Diffuse reflectance spectroelectrochemistry as a probe of the chemically derivatized electrode interface. The derivatized nickel electrode

Brian Humphrey, Sujit Sinha, Andrew B. Bocarsly

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Abstract

Diffuse reflectance spectroelectrochemistry has been employed to directly monitor the interface charge-transfer (CT) behavior of surface-bound [NiII(NC)FeII/III(CN)5]2-/- on a nickel electrode. The technique is shown to be species specific and sensitive to the amount of surface-confined material and the oxidation state of the surface-attached species. It is therefore of utility in observing the time-dependent behavior of the surface species under transient potential conditions. This technique is compared with chronocoulometry carried out on the same system. The two techniques are used to obtain values of apparent diffusion coefficients for the derivatized surface. In the short-time limit both techniques are shown to follow the Cottrell equation. However, it is necessary to incorporate time-dependent diffusion coefficients to obtain agreement for long-time data. The reflectance technique is shown to be superior to chronocoulometry in that it can discriminate against current not associated with the surface species of interest.

Original languageEnglish
Pages (from-to)736-743
Number of pages8
JournalJournal of Physical Chemistry
Volume88
Issue number4
StatePublished - 1 Dec 1984

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Spectroelectrochemistry
Nickel
nickel
reflectance
Electrodes
electrodes
probes
diffusion coefficient
Charge transfer
charge transfer
Oxidation
oxidation

Cite this

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title = "Diffuse reflectance spectroelectrochemistry as a probe of the chemically derivatized electrode interface. The derivatized nickel electrode",
abstract = "Diffuse reflectance spectroelectrochemistry has been employed to directly monitor the interface charge-transfer (CT) behavior of surface-bound [NiII(NC)FeII/III(CN)5]2-/- on a nickel electrode. The technique is shown to be species specific and sensitive to the amount of surface-confined material and the oxidation state of the surface-attached species. It is therefore of utility in observing the time-dependent behavior of the surface species under transient potential conditions. This technique is compared with chronocoulometry carried out on the same system. The two techniques are used to obtain values of apparent diffusion coefficients for the derivatized surface. In the short-time limit both techniques are shown to follow the Cottrell equation. However, it is necessary to incorporate time-dependent diffusion coefficients to obtain agreement for long-time data. The reflectance technique is shown to be superior to chronocoulometry in that it can discriminate against current not associated with the surface species of interest.",
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Diffuse reflectance spectroelectrochemistry as a probe of the chemically derivatized electrode interface. The derivatized nickel electrode. / Humphrey, Brian; Sinha, Sujit; Bocarsly, Andrew B.

In: Journal of Physical Chemistry, Vol. 88, No. 4, 01.12.1984, p. 736-743.

Research output: Contribution to journalArticleResearchpeer-review

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AU - Humphrey, Brian

AU - Sinha, Sujit

AU - Bocarsly, Andrew B.

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AB - Diffuse reflectance spectroelectrochemistry has been employed to directly monitor the interface charge-transfer (CT) behavior of surface-bound [NiII(NC)FeII/III(CN)5]2-/- on a nickel electrode. The technique is shown to be species specific and sensitive to the amount of surface-confined material and the oxidation state of the surface-attached species. It is therefore of utility in observing the time-dependent behavior of the surface species under transient potential conditions. This technique is compared with chronocoulometry carried out on the same system. The two techniques are used to obtain values of apparent diffusion coefficients for the derivatized surface. In the short-time limit both techniques are shown to follow the Cottrell equation. However, it is necessary to incorporate time-dependent diffusion coefficients to obtain agreement for long-time data. The reflectance technique is shown to be superior to chronocoulometry in that it can discriminate against current not associated with the surface species of interest.

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