Electro-oxidation of ethanol at Pt electrodes with the use of a Dynamic Electrochemical Impedance Spectroscopy (DEIS) technique

Abstract

Electro-oxidation of ethanol on smooth platinum surfaces was studied in thetemperature range 21C to 140C for 0.2 M ethanol in 0.5 M sulphuric acid.This was done by use of cyclic voltammetry and electrochemical impedancespectroscopy. In addition cyclic voltammetry with different ethanol concentrationsfrom 0.1 M to 1 M, in 0.5 M sulphuric acid was done at room temperature.Cyclic voltammetry with different ethanol concentrations showed a shift to morepositive potentials for the first oxidation peak in positive going scan as the ethanolconcentration increased. A shift to more positive potentials was also observed forthe oxidation peak in the negative scan as the concentration increased from 0.1M to 1 M. This indicates that the optimum surface condition is reached at higherpotentials for higher ethanol concentrations. This can be because ethanol andadsorbed ethanol derivatives take up more active sites at the surface, thus leavingless active sites available for adsorbed water derivatives which is necessary for theoxidation of ethanol to acetic acid and CO2.Cyclic voltammetry was done for increasing temperatures from 21C up to 140Cfor 0.2 M ethanol in 0.5 M sulphuric acid. These results showed an increasein oxidation current for all oxidation peaks as the temperature increased. Adecrease in peak potential for the first oxidation peak was observed for increasingtemperatures. This indicates that the optimum surface condition for ethanoloxidation is reached at lower potentials at higher temperatures. There was alsoseen an decrease in the apparent onset potential of the first oxidation peak as thetemperature increases. These effects can come from increased thermal activity forwater adsorption at higher temperatures. The peak potential for the oxidationpeak in negative going scan increased with increasing temperatures. This cancome from an easier reduction of platinum oxide at higher temperatures.Dynamic electrochemical impedance spectroscopy measurements was done atdifferent temperatures from 21C up to 140C for 0.2 M ethanol in 0.5 Msulphuric acid solution. The results from the measurements at 60C was fittedto electrochemical equivalent circuits. This gave indications of one kineticallysignificant surface adsorbed species in most potential regions with a notableoxidation current. This in combination with literature suggesting that acetic acidand acetaldehyde is the major products from ethanol electro-oxidation suggestthat the adsorbed intermediate is something other than CO(ads). Results fromthis work together with existing literature on ethanol oxidation was used to givea suggested simplified reaction mechanism for ethanol electro-oxidation.