Photoelectrochemistry of p-lnP in Saturated CaCl2 Solutions

J. M. Rosamilia, Lynn Schneemeyer, B. Miller

Research output: Contribution to journalArticle

4 Citations (Scopus)

Abstract

InP-based cells for photoelectrochemical light to electrical energy conversion are critically dependent on the oxidation state of the semiconductor interface. Cr(III)-Cr(II) electrolytes are favorably placed energetically for p-type cells but are lacking in charge transfer kinetics and prone to causing surface passivation by Cr-containing films. Moving from conventional (0.2M CaCl2) to saturated (5.6M CaCl2) electrolytes with the p-InP/Cr(III)-Cr(II) semiconductor-electrolyte interface provides a dramatic enhancement in electrochemical output and stability. Acceleration of electron transport for Cr(III) → Cr(II) conversion through ligand (Cl-) bridging and prevention of the formation of passivating Cr oxide films in the high chloride-lowered water activity medium are responsible for these beneficial effects. Comparison of the Cr couple's behavior to that of Eu(III)-Eu(II) and of Pt-catalyzed H2 evolution at metal and p-InP electrodes shows a much greater contrast for Cr(III)-Cr(II) voltammetry between the dilute and saturated CaCl2 electrolytes. Ring-disk electrode studies and cyclic voltammetry were used to establish the conclusions, and mass-transfer data (diffusion coefficients, kinematic viscosity) for these various Cr, Eu, and H species were obtained in the two media from rotating disk electrode measurements.

Original languageEnglish
Pages (from-to)1684-1689
Number of pages6
JournalJournal of the Electrochemical Society
Volume134
Issue number7
DOIs
StatePublished - 1 Jan 1987

Fingerprint

photoelectrochemistry
Electrolytes
electrolytes
Electrodes
electrodes
Semiconductor materials
rotating disks
energy conversion
Rotating disks
Voltammetry
electric power
cells
Energy conversion
Passivation
passivity
Cyclic voltammetry
Oxide films
mass transfer
oxide films
Charge transfer

Cite this

Rosamilia, J. M. ; Schneemeyer, Lynn ; Miller, B. / Photoelectrochemistry of p-lnP in Saturated CaCl2 Solutions. In: Journal of the Electrochemical Society. 1987 ; Vol. 134, No. 7. pp. 1684-1689.
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abstract = "InP-based cells for photoelectrochemical light to electrical energy conversion are critically dependent on the oxidation state of the semiconductor interface. Cr(III)-Cr(II) electrolytes are favorably placed energetically for p-type cells but are lacking in charge transfer kinetics and prone to causing surface passivation by Cr-containing films. Moving from conventional (0.2M CaCl2) to saturated (5.6M CaCl2) electrolytes with the p-InP/Cr(III)-Cr(II) semiconductor-electrolyte interface provides a dramatic enhancement in electrochemical output and stability. Acceleration of electron transport for Cr(III) → Cr(II) conversion through ligand (Cl-) bridging and prevention of the formation of passivating Cr oxide films in the high chloride-lowered water activity medium are responsible for these beneficial effects. Comparison of the Cr couple's behavior to that of Eu(III)-Eu(II) and of Pt-catalyzed H2 evolution at metal and p-InP electrodes shows a much greater contrast for Cr(III)-Cr(II) voltammetry between the dilute and saturated CaCl2 electrolytes. Ring-disk electrode studies and cyclic voltammetry were used to establish the conclusions, and mass-transfer data (diffusion coefficients, kinematic viscosity) for these various Cr, Eu, and H species were obtained in the two media from rotating disk electrode measurements.",
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Photoelectrochemistry of p-lnP in Saturated CaCl2 Solutions. / Rosamilia, J. M.; Schneemeyer, Lynn; Miller, B.

In: Journal of the Electrochemical Society, Vol. 134, No. 7, 01.01.1987, p. 1684-1689.

Research output: Contribution to journalArticle

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AB - InP-based cells for photoelectrochemical light to electrical energy conversion are critically dependent on the oxidation state of the semiconductor interface. Cr(III)-Cr(II) electrolytes are favorably placed energetically for p-type cells but are lacking in charge transfer kinetics and prone to causing surface passivation by Cr-containing films. Moving from conventional (0.2M CaCl2) to saturated (5.6M CaCl2) electrolytes with the p-InP/Cr(III)-Cr(II) semiconductor-electrolyte interface provides a dramatic enhancement in electrochemical output and stability. Acceleration of electron transport for Cr(III) → Cr(II) conversion through ligand (Cl-) bridging and prevention of the formation of passivating Cr oxide films in the high chloride-lowered water activity medium are responsible for these beneficial effects. Comparison of the Cr couple's behavior to that of Eu(III)-Eu(II) and of Pt-catalyzed H2 evolution at metal and p-InP electrodes shows a much greater contrast for Cr(III)-Cr(II) voltammetry between the dilute and saturated CaCl2 electrolytes. Ring-disk electrode studies and cyclic voltammetry were used to establish the conclusions, and mass-transfer data (diffusion coefficients, kinematic viscosity) for these various Cr, Eu, and H species were obtained in the two media from rotating disk electrode measurements.

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