Effects of Benzyl-Functionalized Cationic Surfactants on the Inhibition of the Hydrogen Evolution Reaction in CO2 Reduction Systems

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.