Tuning the Electronic Properties of Homoleptic Silver(I) bis-BIAN Complexes towards Efficient Electrocatalytic CO2 Reduction

We report herein the preparation and characterization of six readily assembled bis-coordinated homoleptic silver(I) N,N′-bis(arylimino)acenaphthene (BIAN) complexes of general structure [Ag(I)(BIAN)2]BF4 and the influence of the electronic properties of the ligand substitution pattern on their performance in electrochemical CO2 reduction (CO2R). All the explored catalysts displayed substantial current enhancements in carbon-dioxide-saturated solvents dependent on the ligated BIAN and no significant concurrent H2 evolution when utilizing 2% H2O as a proton source. Additionally, preliminary studies, employing a drop-casted ink of 0.4 mg cm-2 [Ag(I)(4-OMe-BIAN)2]BF4 (Ag4) immobilized onto carbon paper gas diffusion electrodes in a flow cell with 1M KHCO3 aqueous electrolyte, resulted in a propitious Faradaic efficiency of 51% for CO at a current density of 50 mA cm-2.