Engineering Aspects for the Design of a Bicarbonate Zero-Gap Flow Electrolyzer for the Conversion of CO₂ to Formate

CO₂ electrolyzers require gaseous CO₂ or saturated CO₂ solutions to achieve high energy efficiency (EE) in flow reactors. However, CO₂ capture and delivery to electrolyzers are in most cases responsible for the inefficiency of the technology. Recently, bicarbonate zero-gap flow electrolyzers have proven to convert CO₂ directly from bicarbonate solutions, thus mimicking a CO₂ capture medium, obtaining high Faradaic efficiency (FE) and partial current density (CD) toward carbon products. However, since bicarbonate electrolyzers use a bipolar membrane (BPM) as a separator, the cell voltage (V_Cell) is high, and the system becomes less efficient compared to analogous CO₂ electrolyzers. Due to the role of the bicarbonate both as a carbon donor and proton donor (in contrast to gas-fed CO₂ electrolyzers), optimization by using know-how from conventional gas-fed CO₂ electrolyzers is not valid. In this study, we have investigated how different engineering aspects, widely studied for upscaling gas-fed CO₂ electrolyzers, influence the performance of bicarbonate zero-gap flow electrolyzers when converting CO₂ to formate. The temperature, flow rate, and concentration of the electrolyte are evaluated in terms of FE, productivity, V_Cell, and EE in a broad range of current densities (10-400 mA cm^-2). A CD of 50 mA cm^-2, room temperature, high flow rate (5 mL cm^-2) of the electrolyte, and high carbon load (KHCO₃ 3 M) are proposed as potentially optimal parameters to benchmark a design to achieve the highest EE (27% is obtained this way), one of the most important criteria when upscaling and evaluating carbon capture and conversion technologies. On the other hand, at high CD (>300 mA cm^-2), low flow rate (0.5 mL cm^-2) has the highest interest for downstream processing (>40 g L^-1 formate is obtained this way) at the cost of a low EE (<10%).