Membrane Selectivity Determines Energetic Losses for Ion Transport in Bioelectrochemical Systems

Ion transport through ion exchange membranes in Bioelectrochemical Systems (BESs) is different from other electrochemical cells as a result of the complex nature of the electrolyte, as the electrolytes in BESs contain many other cations and anions than H + and OH − . Moreover, these other cations and anions are generally present in high concentrations and therefore determine the ion transport through the membrane. In this work, we provide a theoretical framework for understanding ion transport across ion exchange membranes in BESs. We show that the transport of cations and anions other than H + and OH − determines the pH gradient between anode and cathode, and on top of that, also determines the membrane potential. Experimental data for microbial electrolysis cells with cation and anion exchange membranes are used to support the theoretical framework. In case of cation exchange membranes, the total potential loss consists of both the pH gradient and the concentration gradient of other cations, while in case of anion exchange membranes, the total potential loss is lower because part of the pH gradient loss can be recovered at the membrane. The presented work provides a better theoretical understanding of ion transport through ion exchange membranes in general and in BESs specifically.