Electron-transfer rates through zinc porphyrin multilayers films on gold electrodes
Authors
Robinson, Naomi R.
ORCID
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Other Contributors
Dinolfo, Peter
Korenowski, Gerald
Shelley, Jacob T., 1984-
Korenowski, Gerald
Shelley, Jacob T., 1984-
Issue Date
2020-05
Keywords
Chemistry
Degree
MS
Terms of Use
This electronic version is a licensed copy owned by Rensselaer Polytechnic Institute, Troy, NY. Copyright of original work retained by author.
Full Citation
Abstract
Zn(II) 5,10,15,20-tetra(4-ethynylphenyl)porphyrin (ZnTPEP) was used to fabricate multilayered films, using either 1,3,5-tris(azidomethyl)benzene (N3-Mes) and 1,4 bis(azidomethyl)benzene (N3-Xyl) as linkers, by through a layer-by-layer (LbL) assembly technique utilizing copper(I)-catalyzed azide-alkyne cycloaddition (CuAAC) reactions. Bilayer growth was tracked using UV-Visible specular reflectance, and electrochemistry was performed on these films to determine through-film electron-transfer rates. The chronoamperometric data was analyzed using the Butler-Volmer (B-V) formalism to determine the overall electron-transfer rates (kET), the standard electron-transfer rates (ko), and the self-exchange electron-transfer rates (kse) for varying bilayers of ZnTPEP with the two linkers. ZnTPEP with N3-Mes was found to have better bilayer growth and lower rate constants as compared to ZnTPEP with N3-Xyl. The self-exchange rate constant was shown to have a greater contribution to the overall electron-transfer rate than the standard rate constant. Spectroelectrochemistry (SEC) of the multilayer structures confirmed electrochemical reversibility of the ZnTPEP oxidation. Electrochemical rectification studies using ethynylferrocene provided evidence of uniform multilayer structures.
Description
May 2020
School of Science
School of Science
Department
Dept. of Chemistry and Chemical Biology
Publisher
Rensselaer Polytechnic Institute, Troy, NY
Relationships
Rensselaer Theses and Dissertations Online Collection
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