Publication date: 15th December 2014
The aqueous photocathode activity of regioregularconjugated polymers, a p-type organic semiconductor, is presented. Photocurrents generated under 100 mW cm-2 AM 1.5D irradiation will be described. We examine the electrochemistry of organic films in aqueous and non-aqueous solution in order to gain insight into the mechanism of photocathodic activity. The origin of photoelectrochemical cathodic current in acidic and neutral conditions is presented together with photocurrent generated in the presence of various redox couples. The concentration and pH dependency of photoelectrochemical reduction of redox species at conjugated polymers will also be discussed. Photoelectrolysis is also examined with increasing oxygen concentration, providing evidence that, in some instances, photocurrent is due to the reduction of O2 to O2•-. The increased concentration of dissolved oxygen in solution allows for a higher fraction of photogenerated charges to be transferred from the polymer film to O2 acceptors. These results provide sufficient evidence that that reduction of dissolved oxygen molecules in solution is a competitor for photoreduction, and innovative routes must be adopted to mitigate this.
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