ABSTRACT
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 (VCell) 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, VCell, 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%).
ABSTRACT
Cationic surfactants, mainly hexadecyl cetrimonium bromide (CTAB), are widely used in electrocatalysis to affect the selectivity of the reaction, specifically to inhibit the hydrogen evolution reaction (HER) in CO2 reduction (CO2R) systems. However, little research has been done on the modification of the functional groups present in such surfactants in order to promote this HER-inhibiting effect. In this work, the effectiveness of CTAB was promoted by substituting a methyl group of the quaternary amine for a benzyl group. This cationic surfactant, cetalkonium chloride (CKC), increased the hydrophobicity of the surface of the electrode, promoting the HER inhibition and the CO2R when HCO3- is used as a carbon source, which allows combining capture and conversion in one and the same medium, making it industrially highly attractive. By performing a detailed electrochemical characterization, we proved that the benzyl group formed an enhanced hydrophobic layer on the surface of the electrode in addition to the alkyl chain of the surfactant, showing higher effectiveness compared to CTAB. In fact, the Faradaic efficiency of the CO2R increased from 39 to 66% in saturated HCO3- electrolytes by using CKC instead of CTAB as the HER inhibitor. This opens up a wide range of avenues for research on the application of surfactants in the field of electrocatalysis, because, as proven, a selective modification of it can tune the selectivity of the reaction, adding a new variable in the design of an efficient carbon capture and utilization system.
