Light Activated Electrochemistry: Light Intensity and pH Dependence on Electrochemical Performance of Anthraquinone Derivatized Silicon

We seek to understand how the thermodynamics and kinetics of anthraquinone-containing self-assembled monolayer on silicon electrodes are affected by two key experimental variables: the intensity of the light assisting the anthraquinone/anthrahydroquinone redox process and the local solution environm...

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Main Authors: Yang, Y., Ciampi, Simone, Choudhury, M., Gooding, J.
Format: Journal Article
Published: American Chemical Society 2016
Online Access:http://hdl.handle.net/20.500.11937/24840
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author Yang, Y.
Ciampi, Simone
Choudhury, M.
Gooding, J.
author_facet Yang, Y.
Ciampi, Simone
Choudhury, M.
Gooding, J.
author_sort Yang, Y.
building Curtin Institutional Repository
collection Online Access
description We seek to understand how the thermodynamics and kinetics of anthraquinone-containing self-assembled monolayer on silicon electrodes are affected by two key experimental variables: the intensity of the light assisting the anthraquinone/anthrahydroquinone redox process and the local solution environment. The substrates are chemically passivated poorly doped p-type silicon electrodes. The study presents a strategy for the selective modulation of either the anodic or the cathodic process occurring at the interface. Cyclic voltammetry studies showed that unlike for a proton-coupled electron transfer process performed at metallic electrodes, for the redox reaction of the anthraquinone unit on a silicon electrode it becomes possible to (i) selectively facilitate only the oxidation process by increasing the electrolyte pH or (ii) at a given pH value to increase the illumination intensity to anodically shift the onset of the reduction step only but leave the oxidation process thermodynamic unchanged. A model concerning the proton coupled electron transfer mechanism was proposed, where the electron transfer is the rate-determining step for the anthraquinone reduction while a deprotonation step is the rate-determining event for the anthrahydroquinone oxidation on poorly doped illuminated p-type silicon.
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spelling curtin-20.500.11937-248402017-09-13T15:11:17Z Light Activated Electrochemistry: Light Intensity and pH Dependence on Electrochemical Performance of Anthraquinone Derivatized Silicon Yang, Y. Ciampi, Simone Choudhury, M. Gooding, J. We seek to understand how the thermodynamics and kinetics of anthraquinone-containing self-assembled monolayer on silicon electrodes are affected by two key experimental variables: the intensity of the light assisting the anthraquinone/anthrahydroquinone redox process and the local solution environment. The substrates are chemically passivated poorly doped p-type silicon electrodes. The study presents a strategy for the selective modulation of either the anodic or the cathodic process occurring at the interface. Cyclic voltammetry studies showed that unlike for a proton-coupled electron transfer process performed at metallic electrodes, for the redox reaction of the anthraquinone unit on a silicon electrode it becomes possible to (i) selectively facilitate only the oxidation process by increasing the electrolyte pH or (ii) at a given pH value to increase the illumination intensity to anodically shift the onset of the reduction step only but leave the oxidation process thermodynamic unchanged. A model concerning the proton coupled electron transfer mechanism was proposed, where the electron transfer is the rate-determining step for the anthraquinone reduction while a deprotonation step is the rate-determining event for the anthrahydroquinone oxidation on poorly doped illuminated p-type silicon. 2016 Journal Article http://hdl.handle.net/20.500.11937/24840 10.1021/acs.jpcc.5b12097 American Chemical Society fulltext
spellingShingle Yang, Y.
Ciampi, Simone
Choudhury, M.
Gooding, J.
Light Activated Electrochemistry: Light Intensity and pH Dependence on Electrochemical Performance of Anthraquinone Derivatized Silicon
title Light Activated Electrochemistry: Light Intensity and pH Dependence on Electrochemical Performance of Anthraquinone Derivatized Silicon
title_full Light Activated Electrochemistry: Light Intensity and pH Dependence on Electrochemical Performance of Anthraquinone Derivatized Silicon
title_fullStr Light Activated Electrochemistry: Light Intensity and pH Dependence on Electrochemical Performance of Anthraquinone Derivatized Silicon
title_full_unstemmed Light Activated Electrochemistry: Light Intensity and pH Dependence on Electrochemical Performance of Anthraquinone Derivatized Silicon
title_short Light Activated Electrochemistry: Light Intensity and pH Dependence on Electrochemical Performance of Anthraquinone Derivatized Silicon
title_sort light activated electrochemistry: light intensity and ph dependence on electrochemical performance of anthraquinone derivatized silicon
url http://hdl.handle.net/20.500.11937/24840