Promoting electrocatalytic CO2 reduction via anchoring quaternary piperidinium cations onto copper electrode

Cation identity in the electrolyte is known to have a critical influence on electrocatalytic CO2 reduction reaction (CO2RR). However, the impact of cation aggregation state at the electrode/electrolyte interface, particularly for organic cations, remains unclear for CO2RR. In this study, we investigated the effect of the organic cation aggregation state, by examining the CO2RR behaviors over a copper (Cu) electrode, before and after the surface modification of a polyelectrolyte (i.e., quaternary ammonia poly (N-methyl-piperidine-co-p-terphenyl) with grafted piperidinium cations), in an aqueous electrolyte with free-moving piperidinium (Pip+) cations. Immobilizing the Pip+ cations on Cu surface was found to effectively promote the CO2RR selectivity. The underlying cause was further explored by in-situ attenuated total reflectance surface-enhanced infrared absorption spectroscopy and electrochemical double-layer capacitance measurements, illustrating that the enhanced CO2RR performance was due to the change in electrode/electrolyte interface properties. These findings would contribute to further optimization of the electrode/electrolyte interface for efficient CO2RR.