Electrocatalytic reduction of carbon dioxide to methanol. Part 2. Effects of metal complex and primary alcohol

Abstract

The conversion of CO₂ into methanol by Everitt's salt, K₂Fe^II[Fe^II(CN)₆], has been studied in the presence of various metal complexes and primary alcohols. The activation energies for the methanol formation were 5.8–10.6 kcal mol^–1, approximately twice those for the reduction of CO. The i.r. spectra of the metal complexes indicated that the reduction of CO₂ takes place via a formate-type intermediate. The mechanism is considered to be very similar to that for reduction of CO, but the reduction of CO₂ appears to be more dominated by its insertion into a M(central metal)–OR(primary alcohol) bond than is that of CO.