Electrochemical copolymerization and spectroelectrochemical characterization of 3,4-ethylenedioxythiophene and 3,4-ethylenedioxythiophene-methanol copolymers on indium-tin oxide

Walter J. Doherty, Ronald J. Wysocki, Neal R Armstrong, Steven S Saavedra

Research output: Contribution to journalArticle

38 Citations (Scopus)

Abstract

This work describes the electrochemical copolymerization and spectroelectrochemical characterization of 3,4-ethylenedioxythiophene (EDOT) with a commonly used EDOT derivative: 2,3-dihydrothieno[3,4b]-l,4-dioxyn-2-yl methanol (EDTM), on indium-tin oxide (ITO) electrodes, as a function of the EDTM/EDOT comonomer feed ratio. The potential of initial polymerization and the degree of optical contrast between reduced and oxidized states increased steadily with increasing proportions of EDTM. Reactivity ratios were determined by spectroscopic characterization of the copolymer film and by monitoring the depletion of monomer from the starting solution by liquid chromatography, following the formation of relatively thick PEDOT/PEDTM films. Average reactivity ratios of 1.5 ±0.2 and 0.4 ±0.3 were obtained for EDOT and EDTM, respectively, demonstrating preferential deposition of EDOT on ITO electrode surfaces. Significant differences were noted at low and high degrees of conversion, indicating changes in copolymer composition with film thickness. These results have real significance for the characterization of electron-transfer rates for the first monolayer of PEDOT/ PEDTM on ITO, determined by a new mode of potential-modulated attenuated total reflectance spectroelectrochemistry.

Original languageEnglish (US)
Pages (from-to)4418-4424
Number of pages7
JournalMacromolecules
Volume39
Issue number13
DOIs
StatePublished - Jun 27 2006

Fingerprint

Tin oxides
Indium
Copolymerization
Methanol
Copolymers
Spectroelectrochemistry
Electrodes
Liquid chromatography
Film thickness
Monolayers
Monomers
Polymerization
Derivatives
Electrons
Monitoring
Chemical analysis
3,4-ethylenedioxythiophene
indium tin oxide

ASJC Scopus subject areas

  • Materials Chemistry

Cite this

@article{fd05b2511ddb43919d233622d43f730b,
title = "Electrochemical copolymerization and spectroelectrochemical characterization of 3,4-ethylenedioxythiophene and 3,4-ethylenedioxythiophene-methanol copolymers on indium-tin oxide",
abstract = "This work describes the electrochemical copolymerization and spectroelectrochemical characterization of 3,4-ethylenedioxythiophene (EDOT) with a commonly used EDOT derivative: 2,3-dihydrothieno[3,4b]-l,4-dioxyn-2-yl methanol (EDTM), on indium-tin oxide (ITO) electrodes, as a function of the EDTM/EDOT comonomer feed ratio. The potential of initial polymerization and the degree of optical contrast between reduced and oxidized states increased steadily with increasing proportions of EDTM. Reactivity ratios were determined by spectroscopic characterization of the copolymer film and by monitoring the depletion of monomer from the starting solution by liquid chromatography, following the formation of relatively thick PEDOT/PEDTM films. Average reactivity ratios of 1.5 ±0.2 and 0.4 ±0.3 were obtained for EDOT and EDTM, respectively, demonstrating preferential deposition of EDOT on ITO electrode surfaces. Significant differences were noted at low and high degrees of conversion, indicating changes in copolymer composition with film thickness. These results have real significance for the characterization of electron-transfer rates for the first monolayer of PEDOT/ PEDTM on ITO, determined by a new mode of potential-modulated attenuated total reflectance spectroelectrochemistry.",
author = "Doherty, {Walter J.} and Wysocki, {Ronald J.} and Armstrong, {Neal R} and Saavedra, {Steven S}",
year = "2006",
month = "6",
day = "27",
doi = "10.1021/ma052322z",
language = "English (US)",
volume = "39",
pages = "4418--4424",
journal = "Macromolecules",
issn = "0024-9297",
publisher = "American Chemical Society",
number = "13",

}

TY - JOUR

T1 - Electrochemical copolymerization and spectroelectrochemical characterization of 3,4-ethylenedioxythiophene and 3,4-ethylenedioxythiophene-methanol copolymers on indium-tin oxide

AU - Doherty, Walter J.

AU - Wysocki, Ronald J.

AU - Armstrong, Neal R

AU - Saavedra, Steven S

PY - 2006/6/27

Y1 - 2006/6/27

N2 - This work describes the electrochemical copolymerization and spectroelectrochemical characterization of 3,4-ethylenedioxythiophene (EDOT) with a commonly used EDOT derivative: 2,3-dihydrothieno[3,4b]-l,4-dioxyn-2-yl methanol (EDTM), on indium-tin oxide (ITO) electrodes, as a function of the EDTM/EDOT comonomer feed ratio. The potential of initial polymerization and the degree of optical contrast between reduced and oxidized states increased steadily with increasing proportions of EDTM. Reactivity ratios were determined by spectroscopic characterization of the copolymer film and by monitoring the depletion of monomer from the starting solution by liquid chromatography, following the formation of relatively thick PEDOT/PEDTM films. Average reactivity ratios of 1.5 ±0.2 and 0.4 ±0.3 were obtained for EDOT and EDTM, respectively, demonstrating preferential deposition of EDOT on ITO electrode surfaces. Significant differences were noted at low and high degrees of conversion, indicating changes in copolymer composition with film thickness. These results have real significance for the characterization of electron-transfer rates for the first monolayer of PEDOT/ PEDTM on ITO, determined by a new mode of potential-modulated attenuated total reflectance spectroelectrochemistry.

AB - This work describes the electrochemical copolymerization and spectroelectrochemical characterization of 3,4-ethylenedioxythiophene (EDOT) with a commonly used EDOT derivative: 2,3-dihydrothieno[3,4b]-l,4-dioxyn-2-yl methanol (EDTM), on indium-tin oxide (ITO) electrodes, as a function of the EDTM/EDOT comonomer feed ratio. The potential of initial polymerization and the degree of optical contrast between reduced and oxidized states increased steadily with increasing proportions of EDTM. Reactivity ratios were determined by spectroscopic characterization of the copolymer film and by monitoring the depletion of monomer from the starting solution by liquid chromatography, following the formation of relatively thick PEDOT/PEDTM films. Average reactivity ratios of 1.5 ±0.2 and 0.4 ±0.3 were obtained for EDOT and EDTM, respectively, demonstrating preferential deposition of EDOT on ITO electrode surfaces. Significant differences were noted at low and high degrees of conversion, indicating changes in copolymer composition with film thickness. These results have real significance for the characterization of electron-transfer rates for the first monolayer of PEDOT/ PEDTM on ITO, determined by a new mode of potential-modulated attenuated total reflectance spectroelectrochemistry.

UR - http://www.scopus.com/inward/record.url?scp=33746380228&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=33746380228&partnerID=8YFLogxK

U2 - 10.1021/ma052322z

DO - 10.1021/ma052322z

M3 - Article

AN - SCOPUS:33746380228

VL - 39

SP - 4418

EP - 4424

JO - Macromolecules

JF - Macromolecules

SN - 0024-9297

IS - 13

ER -