Dynamically Formed Surfactant Assembly at the Electrified Electrode–Electrolyte Interface Boosting CO₂ Electroreduction

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Abstract

Electrocatalytic reactions occur in the nanoscale space at the electrified electrode-electrolyte interface. It is well known that the electrode-electrolyte interface, also called as interfacial microenvironment, is difficult to investigate due to the interference of bulk electrolytes and its dynamic evolution in response to applied bias potential. Here, we employ electrochemical co-reduction of CO₂ and H₂O on commercial Ag electrodes as a model system, in conjunction with quaternary ammonium cationic surfactants as electrolyte additives. We probe bias-potential-driven dynamic response of the interfacial microenvironment as well as the mechanistic origin of catalytic selectivity. By virtue of comprehensive in situ vibrational spectroscopy, electrochemical impedance spectroscopy, and molecular dynamics simulations, it is revealed that the structure of surfactants is dynamically changed from a random distribution to a nearly ordered assembly with increasing bias potential. The nearly ordered surfactant assembly regulates the interfacial water environment by repelling isolated water and suppressing water orientation into an ordered structure as well as promotes CO₂ enrichment at the electrified interface. Eventually, the formed hydrophobic-aerophilic interface microenvironment reduces the activity of water dissociation and increases the selectivity of CO₂ electroreduction to CO. These results highlight the importance of regulating the interfacial microenvironment by organic additives as a means of boosting the electrochemical performance in electrosynthesis and beyond.

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