Voltammetric Measurements for CO2 Reduction under Ambient Conditions

"The electrochemical reduction of CO2 was performed in a laboratory-made, divided Htype cell. A copper electrode was used as the cathode. An Aldrich Nafion 117-type ion exchange membrane (0.18mm thickness) was used as the diaphragm. NaHCO3 and KHCO3 were studied as the catholytes. Hydrogen evolution from water reduction and products from CO2 electrochemical conversion were recorded. Higher CO2 reduction enhancement was observed by KHCO3 as compared to NaHCO3. The main conclusion of this work is that in fact CO2 can be electrochemically reduced with copper electrodes.1.-INTRODUCTIONThe direct electrochemical reduction of CO2 may allow for a simple process and, by avoiding high temperature reactors, would enable the process production rate to be quickly varied to follow the time of day availability of surplus electricity [1]. Temperature has a major effect on the electrochemical conversion of CO2 since its solubility increases when temperature decreases [2]. The electrical potential applied to the electrochemical reacting system will have an influence on the product distribution, as well. For example, a narrow potential range during cyclo-voltagraphic studies will determine the detection of a lower number of products. A recommended potential range to study the electrochemical reduction of CO2 is -2V to 2V. Moreover, the reaction rate on the electrode is governed by various processes, such as the kinetics of electron transfer, adsorption/desorption at the electrode surface, and diffusion of CO2 to the Cu electrode. The availability of active species, CO2 for electro-reduction, is extremely low at the vicinity of the electrode surface and it seriously interferes with the rate of mass transfer. In batch type electrolytic reactors, depletion of CO2 at the surface takes place first. CO2 from the bulk then has to diffuse to the electrode surface, resulting in mass transfer controlled kinetic phenomena. During the above process, several other competitive side reactions could suppress the primary reaction even though the cathode has good electro catalytic properties for reduction of carbon dioxide. When the dynamic supply of specific active species is ensured to electrode surface, the mass transfer effects are minimized to certain extent. Hence it is envisaged that a continuous flow reactor is more efficient for the electro-reduction of CO2 in CO2 saturated aqueous electrolytes. The primary reactions that occur at the copper electrode during the reduction of CO2 are listed below (with the standard potentials calculated using formation energies [1] :"