Cobalt Porphyrin Catalyzed Reduction of CO2. Radiation Chemical, Photochemical, and Electrochemical Studies

Several cobalt porphyrins (CoP) have been reduced by radiation chemical, photochemical, and electrochemical methods, in aqueous and organic solvents. In aqueous solutions, the CoIP state is stable at high pH but is shorter lived in neutral and acidic solutions. Stable CoIP is also observed in organic solvents and is unreactive toward CO2. One-electron reduction of CoIP leads to formation of a species that is observed as a transient intermediate by pulse radiolysis in aqueous solutions and as a stable product following reduction by Na in tetrahydrofuran solutions. The spectrum of this species is not the characteristic spectrum of a metalloporphyrin π-radical anion and is ascribed to Co0P. This species binds and reduces CO2. Catalytic formation of CO and HCO2 is confirmed by photochemical experiments in acetonitrile solutions containing triethylamine as a reductive quencher. Catalytic reduction of CO2 is also confirmed by cyclic voltammetry in acetonitrile and butyronitrile solutions and is shown to occur at the potential at which CoIP is reduced to Co0P. As compared with CoTPP, fluorinated derivatives are reduced, and catalyze CO2 reduction, at less negative potentials.