Smart Electrode Surfaces by Electrolyte Immobilization for Electrocatalytic CO₂ Conversion

The activity and selectivity of molecular catalysts for the electrochemical CO₂ reduction reaction (CO₂RR) are influenced by the induced electric field at the electrode/electrolyte interface. We present here a novel electrolyte immobilization method to control the electric field at this interface by positively charging the electrode surface with an imidazolium cation organic layer, which significantly favors CO₂ conversion to formate, suppresses hydrogen evolution reaction, and diminishes the operating cell voltage. Those results are well supported by our previous DFT calculations studying the mechanistic role of imidazolium cations in solution for CO₂ reduction to formate catalyzed by a model molecular catalyst. This smart electrode surface concept based on covalent grafting of imidazolium on a carbon electrode is successfully scaled up for operating at industrially relevant conditions (100 mA cm^-2) on an imidazolium-modified carbon-based gas diffusion electrode using a flow cell configuration, where the CO₂ conversion to formate process takes place in acidic aqueous solution to avoid carbonate formation and is catalyzed by a model molecular Rh complex in solution. The formate production rate reaches a maximum of 4.6 g_HCOO m^-2 min^-1 after accumulating a total of 9000 C of charge circulated on the same electrode. Constant formate production and no significant microscopic changes on the imidazolium-modified cathode in consecutive long-term CO₂ electrolysis confirmed the high stability of the imidazolium organic layer under operating conditions for CO₂RR.