated polymer membranes is of critical importance for many applications, including fuel cells and solar-driven electrochemical cells. In such devices, the undesirable crossover of small organics through a membrane separating halves of the electrochemical cell reduces device efficiency. Our group has shown how molecular transport behavior is different when multiple solutes (for example ethanol and propanol) are diffusing through a membrane compared to the single diffusing solute. This change in transport behavior, so-called emergent transport behavior, is attributed to the complex solute-solute and solute-membrane interactions in these systems impacting the solubility and diffusivity of these solutes in the membrane. Here, to understand the impact of solute-membrane bound ion interactions on molecular transport behavior, hydrated poly(ethylene glycol) diacrylate (PEGDA) membranes with varying the amount of ion exchange functional groups are synthesized. Negatively charged 2-acrylamido-2-methylpropanesulfonic acid (AMPS) is selected as a polymerizable PEGDA comonomer to synthesize cation exchange membranes. A custom-built diffusion cell coupled with an in situ attenuated total reflectance Fourier transform infrared (ATR-FTIR) spectroscopy is used to capture the time-resolved downstream solute concentrations in single and binary solute experiments. Membrane permeabilities are extracted from time-resolved half-cell concentration data using free volume models. The transport behavior of these novel ion exchange membranes is compared with a commercial cation exchange membrane, Nafion 117, towards understanding the impact of interactions between co-solutes, and the solutes and membrane-bound ion exchange functional groups on diffusion behavior. Overall, we observe emergent phenomena the permeability of sodium acetate is impacted by the presence of a co-solute (methanol) whereas the transport behavior of methanol remains unchanged. Understanding this solute-solute-membrane emergent transport behavior is important for the design of ion-containing polymer membranes for electrochemical devices.

Emergent transport phenomena in sulfonated polyether-based ion-containing polymer membranes

Macromolecular Chemistry: The Second Century

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ACS Spring 2020 National Meeting & Expo

The official archive and repository for all ACS Meetings & Expositions abstracts and select posters or presentations.