Bipolar Patterning of Conducting Polymers by Electrochemical Doping and Reaction

Inagi, Shinsuke; Ishiguro, Yutaka; Atobe, Mahito; Fuchigami, Toshio

doi:10.1002/anie.201005671

Cited by 100 publications

(77 citation statements)

References 32 publications

(25 reference statements)

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“…Such a controlled potential slope is very effective for local electrochemical doping and the reactions of conducting polymers. 16 This bipolar electrochemistry with a shielding wall is also powerful for patterning applications. 19 …”

Section: Measurement Of Potential On the Bpe In A U-type Cell-mentioning

confidence: 99%

Measurements of Potential on and Current through Bipolar Electrode in U-Type Electrolytic Cell with a Shielding Wall

Inagi

Ishiguro

Shida

2012

J. Electrochem. Soc.

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The bipolar electrochemistry in a U-type cell equipped with a shielding wall was investigated in detail using a number of electrochemical measurements for the bipolar electrode (BPE). Measurement of the IR-drop in a U-type cell and the potential on the BPE afforded similar sigmoidal potential distribution profiles at around the shielding wall. The current through the BPE was also measured using a split BPE with and without a conducting polymer on its surface. The conducting polymer film lowered the potential threshold for electrochemical reaction at the anode, but prevented cathodic reactions such as the reduction of contaminant oxygen. These results strongly support our preliminary work on the electrochemical modification of conducting polymers using bipolar electrochemistry.Through their long-standing and important role in industry, bipolar electrodes (BPE), which can involve anodic and cathodic reactions on the same substrate, 1 have become applicable to sensor applications, 2-4 the formation of gradient surfaces 5,6 and the deposition of microstructures. 7-13 In a microfluidic space with a thin conducting substrate, an electric field from a pair of external driving electrodes can induce the BPE to realize anodic and cathodic reactions at both sides. The BPE is driven by IR-drop in the electrolyte, so that a low concentration of electrolyte is favorable to induce BPE under low current (moderate) conditions. Thus, there are thresholds of the electrolytic conditions, such as the concentration of electrolyte and the supply of current between the driving electrodes to induce the BPE. Electrochemical reactions on both poles of the BPE can then generate a current flow. Previous intensive research has investigated the BPE induced in the microfluidic space using both experimental and theoretical approaches. 14,15 The potential gradient distribution is applied on the BPE in a manner proportional to the direction of the electric field.We have previously fabricated a U-type electrolytic cell for a bipolar electrolytic system, in which a BPE is positioned to face to the driving anode and cathode. 16,17 The electric field in the cell is controlled by an insulator shielding wall. The BPE fixing conducting polymers was effectively induced by the supply of a constant current between the driving electrodes, which makes it possible to involve electrochemical reactions such as anodic doping and chlorination of the conducting polymers, depending on the supporting salt used. 16 We have also recently demonstrated gradient surface functionalization of a conducting polymer using an electrogenerated copper (I)-mediated azide-alkyne cycloaddition reaction on a BPE. 18 Interestingly, the behavior of the electrochemical reactions indicated that the potential distribution applied on the BPE in a U-type cell was not proportional, but rather sigmoidal, in contrast to that for the microfluidic cell. However, the actual potential distribution on the BPE has not been studied, and therefore warrants further investigation.The main purpose of thi...

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Section: Measurement Of Potential On the Bpe In A U-type Cell-mentioning

confidence: 99%

Measurements of Potential on and Current through Bipolar Electrode in U-Type Electrolytic Cell with a Shielding Wall

Inagi

Ishiguro

Shida

2012

J. Electrochem. Soc.

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“…Björefors et al used bipolar electrochemistry-triggered desorption of self-assembled monolayers for the formation of molecular gradients on gold, 17 Shannon et al reported the bipolar electrodeposition for the fabrication of Au-Ag and CdS solid-state gradients, 18 and Inagi and Fuchigami used bipolar doping to fabricate gradually-doped conducting polymers. 19 In the present paper, we combine for the first time anodization and bipolar electrochemistry in order to fabricate in a few minutes and in a wireless manner self-assembled TiO 2 NT surfaces, which are comprised of NT gradients with tunable length and diameter and we show how these gradients can be used for the rapid screening of the TiO 2 NT properties. Fig.…”

Section: Introductionmentioning

confidence: 99%

Bipolar anodization enables the fabrication of controlled arrays of TiO₂ nanotube gradients

Loget

Hahn

et al. 2014

J. Mater. Chem. A

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We report here a new concept, the use of bipolar electrochemistry, which allows the rapid and wireless growth of self-assembled TiO 2 NT layers that consist of highly defined and controllable gradients in NT length and diameter. The gradient height and slope can be easily tailored with the time of electrolysis and the applied electric field, respectively. As this technique allows obtaining in one run a wide range of self-ordered TiO 2 NT dimensions, it provides the basis for rapid screening of TiO 2 NT properties. In two examples, we show how these gradient arrays can be used to screen for an optimized photocurrent response from TiO 2 NT based devices such as dye-sensitized solar cells.

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“…(b) Photographs of the PMT film produced by bipolar doping (0.02 C) in 0.005 M Bu 4 NPF 6 /acetonitrile and the amounts of phosphorus (P) and fluorine (F) contained at each distance from the cathodic edge of the doped film 26. …”

mentioning

confidence: 99%

Gradient Doping of Conducting Polymer Films by Means of Bipolar Electrochemistry

2011

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In this paper, we report a novel electrochemical doping method for conducting polymer films based on bipolar electrochemistry. The electrochemical doping of conducting polymers such as poly(3-methylthiophene) (PMT), poly(3,4-ethylenedioxythiophene) (PEDOT), and poly(aniline) (PANI) on a bipolar electrode having a potential gradient on its surface successfully created gradually doped materials. In the case of PEDOT film, the color change at the anodic side was also observed to be gradually transparent. PANI film treated by the bipolar doping gave a multicolored gradation across the film. The results of UV-vis and energy dispersive X-ray analyses for the doped films supported the distribution of dopants in the polymer films reflecting the potential gradient on the bipolar electrode. Furthermore, the reversibility of the bipolar doping of the PMT film was demonstrated by a spectroelectrochemical investigation.

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Bipolar Patterning of Conducting Polymers by Electrochemical Doping and Reaction

Cited by 100 publications

References 32 publications

Measurements of Potential on and Current through Bipolar Electrode in U-Type Electrolytic Cell with a Shielding Wall

Measurements of Potential on and Current through Bipolar Electrode in U-Type Electrolytic Cell with a Shielding Wall

Bipolar anodization enables the fabrication of controlled arrays of TiO₂ nanotube gradients

Gradient Doping of Conducting Polymer Films by Means of Bipolar Electrochemistry

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Bipolar Patterning of Conducting Polymers by Electrochemical Doping and Reaction

Cited by 100 publications

References 32 publications

Measurements of Potential on and Current through Bipolar Electrode in U-Type Electrolytic Cell with a Shielding Wall

Measurements of Potential on and Current through Bipolar Electrode in U-Type Electrolytic Cell with a Shielding Wall

Bipolar anodization enables the fabrication of controlled arrays of TiO2 nanotube gradients

Gradient Doping of Conducting Polymer Films by Means of Bipolar Electrochemistry

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Bipolar anodization enables the fabrication of controlled arrays of TiO₂ nanotube gradients