Electrocatalytic reduction of CO2 using rhenium complexes with dipyrido[3,2-a:2′,3′-c]phenazine ligands

A series of rhenium(l) complexes (1-4) with substituted dipyrido[3,2-a:2',3'-c]phenazine (dppz) ligands were synthesized and analyzed as electrocatalysts for CO2 reduction. Cyclic voltammetry study shows that complexes 1-4 exhibit dppz ligand-based and metal center-based quasi-reversible reductions under N-2. Under a CO2 atmosphere, complexes 1-4 exhibit electrocatalytic response consistent with CO2 -> CO reduction with the presence of the gaseous phase product CO confirmed by gas chromatography (GC). Re(2,2'-bpy)(CO)(3)Br (Lehn catalyst), a benchmark for electrocatalytic reduction of CO2 to CO, was also prepared and tested for electrocatalytic properties for comparison. The results suggest that chemical modification on the dppz ligand leads to interesting electrocatalytic properties and the large conjugation of the dppz ligand can help store multiple electrons and lower the energy barrier for CO2 reduction. (C) 2017 Published by Elsevier B.V.