Advanced functional materials

Advanced Functional Materials

Scrivener Publishing

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Beverly, MA 01915-6106

Advanced Materials Series

Th e Advanced Materials Series provides recent advancements of the fascinating

fi eld of advanced materials science and technology, particularly in the area of

structure, synthesis and processing, characterization, advanced-state properties,

and applications. Th e volumes will cover theoretical and experimental

approaches of molecular device materials, biomimetic materials, hybrid-type

composite materials, functionalized polymers, supramolecular systems,

information- and energy-transfer materials, biobased and biodegradable or

environmental friendly materials. Each volume will be devoted to one broad

subject and the multidisciplinary aspects will be drawn out in full.

Series Editor: Dr. Ashutosh Tiwari

Biosensors and Bioelectronics Centre

Linköping University

SE-581 83 Linköping

Sweden

E-mail: [email protected]

Publishers at Scrivener

Martin Scrivener([email protected])

Phillip Carmical ([email protected])

Advanced Functional

Materials

Edited by

Ashutosh Tiwari and Lokman Uzun

Copyright © 2015 by Scrivener Publishing LLC. All rights reserved.

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Cover design by Russell Richardson

Library of Congr ess Cataloging-in-Publication Data:

ISBN 978-1-118-99827-4

Printed in the United States of America

10 9 8 7 6 5 4 3 2 1

Contents

Preface xv

Part 1: Functional Metal Oxides: Architecture, Design,

and Applications

1 Development of Toxic Chemicals Sensitive Chemiresistors

Based on Metal Oxides, Conducting Polymers and

Nanocomposites Th in Films 3

Sadia Ameen, M. Shaheer Akhtar, Hyung-Kee Seo, and

Hyung-Shik Shin

1.1 Introduction 4

1.2 Semiconducting Metal Oxide Nanostructures

for Chemiresistor 6

1.2.1 Prospective Electrode of TiO2

Nanotube Arrays

for Sensing Phenyl Hydrazine 6

1.2.2 Aligned ZnO Nanorods with Porous Morphology

as Potential Electrode for the Detection of

p-Nitrophenylamine 10

1.2.3 ZnO Nanotubes as Smart Chemiresistor for the

Eff ective Detection of Ethanolamine Chemical 17

1.3 Conducting Polymers Nanostructures for

Chemiresistors 21

1.3.1 Sea-Cucumber-Like Hollow Polyaniline Spheres

as Effi cient Electrode for the Detection of

Aliphatic Alcohols 21

1.3.2 Th e Sensing Properties of Layered Polyaniline

Nanosheets toward Hazardous Phenol Chemical 30

1.3.3 Prospective Electrode of Polypyrrole Nanobelts

for the Detection of Aliphatic Alcohols 36

vi Contents

1.4 Semiconducting Nanocomposites for Chemoresistors 44

1.4.1 Hydrazine Chemical Sensing by Modifi ed

Electrode of Polyaniline/Graphene

Nanocomposite Th in Film 44

1.5 Conclusions and Outlook 48

Acknowledgments 49

References 49

2 Th e Synthetic Strategy for Developing Mesoporous Materials

through Nanocasting Route 59

Rawesh Kumar and Biswajit Chowdhury

2.1 Introduction to Nanocasting 59

2.2 Steps of Nanocasting 61

2.2.1 Infi ltration 61

2.2.2 Th e Casting Step 67

2.2.3 Template Removal by Dissolution or by

Oxidation at High Temperatures 68

2.3 Porous Silica as Template for Inorganic Compounds 68

2.3.1 Nanocast Cobalt Oxides, Cerium Oxide, and

Copper Oxide 71

2.3.2 Nanocast Chromium Oxides 73

2.3.3 Nanocast Indium Oxides and Nickel Oxide 74

2.3.4 Nanocast Molybdenum and Manganese Oxide 75

2.3.5 Nanocast Iron Oxide 76

2.3.6 Nanocast Tungsten Oxide 77

2.3.7 Nanocast Tin Oxide 77

2.3.8 Nanocast BiVO4

and B4

C 78

2.3.9 Nanocast Metal 79

2.3.10 Nanocast Metal Sulfi des 80

2.3.11 Nanocasted Ceramics 83

2.3.12 Nanocasted Mesoporous YPO4

84

2.3.13 Potential Application 84

2.4 Porous Silica as Template for Mesoporous Carbon 86

2.4.1 CMK Family 86

2.4.2 NCC-1, UF-MCN, SNU-1, MCF, and MCCF 89

2.4.3 Hollow Mesoporous Carbon Sphere/Prism 92

2.4.4 Ordered Mesopores Carbon with Surface Graft ed

Magnetic Particles 94

2.4.5 Surface Modifi ed Mesoporous Nitrogen Rich

Carbon by Nanocasting 98

2.4.6 Potential Application 100

Contents vii

2.5 Porous Carbon as Template for Inorganic Compound 104

2.5.1 Nanocasted Silica by Porous Carbon Template 104

2.5.2 Nanocasted Alumina and Nanocasted MgO 106

2.5.3 Nanocasted CeO2

and ZnO 107

2.5.4 Nanocasted CuO 109

2.5.5 Nanocasted Other Metal Oxide 109

2.5.6 Mesoporous Sphere of Metal Oxide and Phosphate 110

2.5.7 Nanocast Ceramics 110

2.5.8 Mesoporous Hydroxyapatite and Phosphates 112

2.5.9 Potential Application 113

2.6 Future Prescriptive 113

2.7 Limitation 114

2.8 Conclusion 115

Acknowledgments 116

References 116

3 Spray Pyrolysis of Nano-Structured Optical and Electronic

Materials 127

Nurdan Demirci Sankir, Erkan Aydin, Esma Ugur, and

Mehmet Sankir

3.1 Introduction 128

3.2 Spray Pyrolysis Technology 128

3.2.1 Flame Spray Pyrolysis 131

3.2.2 Mist Generation Technologies 132

3.3 Nanoparticles Created via Spray Pyrolysis Method 134

3.3.1 Copper Oxides 136

3.3.2 Indium Oxide 136

3.3.3 Tin Oxide 138

3.3.4 Titanium Dioxide 139

3.3.5 Zinc Oxide 141

3.4 Nanopillars and Nanoporous Structures 142

3.4.1 Hematite (α-Fe2

O3

) 143

3.4.2 Tin Oxide (SnO2

) 146

3.4.3 Titanium Dioxide 146

3.4.4 Zinc Oxide 147

3.5 Nanocrystalline Th in Film Deposition

by Spray Pyrolysis 150

3.5.1 Nanocrystalline Cu-Based Chalcopyrite Th in

Films 150

3.5.2 Nanocrystalline Kesterite Th in Films 156

viii Contents

3.5.3 Nanocrystalline Metal Oxide Th in Films 161

3.5.4 Nanocrystalline Chalcogenide Th in Films 165

3.6 Conclusion 167

Acknowledgments 168

References 168

4 Multifunctional Spinel Ferrite Nanoparticles for Biomedical

Application 183

Noppakun Sanpo, Cuie Wen, Christopher C. Berndt,

and James Wang

4.1 Introduction 183

4.2 Ferrites 187

4.2.1 Cubic Ferrites 187

4.2.2 Hexagonal Ferrites 189

4.3 Th e Sol–Gel Method 189

4.3.1 Th e Sol–Gel Processing Method 189

4.3.2 Applications 194

4.4 Chelating Agents 195

4.4.1 Mineral Processing Examples of Using Chelating

Agents 195

4.4.2 Organic Acids 198

4.5 Approach and Methodology 199

4.5.1 Fabrication of Spinel Ferrite Nanoparticles 199

4.5.2 Analytical Techniques Employed 200

4.5.3 Biocompatibility Study 201

4.6 Experimental Results 202

4.6.1 Diff erential Scanning Calorimetry and Th ermo

Gravimetric Analyses 202

4.6.2 Raman Analyses 202

4.6.3 Particle Size Analysis 204

4.6.4 Microstructure of Spinel Ferrite Nanoparticles 205

4.6.5 XRD Analysis 206

4.6.6 Contact Angle Measurement and Roughness

Parameters 210

4.6.7 Antibacterial Activities of the Spinel Ferrite

Nanoparticles 210

4.6.8 Biocompatibility of Spinel Ferrite Nanoparticles 212

Contents ix

4.7 Concluding Remarks 213

Acknowledgements 214

References 214

5 Heterostructures Based on TiO2

and Silicon for Solar

Hydrogen Generation 219

Dilip Kumar Behara, Arun Prakash Upadhyay, Gyan

Prakash Sharma, B.V. Sai Krishna Kiran, Sri Sivakumar

and Raj Ganesh S. Pala

5.1 Introduction 220

5.2 Overview of Heterostructures 221

5.2.1 Motivation/Importance of Heterostructured

Nanomaterials 221

5.2.2 Classifi cation of Heterostructures 223

5.2.3 Discussion on Other Heterostructure

Classifi cations 232

5.2.4 Challenges/Key Issues in Forming

Heterostructures 233

5.3 TiO2

Heterostructures 234

5.3.1 Heterojunctions of TiO2

Polymorphic Phases 234

5.3.2 TiO2

Heterojunctions with Metals

(Metal-Semiconductor Junctions) 238

5.3.3 Core–Shell Structures 245

5.3.4 Janus Structures 251

5.4 Silicon Based Heterostructures 253

5.4.1 Silicon Based Heterostructures for PEC

Application 253

5.4.2 Heterojunctions vs Multijunction Silicon 258

5.4.3 Pros/Cons in Improvement of Si Heterostructures

for Energy Harvesting and Conversion 261

5.5 Some Unaddressed Issues of Heterostructures in Relation

to Photocatalysis 261

5.5.1 Measures to be Taken in Perspective of

Photocatalysis of Heteronanostructures 262

5.6 Summary/Conclusions and Future Outlook 262

Acknowledgment 263

Notes on Contributors 263

References 264

x Contents

6 Studies on Electrochemical Properties of MnO2

and CuO

Decorated Multi-Walled Carbon Nanotubes as

High-Performance Electrode Materials 283

Mohan Raja

6.1 Introduction 283

6.2 Experimental 285

6.2.1 Materials 285

6.2.2 Preparation and Fabrication of Supercapacitor

Cell 285

6.3 Characterization 286

6.4 Results and Discussion 286

6.5 Conclusion 292

References 293

Part 2: Multifunctional Hybrid Materials:

Fundamentals and Frontiers

7 Discotic Liquid Crystalline Dimers: Chemistry and

Applications 297

Shilpa Setia, Sandeep Kumar and Santanu Kumar Pal

7.1 Introduction 298

7.2 Structure-Property Relationship of Discotic Dimers 300

7.2.1 Discotic Dimers Based on Anthraquinone Core 300

7.2.2 Discotic Dimers Based on Benzene Core 304

7.2.3 Discotic Dimers Based on Cyclotetraveratrylene

Core 309

7.2.4 Discotic Dimers Based on Dibenzo[a,c]phenazine

Core 309

7.2.5 Discotic Dimers Based on Hexa-peri￾Hexabenzocoronene (HBC) Core 313

7.2.6 Discotic Dimers Based on Phthalocyanine Core 316

7.2.7 Discotic Dimers Based on Porphyrin Core 325

7.2.8 Discotic Dimers Based on Pyranose Sugars 330

7.2.9 Discotic Dimers Based on Pyrene Core 332

7.2.10 Discotic Dimers Based on Scylloinositol Dimer 334

7.2.11 Discotic Dimers Based on Triphenylene Core 334

7.3 Applications 357

7.3.1 Dopants for Liquid Crystal Display Mixtures 357

7.3.2 Organic Light-Emitting Diodes (OLEDs) 360

7.4 Conclusions and Outlook 361

References 362

Contents xi

8 Supramolecular Nanoassembly and Its Potential 367

Alok Pandya, Heena Goswami, Anand Lodha and Pinkesh

Sutariya

8.1 Supramolecular Chemistry 368

8.1.1 Supramolecular Interactions 371

8.1.2 Types of Supramolecules 373

8.2 Nanochemistry 376

8.2.1 Why Nano 379

8.2.2 Chemical Approach of Nanomaterials 379

8.2.3 Gold and Silver Nanoparticles 382

8.2.4 Self-Assembled Monolayer 383

8.3 Supramolecular Nanoassembly 384

8.3.1 Cations Receptors 384

8.3.2 Anion Receptors 387

8.3.3 Biomolecule Receptor 388

8.3.4 Pesticide Detection 390

8.3.5 Other Nanomaterials Supported Supramolecules 391

8.4 Conclusion and Future Prospects 394

References 396

Suggested Further Reading 397

9 Carbon-Based Hybrid Composites as Advanced Electrodes

for Supercapacitors 399

S.T. Senthilkumar, K. Vijaya Sankar , J. S. Melo,

A. Gedanken, and R. Kalai Selvana

9.1 Introduction 400

9.1.1 Background 400

9.2 Principle of Supercapacitor 402

9.2.1 Basics of Supercapacitor 402

9.2.2 Charge Storage Mechanism of SC 404

9.3 Activated Carbon and their Composites 410

9.4 Carbon Aerogels and Th eir Composite Materials 411

9.5 Carbon Nanotubes (CNTs) and their Composite

Materials 415

9.6 Two-Dimensional Graphene 417

9.6.1 Electrochemical Performance of Graphene 418

9.6.2 Graphene Composites 419

9.6.3 Doping of Graphene with Heteroatom 423

9.7 Conclusion and Outlook 424

Acknowledgements 425

References 425

xii Contents

10 Synthesis, Characterization, and Uses of Novel-Architecture

Copolymers through Gamma Radiation Technique 433

H. Iván Meléndez-Ortiz and Emilio Bucio

10.1 Introduction 434

10.2 Ionizing Radiation 435

10.2.1 Type of Radiation 435

10.2.2 X-Ray and Gamma-Rays 436

10.2.3 Electron Beam 437

10.2.4 Alpha Particles 437

10.2.5 Neutrons 438

10.3 Gamma-Ray Measurements 438

10.3.1 Dosimetry 438

10.3.2 Fricke Dosimetry Method 440

10.3.3 Units of Radioactivity and Radiation Absorption 441

10.4 Synthesis of Graft Polymers by Gamma-Rays 441

10.4.1 Radiation Graft ing 441

10.4.2 Simultaneous or Mutual Method 442

10.4.3 Pre-irradiation Method 443

10.4.4 Pre-irradiation Oxidative Method 444

10.4.5 Parameter Infl uencing Graft ed Copolymers

Synthesis 444

10.5 Diff erent Architecture of Polymers 449

10.5.1 Stimuli-Responsive Networks Graft ed onto

Polypropylene for the Sustained Delivery of

NSAIDs 449

10.5.2 Radiation Graft ing of Glycidyl Methacrylate

onto Cotton Gauzes for Functionalization with

Cyclodextrins and Elution of Antimicrobial

Agents 450

10.5.3 Binary Graft Modifi cation of Polypropylene for

Anti-infl ammatory Drug-Device Combo

Products 450

10.5.4 Temperature- and pH-Sensitive IPNs Graft ed

onto Polyurethane by Gamma Radiation for

Antimicrobial Drug-Eluting Insertable Devices 452

10.5.5 Temperature-Responsiveness and

Biocompatibility of DEGMA/OEGMA Radiation

Graft ed onto PP and LDPE Films 453

10.5.6 Acrylic Polymer-Graft ed Polypropylene Sutures

for Covalent Immobilization or Reversible

Adsorption of Vancomycin 453

Contents xiii

10.6 Polymer Characterization 455

10.6.1 Swelling Measurements 455

10.6.2 Surface Plasmon Resonance Spectroscopy (SPR) 455

10.6.3 Infrared (IR) 456

10.6.4 Nuclear Magnetic Resonance Spectroscopy

(NMR) 456

10.6.5 Th ermal Transition 456

10.6.6 Contact Angle 457

10.6.7 Atomic Force Microscopy (AFM) 457

Acknowledgments 458

References 458

11 Advanced Composite Adsorbents: Chitosan versus Graphene 463

George Z. Kyzas

11.1 Introduction 463

11.2 Chitosan-Based Materials 465

11.2.1 Synthesis and Various Modifi cations 466

11.3 Graphene-Based Materials 478

11.3.1 Adsorption Applications 479

11.4 Graphene/Chitosan Composite Adsorbents 483

11.5 Conclusions 488

References 489

12 Antimicrobial Biopolymers 493

S. Sayed and M.A. Jardine

12.1 Introduction 493

12.2 Biopolymers 496

12.2.1 ε-Poly-l-Lysine 496

12.2.2 Chitin and Chitosan 500

12.3 Synthetic Biodegradable Polymers 506

12.3.1 Quaternary Polymers 506

12.3.2 Polyethylenimine 510

12.3.3 Antimicrobial Peptide Mimics 511

12.4 Metal Loading 514

12.4.1 Silver 515

12.4.2 Magnesium 516

12.4.3 Zinc 517

12.4.4 Titanium 517

12.5 Assessment of Antimicrobial/Antifungal Testing

Methods 518