A timely overview of fundamental and advanced topics of conjugated polymer nanostructures
Conjugated Polymer Nanostructures for Energy Conversion and Storage Applications is a comprehensive reference on conjugated polymers for energy applications. Distinguished academic and editor Srabanti Ghosh offers readers a broad overview of the synthesis, characterization, and energy-related applications of nanostructures based on conjugated polymers. The book includes novel approaches and presents an interdisciplinary perspective rooted in the interfacing of polymer and synthetic chemistry, materials science, organic chemistry, and analytical chemistry.
This book provides complete descriptions of conjugated polymer nanostructures and polymer-based hybrid materials for energy conversion, water splitting, and the degradation of organic pollutants. Photovoltaics, solar cells, and energy storage devices such as supercapacitors, lithium ion battery electrodes, and their associated technologies are discussed, as well.
Conjugated Polymer Nanostructures for Energy Conversion and Storage Applications covers both the fundamental topics and the most recent advances in this rapidly developing area, including:
- The design and characterization of conjugated polymer nanostructures, including the template-free and chemical synthesis of polymer nanostructures
- Conjugated polymer nanostructures for solar energy conversion and environmental protection, including the use of conjugated polymer-based nanocomposites as photocatalysts
- Conjugated polymer nanostructures for energy storage, including the use of nanocomposites as electrode materials
- The presentation of different and novel methods of utilizing conjugated polymer nanostructures for energy applications
Perfect for materials scientists, polymer chemists, and physical chemists, Conjugated Polymer Nanostructures for Energy Conversion and Storage Applications also belongs on the bookshelves of organic chemists and any other practicing researchers, academics, or professionals whose work touches on these highly versatile and useful structures.
Table of Contents
Preface xiii
Acknowledgment xv
Part I Design and Characterization of Conjugated Polymer Nanostructures 1
1 Fundamentals of Conjugated Polymer Nanostructures 3
Thanh-Hai Le and Hyeonseok Yoon
1.1 Introduction 3
1.2 Electronic and Electrical Properties 4
1.2.1 Conductive Mechanism 4
1.2.1.1 Inherent Molecular Structure 4
1.2.1.2 Doping and Band Structure Evolution 5
1.2.2 Charge Carrier Transport Models 9
1.2.3 Temperature Dependence 13
1.3 Electrochemical Properties 16
1.3.1 Reversible Oxidation/Reduction Process and Charge Storage Behavior 16
1.3.2 Swelling and De-swelling Behavior 20
1.3.3 Electrochromism 22
1.4 Optical Properties 23
1.4.1 Band Gap of Conjugated Polymers 23
1.4.2 Absorption and Emission 27
1.4.3 Coherent Exciton Diffusion and Energy Transfer 30
1.5 Unique Properties at the Nanoscale 33
1.6 Conclusion 34
References 35
2 Chemical Synthesis of Conducting Polymers Nanostructures 43
Srabanti Ghosh and Dipanwita Majumdar
2.1 Introduction 43
2.2 Template-Based Synthesis 44
2.2.1 Hard-Template Method 44
2.2.2 Soft-Template Method 46
2.3 Template-Free Synthesis 53
2.3.1 Self Assembly via Interfacial Polymerization 54
2.3.2 Post-synthetic Self-assembly Process 57
2.3.3 Wet Spinning Process 58
2.3.4 Melt Spinning 59
2.3.5 Dry Spinning 59
2.3.6 Electrospinning 60
2.3.7 Seeding Approach 61
2.3.8 Whisker Method of Polymer Synthesis 63
2.3.9 Mixed-Solvent Technique 64
2.3.10 Reprecipitation Technique 64
2.4 Conducting Polymer Hydrogels 64
2.5 Nanolithography 67
2.5.1 Dip-Pen Nanolithography (DPN) 67
2.5.2 Nanoimprint Lithography 69
2.6 Conclusion and Future Prospects 71
References 72
3 Template-Free Synthesis of Nanostructured Conjugated Polymer Films 85
Gabriela Ramos Chagas, Thierry Darmanin, and Frédéric Guittard
3.1 Introduction 85
3.2 Template-Free Synthesis 86
3.2.1 Electrochemical Polymerization 86
3.2.2 Electrospinning 96
3.2.3 Vapor Phase Polymerization 100
3.2.4 Plasma Polymerization 103
3.3 Conclusions 105
References 106
4 Use of High Energy Radiation for Synthesis and Kinetic Study of Conjugated Polymers 117
Teseer Bahry, Zhenpeng Cui, and Samy Remita
4.1 Recent Advancements Toward Facile Preparation of Processable CPs 117
4.2 Preface to Radiation Induced Oxidative Polymerization of CPs Nanostructures in Aqueous Solutions 118
4.2.1 Studying Kinetic Mechanism of HO⋅- Induced EDOT Polymerization in Aqueous Solution 120
4.2.2 Gamma-Radiation Induced Oxidative Polymerization of EDOT in Aerated Aqueous Solutions at Neutral pH 124
4.2.3 Effect of Oxidizing Species on Gamma-Radiation-Induced Synthesis of PEDOT 126
4.2.4 Extension of the Radiolytic Procedure to the Synthesis of Polypyrrole (PPy) Nanostructures 131
4.2.5 Effect of pH on the Polymerization of EDOT Monomers 132
4.3 Radiation-Induced Synthesis of CPs Nanostructures by Reduction-Polymerization Route 134
4.4 Radiation-Induced Synthesis of CPs/Metal Nanocomposites 137
4.5 Toward Radiation-Induced Synthesis of CPs Nanostructures in Organic Solvents 141
4.6 The Electrical and Physical Properties of Radiosynthesized CPs 145
4.6.1 CPs Chain Lengths 146
4.6.2 Optical and Electronic Band Gaps of CPs 147
4.6.3 Electrical Conductivities of CPs 147
4.6.4 Thermal Properties of CPs 148
4.7 Comparative Studies Between Radiolytic Methodology and Conventional Methods 149
4.8 Summary 150
References 151
5 Conjugated Polymer Nanostructures: Characterization 159
Samim Sardar and Srabanti Ghosh
5.1 Introduction 159
5.2 Morphological Characterization 161
5.2.1 Transmission Electron Microscopy (TEM) 161
5.2.1.1 Cryo-TEM 163
5.2.1.2 Scanning Transmission Electron Microscopy (STEM) 166
5.2.1.3 Scanning Tunneling Microscopy (STM) 170
5.2.2 Field Emission Scanning Electron Microscopy (FESEM) 172
5.2.3 Atomic Force Microscopy (AFM) 173
5.3 Surface Characterization 176
5.3.1 Scanning Kelvin Probe Microscopy (SKPM) and Kelvin Probe Force Microscopy (KPFM) 176
5.3.2 X-Ray Photoelectron Spectroscopy (XPS) 178
5.4 Electrochemical Characterization 181
5.5 Spectroscopic Characterization 185
5.5.1 UV-Vis and Photoluminescence Spectroscopy 185
5.5.2 Fourier Transform Infrared Spectroscopy 190
5.5.3 Nuclear Magnetic Resonance Spectroscopy 191
5.6 Other Techniques 191
5.7 Conclusion 196
References 196
Part II Conjugated Polymer Nanostructures for Solar Energy Conversion and Environmental Protection 205
6 Conjugated Polymer Nanostructures for Catalysts Support in Fuel Cells Application 207
Srabanti Ghosh and Rajendra N. Basu
6.1 Introduction 207
6.2 Conducting Polymer Nanostructures for Electrocatalysts Support 209
6.2.1 Metal Catalysts Deposited on Conducting Polymer Nanostructures 211
6.2.2 Metal Catalysts Deposited on Modified Conducting Polymer Nanostructures 219
6.3 Conclusion 224
References 225
7 Conjugated Polymer Nanostructures for Photocatalysis 233
Srabanti Ghosh
7.1 Introduction 233
7.2 Application of Conjugated Polymer Nanostructures as Photocatalysts 235
7.2.1 Photocatalysis for Environmental Protection and Organic Pollutant Degradation 235
7.2.2 Photocatalysis for Water Splitting and H2 Generation 248
7.2.3 Conjugated Polymer Nanostructures for CO2 Photo Reduction 254
7.3 Conclusion 256
References 256
8 Conjugated Polymer-Based Nanocomposites as Photocatalysts 267
Rituporn Gogoi, Sunil Dutt, and Prem F. Siril
8.1 Introduction 267
8.2 General Methods of Synthesis of Conjugated Polymer Nanocomposites 268
8.3 Classification of the Approaches for the Synthesis of Conjugated Polymer Nanocomposites 269
8.3.1 Template Assisted Methods 270
8.3.2 Template Free Method 270
8.4 Fundamental Principles of Photocatalysis 271
8.5 Conjugated Polymer Nanocomposites and Current Challenges in Their Photocatalysis 272
8.6 Band Structure Engineering in Conjugated Polymer Nanocomposites 273
8.6.1 Solid-Solid (S-S) Interface 274
8.6.1.1 SC-SC Heterojunction 274
8.6.1.2 Semiconductor-Metal (SC-M) Heterojunction 279
8.6.2 Solid-Liquid Interface 281
8.7 Photocatalytic Applications of Conducting Polymer Nanocomposites 283
8.7.1 Water Remediation Using CPNCs 284
8.7.1.1 Inorganic Semiconductor Based CP Nanocomposites as Photocatalysts for Water Remediation 284
8.7.1.2 Plasmonic Metal-Based CPNCs 286
8.7.1.3 Conjugated Polymer-Conjugated Polymer-Based Nanocomposites 286
8.7.2 Hydrogen Generation Application 287
8.7.3 Other Applications of CP Nanocomposites 289
8.8 Conclusion 290
References 290
9 Nanostructured Conjugated Polymer for Solar Cell Applications 297
Emilie Dauzon, Guillaume Noirbent, Cedric Vancaeyzeele, Thanh-Tuan Bui, Frederic Dumur, and Fabrice Goubard
9.1 Introduction 297
9.2 Architectures of Organic Cells 300
9.2.1 Schottky Cell 300
9.2.2 Bilayer Structure 300
9.2.3 Bulk Heterojunctions 301
9.3 Chemical Strategy for Developing the Nanostructure of the Active Layer 301
9.3.1 Block Copolymers 301
9.3.2 Polymer Nanowires 305
9.3.3 Polymer Nanoparticles (PNPs) 309
9.3.3.1 Synthesis of PNPs via Precipitation Methods 309
9.3.4 Polymer Nanofiber (PNF) 311
9.4 Physical Strategies for Fabricating Polymer Nanostructures 316
9.4.1 Template Methods 316
9.4.1.1 Miniemulsion 321
9.4.1.2 Microemulsion 332
9.4.2 Porous Inorganic Materials 334
9.4.3 Electropolymerization 337
9.4.3.1 Poly(thiophenes) 338
9.4.3.2 Poly(carbazole) 342
9.4.3.3 Poly(triphenylamine) 343
9.5 Conclusion 344
References 344
Part III Conjugated Polymer Nanostructures for Energy Storage 357
10 Conjugated Polymer Nanostructures for Electrochemical Capacitor and Lithium-Ion Battery Applications 359
Thanh-Hai Le and Hyeonseok Yoon
10.1 Introduction 359
10.2 Terminology and Differences Between ECs and LIBs 360
10.3 CPNs for ECs 362
10.3.1 Fundamentals of ECs 362
10.3.2 Pseudocapacitive CPNs in ECs 366
10.3.2.1 Conventional Heterocyclic CPNs 366
10.3.2.2 Microporous Conjugated Polymers 372
10.3.3 Conjugated Polymer Nanocomposites 374
10.4 CPNs for LIBs 379
10.4.1 Fundamentals of LIBs 379
10.4.2 Conjugated Polymer Nanostructures for LIBs 381
10.4.2.1 Conjugated Polymers as Fully Active Electrode Materials for LIBs 382
10.4.2.2 Conjugated Polymers as Protective/Network Layers for LIBs 384
10.4.2.3 Heterocyclic Conjugated Polymer Nanostructures and Their Composites for LIBs 386
10.5 Conclusion 391
References 392
11 Conjugated Polymer Based Nanocomposites as Electrode Materials 401
Saptarshi Dhibar, Puspendu Das, Sanjoy Mondal, Utpal Rana, and Sudip Malik
11.1 Introduction 401
11.1.1 Polypyrrole 402
11.1.2 Polyaniline 402
11.1.3 Polythiophene 403
11.2 Conducting Polymer Based Electrode Materials 405
11.2.1 Polypyrrole 407
11.2.1.1 Different Nano-Architectures of Polypyrrole 407
11.2.1.2 Polypyrrole Nanostructures as Electrode Materials 408
11.2.1.3 Graphene and CNT Based Polypyrrole Nanocomposites 409
11.2.2 Polyaniline 416
11.2.2.1 Different Nano-Architectures of Polyaniline 416
11.2.2.2 Effect of Dopant Size in Nanostructure 420
11.2.2.3 Polyaniline Nanostructures as Electrode Materials 420
11.2.2.4 Graphene and CNT Based Polyaniline Nanocomposites 423
11.2.3 Polythiophene 426
11.2.3.1 Different Nano-Architectures of Polythiophene 430
11.2.3.2 Polythiophene Nanostructures as Electrode Materials 430
11.2.3.3 Graphene and CNT Based Polythiophene Nanocomposites 432
11.3 Summary 433
Acknowledgment 435
References 436
12 Conducting Polymers Nanowires with Carbon Nanotubes or Graphene-Based Nanocomposites for Supercapacitors Applications 445
Thuan Nguyen Pham Truong, Philippe Banet, and Pierre-Henri Aubert
12.1 Introduction on Electrochemical Storage Using Electronic Conducting Polymers (ECP) 445
12.1.1 Electronic Conducting Polymers (ECP) 446
12.1.2 Synthesis of ECPs 447
12.1.3 Electrochemical Storage Properties of ECPs 448
12.1.4 Morphology and Nanostructuration of ECP 449
12.2 Porous Carbon-Based Nanocomposites 453
12.2.1 Polypyrrole/Porous Carbon Nanocomposites 454
12.2.2 Polyaniline/Porous Carbon Nanocomposites 455
12.2.3 Polyethylenedioxythiophene/Porous Carbon Nanocomposites 456
12.3 CNT-Based Nanocomposites 457
12.3.1 ECP with Entangled CNT Composites 458
12.3.2 ECP with Vertically Aligned CNT Composites 460
12.4 Graphene-Based Nanocomposites 465
12.4.1 Polymer/Graphene Composites 466
12.4.2 Polyaniline/Graphene 466
12.4.3 Polypyrrole/Graphene 471
12.4.4 Thiophene-Based Polymers/Graphene 478
12.5 Conclusion and Outlook 482
References 485
Index 499
