Electropolymerization E-Book

• Herausgeber: Wiley-VCH
• Kategorie: Wissenschaft und neue Technologien
• Sprache: Englisch

Seitenzahl: 537

Veröffentlichungsjahr: 2011

Beschreibung

Providing extensive coverage, including conducting, insulating and electroactive films, this handbook and ready reference deals with introductory topics and fundamentals as well as advanced insights. Clearly structured, in the first part of the book readers learn the fundamentals of electropolymerizatoin for all important types of polymers, mechanisms of film formation and functionalization, while the second part covers a wide range of applications in biochemistry, analytics, photovoltaics, energy and the environment as well as actuators.

Leseprobe

Contents

Preface

List of Contributors

1 Electropolymerized Films of π-Conjugated Polymers. A Tool for Surface Functionalization: a Brief Historical Evolution and Recent Trends

1.1 Introduction

1.2 Electropolymerization: Epistemological Analysis within the ICP Saga

1.3 Electropolymerization: from Pristine Heterocyclic to Sophisticated Functional and Conjugated Architectures

1.4 Conclusion

References

2 Mechanisms of Electropolymerization and Redox Activity: Fundamental Aspects

2.1 Electropolymerization: General Aspects

2.2 Redox Activity of Polymer Films

2.3 Effect of Polymerization Parameters on Properties of Deposited Polymer Films

2.4 Conclusions

References

3 Electrochemical Impedance Spectroscopy (EIS) for Polymer Characterization

3.1 Introduction

3.2 Experimental Arrangements

3.3 Impedance Spectra of Polymer Films

3.4 Analysis of the Impedance Spectra

3.5 Models of Polymeric Layers

3.6 Summary

Acknowledgment

References

4 Recent Trends in Polypyrrole Electrochemistry, Nanostructuration, and Applications

4.1 Introduction

4.2 Advances in Synthetic Procedures – New Polymers

4.3 Nanostructuration of Polypyrrole

4.4 Applications

4.5 Conclusion

References

5 Electropolymerized Azines: a New Group of Electroactive Polymers

5.1 Introduction

5.2 Electropolymerized Azines as a New Group of Electroactive Polymers

5.3 Polyazines in Electroanalysis

5.4 Electropolymerized Azines as Promoters for Bioelectrocatalysis

5.5 Conclusion

References

6 Electropolymerization of Phthalocyanines

6.1 Introduction

6.2 Immobilization of Transition-Metal Phthalocyanines on Conducting and Nonconducting Substrates

6.3 Electropolymerization of Phthalocyanines

6.4 Conclusion

References

7 Imprinted Polymers

7.1 Introduction

7.2 Molecular Imprinting in Conjugated Polymers

7.3 Solgel Imprinted Films Prepared by Electropolymerization

7.4 Integration of MIPs with the Surface of Transducers

7.5 Nanostructured Materials

7.6 Other MIP-Based Sensors

7.7 Conclusion

References

8 Gas Sensing with Conducting Polymers

8.1 Introduction

8.2 Electronic Properties of Conducting Polymers

8.3 Preparation of Polymer Gas-Sensing Layers

8.4 Mechanism of Gas/Polymer Interactions

8.5 Types of Conducting Polymer-Based Gas Sensors

8.6 Conclusion

References

9 Chemical Sensors Based on Conducting Polymers

9.1 Introduction

9.2 Electrochemical Signal Transduction

9.3 Optical Signal Transduction

9.4 Conclusions

Acknowledgments

References

10 Biosensors Based on Electropolymerized Films

10.1 Introduction

10.2 Chronological Evolution of the Concept of Biosensors Based on Electropolymerized Films: Principal Stages

10.3 Formation of Polymer Films by Direct Electropolymerization of the Biomolecule

10.4 Adsorption on Electrogenerated Polymers

10.5 Mechanical Entrapment within Electropolymerized Films

10.6 Covalent Binding at the Surface of Electropolymerized Films

10.7 Noncovalent Binding by Affinity Interactions with the Electropolymerized Films

10.8 Outlook

References

11 Inherently Conducting Polymers via Electropolymerization for Energy Conversion and Storage

11.1 Introduction

11.2 Energy Conversion

11.3 Energy Storage

11.4 Electropolymerization to Form Electrodes for Energy Storage Applications

11.5 Nanostructured Conducting Polymers

11.6 Conducting Polymer Composites

11.7 Conclusions

References

12 Electrochemomechanical Devices: Artificial Muscles

12.1 Introduction

12.2 Conducting Polymers as Reactive Materials: Electrochemical Reactions

12.3 Electrochemical Properties: Multifunctionality and Biomimetism

12.4 Macroscopic Dimensional Changes and Mechanical Properties

12.5 Anisotropy Obtained from Isotropic Changes: Macroscopic Devices

12.6 Electrochemical Characterization

12.7 Sensing Capabilities of Artificial Muscles

12.8 Tactile Sensitivity

12.9 Intelligent Devices

12.10 Muscles Working in Air

12.11 Advantages, Limitations, and Challenges

12.12 Artificial Muscles as Products

References

Index

Further Reading

Leclerc, M., Morin, J.-F. (eds.)

Design and Synthesis of Conjugated Polymers

2010

Hardcover

ISBN: 978-3-527-32474-3

Kumar, C. S. S. R. (ed.)

Nanostructured Thin Films and Surfaces

2010

Hardcover

ISBN: 978-3-527-32155-1

Eftekhari, A. (ed.)

Nanostructured Materials in Electrochemistry

2008

Hardcover

ISBN: 978-3-527-31876-6

Hadziioannou, G., Malliaras, G. G. (eds.)

Semiconducting Polymers

Chemistry, Physics and Engineering

2007

Hardcover

ISBN: 978-3-527-31271-9

Staikov, G. T. (ed.)

Electrocrystallization in Nanotechnology

2007

Hardcover

ISBN: 978-3-527-31515-4

Geckeler, K. E., Nishide., H. (eds.)

Advanced Nanomaterials

2 Volumes

2010

Hardcover

ISBN: 978-3-527-31794-3

The Editors

Dr. Serge CosnierUniversité Joseph FourierDépartment de Chimie MoléculaireUMR-5250Boite postale 5338041 Grenoble Cedex 9France

Prof. Arkady KaryakinMoscow State UniversityAnalytical Chemistry DepartmentLenin Hills, GSP -311991 MoscowRussia

All books published by Wiley-VCH are carefully produced. Nevertheless, authors, editors, and publisher do not warrant the information contained in these books, including this book, to be free of errors. Readers are advised to keep in mind that statements, data, illustrations, procedural details or other items may inadvertently be inaccurate.

Library of Congress Card No.: applied for

British Library Cataloguing-in-Publication DataA catalogue record for this book is available from the British Library.

Bibliographic information published by the Deutsche NationalbibliothekThe Deutsche Nationalbibliothek lists this publication in the Deutsche Nationalbibliografie; detailed bibliographic data are available on the Internet at <http://dnb.d-nb.de>.

© 2010 WILEY-VCH Verlag & Co. KGaA, Boschstr. 12, 69469 Weinheim, Germany

All rights reserved (including those of translation into other languages). No part of this book may be reproduced in any form – by photoprinting, microfilm, or any other means – nor transmitted or translated into a machine language without written permission from the publishers. Registered names, trademarks, etc. used in this book, even when not specifically marked as such, are not to be considered unprotected by law.

Cover Design Adam Design, WeinheimTypesetting Laserwords Private Ltd., Chennai, IndiaPrinting and Bookbinding Strauss GmbH, Mörlenbach

ISBN: 978-3-527-32414-9

Preface

Well before the activity explosion in the nanosciences and their huge success, electropolymerization, from a fundamental point of view, had already become one of the key methods making the creation of molecular wires or nets possible. The process of electropolymerization leads to a simple and reproducible formation of organic or organometallic films with precise spatial resolution over surfaces, whatever their size and geometry. This formation of polymer films led to a broad material diversity of applications which extended from automobile industry to biotechnologies using, for example, the DNA chip. Thanks to the versatility of the monomer design and the polymer processability, a fascinating range of conductive, electromagnetic, mechanical, electrochromic, light-emitting, and optical properties was ascribed to these films. The functionalization of repeating units opens a broad field of application of polymers in the fields of corrosion protection, biochemistry, analytics, photovoltaics, renewable energy and the environment, as well as actuators.

Electropolymerization presumes polymer formation upon oxidation or reduction of certain organic compounds. Upon electropolymerization, new covalent bonds are formed between these monomer precursors distinguishing this process from simple electrodeposition.

Electropolymerization is thus a powerful tool for development of modified electrodes. First, electropolymerization provides simplicity of targeting in the selective modification of multielectrode structures. Indeed, even by exposing the whole structure to the precursor solution, one can target polymer formation on the electrode of interest, applying to it the required current or potential. Second, the electropolymerized films are usually much more stable on electrode surfaces compared to both adsorbed and covalently linked modifiers such as low-molecular-weight organic compounds or chemically synthesized polymers. Third, the electropolymerized materials usually possess some unique properties that are not those of the corresponding monomers. These properties mainly concern electroactive polymers, which demonstrate new sets of peaks in cyclic voltammograms due to the appearance of new conjugative chains or modification of the existing ones in their structure.

The formation of electroactive polymers upon reduction or oxidation of different organic compounds became one of the major topics in modern electrochemistry following the discovery of conducting polymers. Electrochemical synthesis of the latter undoubtedly dominates over chemical synthesis.

We invited world-recognized scientists who are specialists in different fields to contribute specific chapters to this book. This was in order to cover major aspects of electropolymerization from the fundamentals to various applications. We believe the book will be accepted by the wide scientific audience as well as by graduate students.

Serge Cosnier (Grenoble)Arkady Karyakin (Moscow)

February 2010

List of Contributors

Ninel M. Alpatova

A.N. Frumkin Institute of Physical Chemistry and Electrochemistry

Russian Academy of Sciences

Leninskii Prospect 31

119991 Moscow

Russia

Pierre Audebert

Ecole Normale

Supérieure de Cachan

Laboratory of Supramolecular and Macromolecular Photophysic and Photochemistry

Bâtiment d’Alembert

61, avenue du Président Wilson

94235 Cachan Cédex

France

Joaquín Arias-Pardilla

Technical University of Cartagena

Center for Electrochemistry and Intelligent Devices

School of Industrial Engineers

C/Carlos III

30203 Cartagena

Spain

Gérard Bidan

CEA/Institut Nanosciences et

Cryogénie

17 rue des Martyrs

38054 Grenoble cedex 09

France

Johan Bobacka

Åbo Akademi University

Process Chemistry Centre

Laboratory of Analytical

Chemistry

Biskopsgatan 8

FI-20500 Åbo-Turku

Finland

Serge Cosnier

Université Joseph Fourier

Département de Chimie

Moléculaire

UMR CNRS 5250

BP-53

38041 Grenoble Cedex 9

France

Michael Holzinger

Université Joseph Fourier

Département de Chimie

Moléculaire

UMR CNRS 5250

BP-53

38041 Grenoble Cedex 9

France

György Inzelt

Eötvös Loránd University

Institute of Chemistry

Laboratory of Electrochemistry

and Electroanalytical Chemistry

Pázmány Péter Sétány 1A

1117 Budapest

Hungary

Ari Ivaska

Åbo Akademi University

Process Chemistry Centre

Laboratory of Analytical

Chemistry

Biskopsgatan 8

FI-20500 Åbo-Turku

Finland

Arkady A. Karyakin

M.V. Lomonosov Moscow

State University

Department of Chemistry

119991 Moscow

Russia

Dmitry V. Konev

University of Bourgogne

ICMUB - UMR 5260 CNRS

Bat. Mirande

9 avenue A. Savary

BP 47 870

21078 Dijon Cedex

France

Dhana Lakshmi

Cranfield University

Cranfield Health

Vincent Building

Cranfield

Bedfordshire

MK43 0AL

UK

Gyz G. Láng

Eötvös Loránd University

Institute of Chemistry

Laboratory of Electrochemistry and Electroanalytical Chemistry

Pázmány Péter Sétány 1A

1117 Budapest

Hungary

Toribio F. Otero

Technical University of Cartagena

Center for Electrochemistry and Intelligent Devices

School of Industrial Engineers

C/Carlos III

30203 Cartagena

Spain

Elena V. Ovsyannikova

A.N. Frumkin Institute of Physical Chemistry and Electrochemistry

Russian Academy of Sciences

Leninskii Prospect 31

119991 Moscow

Russia

Karin Potje-Kamloth

Institut für Mikrotechnik Mainz

Carl-Zeiss-Strasse 18–20

55129 Mainz

Germany

George Tsekouras

University of St Andrews

School of Chemistry

North Haugh

St. Andrews

Fife KY16 8DA

Scotland

UK

Mikhail A. Vorotyntsev

University of Bourgogne

ICMUB - UMR 5260 CNRS

Bat. Mirande

9 avenue A. Savary

BP 47 870

21078 Dijon Cedex

France

Gordon G. Wallace

University of Wollongong

Intelligent Polymer Research

Institute

ARC Centre of Excellence for Electromaterials Science

Wollongong

NSW 2522

Australia

Caiyun Wang

University of Wollongong

Intelligent Polymer Research

Institute

ARC Centre of Excellence for Electromaterials Science

Wollongong

NSW 2522

Australia

Michael J. Whitcombe

Cranfield University

Cranfield Health

Vincent Building

Cranfield

Bedfordshire

MK43 0AL

UK

Veronika A. Zinovyeva

University of Bourgogne

ICMUB - UMR 5260 CNRS

Bat. Mirande

9 avenue A. Savary

BP 47 870

21078 Dijon Cedex

France

1

Electropolymerized Films of π-Conjugated Polymers. A Tool for Surface Functionalization: a Brief Historical Evolution and Recent Trends

Gérard Bidan

1.1 Introduction

Electrodeposition of conducting polymer films at the surface of an electrode has opened a field at the convergence between two rich domains: electrochemistry of modified electrode[1–3] and conjugated systems[4]. Consequently, applications of modified electrodes in electrocatalysis, electrochromism, energy storage, electroanalysis, and sensors have been enriched by the specific properties of intrinsically conducting polymers (ICPs), for example, electrochemically tunable doping and de-doping (equivalent to adjustable redox states), polymeric matrix affording electrical wiring, use as immobilized redox mediators, and the capacity to induce new functionalities by the use of specific gratings. Reciprocally, electrochemistry has opened up the route to easy-to-handle polymer films in a manner similar to the way that polyacetylene, (CH) x, prepared as a film by a modification of the Natta reaction [5], resulted in the discovery, in 1977, of the doping effect as presented in the seminal paper of Shirakawa and coworkers [6]. In addition, this cross-fertilization enlarged the panel of new ICP-based materials, such as electrogenerated composites [7], and strengthened or brought in new applications such as energy conversion and storage (Chapter 11); electrotriggered drug delivery [8]; soft actuators (Chapter 11); chemical, bio-, and gas sensors (Chapters 8–10); biocompatible films [9]; and artificial muscles (Chapter 12).

Considering the intense and widespread research activities in these fields, the aim of this historical survey is not to cover the entire field of the various electropolymerization facets detailed in the following chapters, but to give an overview of the successive contributions to and acquisition of knowledge.

The electropolymerization reported here is restricted to oxidative condensation; as a matter of fact, it should be mentioned that as early as in 1983, Fauvarque [10] reported the synthesis of poly(p-phenylene) film by electroreduction-assisted catalysis by Ni(0) complex. In the first part, electropolymerization is described in the context of π-conjugated polymers. Four generations have been distinguished in this saga: the “era of physicists,” the “era of electrochemists,” the “era of polymerists,” and the “era of molecular electronics.” This division appears a little artificial, since the progress in each of these eras resulted from mutual enrichment between these scientific communities; however, this book provides an enlightening presentation of each determining step of the evolution. The “era of electrochemists” starts with the early use of electropolymerization in the 1980s. The second part presents the major milestones reached by the process of electropolymerization in the light of the functionalization of surfaces for the electrodeposition of increasingly sophisticated conjugated architectures endowed with specific functionalities from sensors to active photovoltaic layers. Recent trends in the use of the electropolymerization concerning the elaboration of nanowires or nanotubes of ICPs for sensors or molecular electronics, nanostructured materials (interpenetrated networks with ICPs, carbon nanotubes/ICPs combination, etc.) are not presented here.