Carbonate species as OH^- carriers for decreasing the pH gradient between cathode and anode in biological fuel cells

Anodes of biological fuel cells (BFCs) normally must operate at a near-neutral pH in the presence of various ionic species required for the function of the biological catalyst (e.g., substrate, nutrients, and buffers). These ionic species are in higher concentration than protons (H⁺) and hydroxides (OH^-); slow transport of H⁺ and OH^- equivalents between anode and cathode compartments can lead to a large pH gradient that can inhibit the function of biological components, decrease voltage efficiency in BFCs, or both. We evaluate the use of carbonate species as OH^- carriers from the cathode to the anode compartment This is achieved by adding CO₂ to the influent air in the cathode. CO ₂ is an acid that combines with OH^- in the cathode to produce bicarbonate and carbonate. These species can migrate to the anode compartment as OH^- carriers at a rate much greater than can OH ^- itself when the pH is not extremely high in the cathode compartment We demonstrate this concept by feeding different air/CO₂ mixtures to the cathode of a dual-chamber microbial fuel cell (MFC) fed with acetate as substrate. Our results show a 45% increase in power density (from 1.9 to 2.8 W/m²) by feeding air augmented with 2-10% CO₂. The cell voltage increased by as much as 120 mV, indicating that the pH gradient decreased by as much as 2 pH units. Analysis of the anode effluent showed an average increase of 4.9 mM in total carbonate, indicating that mostly carbonate was transferred from the cathode compartment. This process provides a simple way to minimize potential losses in BFCs due to pH gradients between anode and cathode compartments.