Transport and co‐transport of carboxylate ions and alcohols in cation exchange membranes

Understanding multi‐component transport behavior through hydrated dense membranes is of interest for numerous applications. For the particular case of photoelectrochemical CO2 reduction cells (PEC‐CRC), it is important to understand the multi‐component transport behavior of CO2 electrochemical reduction products including mobile carboxylates (formate and acetate) and alcohols (methanol and ethanol) in the ion exchange membranes as one role of the membrane in these devices is to minimize the permeation of these CO2 reduction products to the anolyte as they often oxidize back to CO2. Cation exchange membranes (CEM) are promising candidates for such devices as they act to minimize the permeation of mobile anions, such as carboxylates. However, the design of new CEMs is necessary as the permeation of carboxylates often increases in co‐permeation with alcohols. Here, we investigate the transport behavior of carboxylates and alcohols in two types of CEMs (1) a crosslinked CEM was prepared by free‐radical copolymerization of a sulfonated monomer (AMPS) with a crosslinker (PEGDA), and (2) Nafion® 117. We observe an increase in both PEGDA‐AMPS and Nafion® 117 diffusivities to carboxylates in co‐diffusion with alcohols. We attribute this behavior to charge screening by co‐diffusing alcohol that reduces the electrostatic repulsion between bound sulfonates and mobile carboxylates.