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Updated: May 31, 2026
09:17
Reductive Electropolymerization of a Vinyl-containing Poly-pyridyl Complex on Glassy Carbon and Fluorine-doped Tin Oxide Electrodes
Published on: January 30, 2015
Realization of Self-Terminating Underpotential Electropolymerization by Strong Supramolecular Monomer-Electrode
Yudai Yokoyama1, Yuzu Kobayashi2,3, Yasuyuki Yokota3
1Department of Chemistry and Biotechnology, School of Engineering, The University of Tokyo, 7-3-1 Hongo, Bunkyo, Tokyo 113-8656, Japan.
Journal of the American Chemical Society
|May 29, 2026
Summary
Electropolymerization of 3,4-ethylenedioxythiophene (EDOT) occurs at a lower voltage (0.4 V) on gold surfaces, enabling self-terminating polymer growth. This controlled polymerization is crucial for advanced materials and coatings.
Area of Science:
- Materials Science
- Electrochemistry
- Surface Chemistry
Background:
- Electropolymerization of 3,4-ethylenedioxythiophene (EDOT) typically requires high voltages (1.0 V).
- Controlling polymer film growth during electropolymerization is essential for various applications.
- Understanding monomer-surface interactions is key to tailoring polymerization processes.
Purpose of the Study:
- To investigate the electropolymerization of EDOT on gold (Au) electrodes at significantly lower voltages.
- To elucidate the mechanism behind self-terminating polymerization.
- To explore the role of surface interactions in controlling polymerization.
Main Methods:
- Electropolymerization of EDOT on Au working electrodes at 0.4 V.
- Density Functional Theory (DFT) calculations to study monomer-surface interactions and electronic properties.
- In situ electrochemical surface-enhanced Raman spectroscopy (EC-SERS) and current profile analysis.
Main Results:
- EDOT electropolymerization was achieved at 0.4 V on Au in a self-terminating manner.
- DFT revealed that EDOT's highest occupied molecular orbital (HOMO) is elevated by ~1 eV upon adsorption on Au, increasing reactivity.
- Polymer formation on the Au surface halts further monomer interaction and polymerization.
- EC-SERS and current profiles confirmed the self-terminating behavior, contrasting with continuous growth at higher voltages.
Conclusions:
- Electropolymerization of EDOT on Au surfaces can be controlled to achieve self-terminating growth at low voltages.
- This method offers a pathway for precise control of polymer film formation on solid surfaces.
- Potential applications include adhesives, coatings, solid electrolyte interphase (SEI) formation, and the synthesis of functional monolayer polymers.
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