Rational Electrolyte Modification of n ‐ CdSe / ( [ KFe ( CN ) 6 ] 3 − / 2 − ) Photoelectrochemistry

Abstract
Cyanide effects on photoelectrochemical cells (PECs) result in the highest solar to electrical conversion efficiency for a PEC. We report that appropriate solution modification stabilizes not only photoelectrode, but also the photoelectrolyte, against decomposition. We also investigate a suggestion that a substantial fraction of this efficiency and 26% of the observed photocurrent was due to a “virtual battery” resulting from electrochemical discharge of cyanide, rather than the photoinduced oxidation of ferrocyanide. This battery effect is not observed at either Pt or PEC systems, and results supporting that effect are simple artifacts of the experimental configuration in that study.

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