Electrocatalytic Conversion of CO(2) to Formate at Low Overpotential by Electrolyte Engineering in Model Molecular Catalysis

An electrolyte engineering strategy was developed for CO(2) reduction into formate with a model molecular catalyst, [Rh(bpy)(Cp*)Cl]Cl, by modifying the solvent (organic or aqueous), the proton source (H(2)O or acetic acid), and the electrode/solution interface with imidazolium‐ and pyrrolidinium‐based ionic liquids (ILs). Experimental and theoretical density functional theory investigations suggested that π(+)‐π interactions between the imidazolium‐based IL cation and the reduced bipyridine ligand of the catalyst improved the efficiency of the CO(2) reduction reaction (CO(2)RR) by lowering the overpotential, while granting partial suppression of the hydrogen evolution reaction. This allowed tuning the selectivity towards formate, reaching for this catalyst an unprecedented faradaic efficiency (FE(HCOO)−) ≥90 % and energy efficiency of 66 % in acetonitrile solution. For the first time, relevant CO(2) conversion to formic acid/formate was reached at low overpotential (0.28 V) using a homogeneous catalyst in acidic aqueous solution (pH=3.8). These results open up a new strategy based on electrolyte engineering for enhancing carbon balance in CO(2)RR.