Enhancement of electrocatalytic abilities toward CO2 reduction by tethering redox-active metal complexes to the active site.

Tethering metal complexes, like [Ru(bpy)2Cl2] (bpy = 2,2'-bipyridine), which are redox-active at low reduction potentials and have the ability to transfer electrons to another complex, to a [Ni(cyclen)]2+ electrocatalyst enhanced the reduction of CO2 to CO at low overpotentials. The [Ni(cyclen)]2+ electrocatalyst was modified by tethering redox-active metal complexes via 4-methylpyridyl linkers. The redox-active metal complexes were reduced after CO2 bound to the active site. In controlled potential electrolysis (CPE) experiments in 95 : 5 (v/v) CH3CN/H2O, [{([Ru]pic)4cyclen}NiCl]5+ ([Ru]+ = {Ru(bpy)2Cl}+; pic = 4-methylpyridyl) could be used to reduce CO2 into CO at a turnover frequency (TOF) of 708 s-1 with a faradaic efficiency (FE) of 80% at an onset potential of -1.60 V vs. NHE. At the same time, this electrocatalyst was active at an onset potential of -1.25 V vs. NHE, which is the reduction potential of one of the bpy ligands of the [Ru]+ moieties, with FE = 84% and TOF = 178 s-1. When the electrocatalysis was performed using [bn4cyclenNiCl]Cl (bn = benzyl) without tethered redox-active metal complexes, the TOF value was determined to be 8 s-1 with FE = 77% at an onset potential of -1.45 V vs. NHE. The results show that tethering redox-active metal complexes significantly improves the electrocatalytic activities by lowering the potential needed to reduce CO2.

Correction: Ionic-caged heterometallic bismuth-platinum complex exhibiting electrocatalytic CO2 reduction.

Correction for 'Ionic-caged heterometallic bismuth-platinum complex exhibiting electrocatalytic CO2 reduction' by Takefumi Yoshida et al., Dalton Trans., 2020, 49, 2652-2660.