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[3,4-b]-1,4-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. 1

Copolymer formation of 9-(2-(benzyloxy)ethyl)-9H-carbazole and 1-tosyl-1H-pyrrole coated on glassy carbon electrode and electrochemical impedance spectroscopy

“…For the design of specific copolymeric systems and control of the degree of functionalization, it is important to be able to predict the copolymer composition, i.e., the relative proportions of each monomer constituent. This requires accurate knowledge of the relative reactivity of the two monomers toward a radical species and, in the case of electropolymerization, reactivity toward the electrode surface [29].…”

Electrochromic properties of electrochemically synthesized porphyrin/3-substituted polythiophene copolymers

“…In addition, it might be concluded from these results that the copolymers could be formed in random structures. In general, electropolymerization of two different conjugated monomers have been resulted in a random copolymer [43,44].…”

Final Scientific/Technical Report - Biomimetic Energy Transduction: Artificial Photosynthesis in a Stabilized Lipid Membrane Coupled to a Semiconductor

“…More detailed accounts of the research supported in whole or part by this grant have appeared or will appear in publications. [1][2][3][4][5][6][7][8][9][10][11][12][13] B. Transduction of an ion gradient across a PSLB coupled to an electroactive waveguide through a conductive polymer film. A number of liposome-based systems have been developed that allow for chemically-or light-induced transport of ions into or out of the vesicle interior.…”

“…[44][45][46][47] In a recent paper, 3 we described use of this approach to prepare solgels "wired" with poly(3,4-ethylenedioxythiophene) (PEDOT), a polymer used in our previous work with electropolymerized CP thin films. 7,8 EDOT monomer is introduced either by dissolving it in the sol or by soaking the PSG layer in an EDOT solution. In Figure 6, a scanning electron microscograph of a cross-sectioned sol-gel layer illustrates PEDOT wires grown through a PSG layer that has been spin-coated on ITO.…”