Overlayer formation as a source of stability in the n-type photoelectrochemical cell the N-CdS/Fe(CN)64-/3-cell

Holly Dee Rubin, Douglas J. Arent, Brian Humphrey, Andrew B. Bocarsly

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Abstract

The stability of n-CdS in a Fe(CN64-/3- electrolyte is demonstrated to be due to the formation of a CdFe(CN62-/1-overlayer. Mediated hole transfer through the overlayer to solution Fe(CN64- competes with photoanodic decomposition of the electrode. The charge transfer energetics and kinetics of the overlayer are very sensitive to the supporting electrolyte cation. Variations in supporting electrolyte allow maximization of overlap between the semiconductor states and the filled levels of the surface CdFe(CN62/1 couple. This leads to enhanced energy conversion efficiencies and minimization of electrode decomposition. For the n-CdS electrode, a supporting electrolyte containing both K+ and Cs+ is found to maximize cell performance, A surface state responsible for deleterious electron transfer through the barrier is observed —600 mV positive of the conduction bandedge. Cells with monochromatic efficiencies in excess of 20% (488 nm) can be obtained by considering the CdFe(CN62-/1- overlayer properties.

Original languageEnglish
Pages (from-to)93-101
Number of pages9
JournalJournal of the Electrochemical Society
Volume134
Issue number1
DOIs
StatePublished - 1 Jan 1987

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Photoelectrochemical cells
Electrolytes
Electrodes
Decomposition
Surface states
Energy conversion
Conversion efficiency
Cations
Charge transfer
Positive ions
Semiconductor materials
Kinetics
Electrons

Cite this

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title = "Overlayer formation as a source of stability in the n-type photoelectrochemical cell the N-CdS/Fe(CN)64-/3-cell",
abstract = "The stability of n-CdS in a Fe(CN64-/3- electrolyte is demonstrated to be due to the formation of a CdFe(CN62-/1-overlayer. Mediated hole transfer through the overlayer to solution Fe(CN64- competes with photoanodic decomposition of the electrode. The charge transfer energetics and kinetics of the overlayer are very sensitive to the supporting electrolyte cation. Variations in supporting electrolyte allow maximization of overlap between the semiconductor states and the filled levels of the surface CdFe(CN62/1 couple. This leads to enhanced energy conversion efficiencies and minimization of electrode decomposition. For the n-CdS electrode, a supporting electrolyte containing both K+ and Cs+ is found to maximize cell performance, A surface state responsible for deleterious electron transfer through the barrier is observed —600 mV positive of the conduction bandedge. Cells with monochromatic efficiencies in excess of 20{\%} (488 nm) can be obtained by considering the CdFe(CN62-/1- overlayer properties.",
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Overlayer formation as a source of stability in the n-type photoelectrochemical cell the N-CdS/Fe(CN)64-/3-cell. / Rubin, Holly Dee; Arent, Douglas J.; Humphrey, Brian; Bocarsly, Andrew B.

In: Journal of the Electrochemical Society, Vol. 134, No. 1, 01.01.1987, p. 93-101.

Research output: Contribution to journalArticleResearchpeer-review

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T1 - Overlayer formation as a source of stability in the n-type photoelectrochemical cell the N-CdS/Fe(CN)64-/3-cell

AU - Rubin, Holly Dee

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AU - Humphrey, Brian

AU - Bocarsly, Andrew B.

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AB - The stability of n-CdS in a Fe(CN64-/3- electrolyte is demonstrated to be due to the formation of a CdFe(CN62-/1-overlayer. Mediated hole transfer through the overlayer to solution Fe(CN64- competes with photoanodic decomposition of the electrode. The charge transfer energetics and kinetics of the overlayer are very sensitive to the supporting electrolyte cation. Variations in supporting electrolyte allow maximization of overlap between the semiconductor states and the filled levels of the surface CdFe(CN62/1 couple. This leads to enhanced energy conversion efficiencies and minimization of electrode decomposition. For the n-CdS electrode, a supporting electrolyte containing both K+ and Cs+ is found to maximize cell performance, A surface state responsible for deleterious electron transfer through the barrier is observed —600 mV positive of the conduction bandedge. Cells with monochromatic efficiencies in excess of 20% (488 nm) can be obtained by considering the CdFe(CN62-/1- overlayer properties.

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