Electrochemical Reduction of Carbon Dioxide

"Considerable research has been conducted on the anodic oxidation of methanol in fuel cells. The electrochemical reduction of carbon dioxide in aqueous solutions to form methanol is the same reaction in reverse, i.e. CO2 + 6 H+ + 6 e- ? CH3OH + H2O. The same catalysts and conditions may operate for both reaction directions. This carbon dioxide reduction reaction, however, must be able to compete with the electrochemical reduction of water to form hydrogen gas. Thermodynamically, the reduction of CO2 to form CH3OH is slightly more favorable than the reduction of water. The use of nearly neutral electrolytes rather than acidic electrolytes makes the reduction of CO2 kinetically more favorable. The thermodynamics of various reaction steps are presented. Similarities exist with the electrochemical reduction of CO2 and the green-plant photosynthesis process that converts CO2 to carbohydrates.IntroductionVirtually all of the oxygen in the earth’s atmosphere is of biological origin having been generated by green-plant photosynthesis from water and carbon dioxide [1]. The net reaction can be represented byCO2 + H2O ? O2 + [CH2O] (carbohydrates, etc.) (1)Chlorophyll and enzymes promote this reaction, and the energy required comes from sunlight. The actual photosynthesis process is a complex multistage reaction and requires 469 kJ mol-1 of energy supplied by the sun. Isotope tracer experiments using 18O have shown that both the oxygen atoms in the O2 molecule originate from H2O, whereas oxygen atoms in the carbohydrates come from CO2 [1]. The total amount of water on the earth is split by photosynthesis and reconstituted by respiration and combustion once every 2 million years or so. The photosynthetically generated oxygen gas temporarily enters the atmosphere and is recycled about once every 2000 years [1]. The carbon dioxide is partly recycled in the atmosphere and oceans after an average residence time of 300 years and is partly fixed by precipitation of CaCO3 and other carbonate minerals [1]."