Synthesis and Applications of Nanocarbons

Editors Jean-Charles Arnault, Diamond Sensors Laboratory, CEA LIST, Gif-sur-Yvette, France Dominik Eder, Institute of Materials Chemistry, Vienna University of Technology, Vienna, Austria

• List of Contributors xiSeries Preface xiiiPreface xv1 Properties of Carbon Bulk Materials: Graphite and Diamond 1Kamatchi Jothiramalingam Sankaran and Ken Haenen1.1 Introduction 11.2 Graphite 21.2.1 History 21.2.2 sp2 Hybridization 31.2.3 Structure of Graphite 31.2.3.1 Hexagonal Graphite 31.2.3.2 Rhombohedral Graphite 31.2.3.3 Polycrystalline Graphite 41.2.3.4 Crystallite Imperfections 51.2.4 Natural and Synthetic Graphite 51.2.4.1 Natural Graphite 51.2.4.2 Synthetic Graphite 61.3 Diamond 71.3.1 History 71.3.2 sp3 Hybridization 81.3.3 Structure of Diamond 91.3.3.1 Crystal Forms of Diamond 91.3.4 Impurities in Diamond 101.3.4.1 Lattice Impurities 111.3.4.2 Inclusions 111.3.5 Natural and Synthetic Diamond 111.3.5.1 Natural Diamond 111.3.5.2 Synthetic Diamond 121.4 Characterization of Graphite and Diamond 141.4.1 Raman Spectroscopy 141.4.2 X-ray Diffraction 151.4.3 Electron Energy Loss Spectroscopy 151.4.4 X-ray Photoelectron Spectroscopy 171.4.5 Scanning Electron Microscopy 171.4.6 Transmission Electron Microscopy 171.5 Properties of Graphite and Diamond 181.6 Applications of Graphite and Diamond 201.6.1 Graphite 201.6.2 Diamond 20References 212 Endohedral and Exohedral Single-Layered Fullerenes 25Diana M. Bobrowska and Marta E. Plonska-Brzezinska2.1 Introduction 252.2 Structure and Physicochemical Properties of “Empty” Single-Layered Fullerenes 252.3 Structure and Physicochemical Properties of Endohedral Fullerenes 292.4 Functionalization and Application of Single-Layered Fullerenes 322.4.1 Functionalization and Application of Exohedral Fullerenes 322.4.2 Functionalization and Application of Endohedral Metallofullerenes 382.5 Summary 42Acknowledgments 42References 423 Spherical Onion-Like Carbons 63Diana M. Bobrowska and Marta E. Plonska-Brzezinska3.1 Introduction 633.2 Structure of Onion-Like Carbons and Their Physicochemical Properties 633.3 Covalent and Noncovalent Functionalization of OLCs 693.4 Doping of OLCs by Heteroatoms 823.5 Applications of OLCs 843.5.1 Bioimaging 843.5.2 (Bio)Sensors 853.5.3 Energy Storage Devices 863.5.4 Solar Cells 883.5.5 Electronic and Photonic Applications 883.5.6 Sorbents 893.5.7 Catalysis and Electrocatalysis 893.5.8 Tribology 903.6 Summary 90Acknowledgments 91References 914 Carbon Nanotubes: Synthesis, Properties, and New Developments in Research 107Marianna V. Kharlamova and Dominik Eder4.1 Introduction 1074.2 Atomic Structure of Carbon Nanotubes 1084.3 Properties of Carbon Nanotubes 1094.3.1 Electronic Properties 1094.3.2 Mechanical Properties 1104.3.3 Thermal Properties 1114.4 Synthesis of Carbon Nanotubes 1114.4.1 Arc-Discharge 1114.4.2 Laser Ablation 1124.4.3 Molten Salt Route/Electrolytic Process 1134.4.4 Chemical Vapor Deposition 1134.5 Postsynthesis Treatments of Carbon Nanotubes 1144.5.1 Purification 1144.5.2 Separation of Metallic and Semiconducting SWCNTs 1154.5.3 Functionalization 1164.6 New Developments in Carbon Nanotube Research: Toward Controllable Properties of Nanotubes 1174.6.1 Chirality Selective Synthesis of SWCNTs 1174.6.2 Chirality Selective Separation of SWCNTs 1204.6.3 Substitutional Doping of SWCNTs 1224.6.4 Exohedral Modification of CNTs: Nanotube Hybrids 1234.6.5 Filling of SWCNT Interior Channels 1244.7 Conclusions and Outlook 125Acknowledgments 128References 1295 CNT Fiber-Based Hybrids: Synthesis, Characterization, and Applications in Energy Management 149Moumita Rana, Cleis Santos, Alfonso Monreal-Bernal and Juan J. Vilatela5.1 Introduction: What are CNT Fibers andWhy Do they Form Interesting Hybrids and Composites? 1495.1.1 CNT Fiber Structure and Properties 1495.1.2 Design Principles in CNT Fiber Hybrids 1525.2 Hybridization with Metal Oxides 1535.2.1 Surface Chemistry and Functionalization 1545.2.2 Examples of Common Architectures: Layered, Particulates, Conformal 1565.2.2.1 Particulate Systems 1565.2.2.2 Layered Systems 1615.2.2.3 Conformal CNT Fiber Hybrids 1625.2.3 Hybrid Structure and Interfacial Characterization 1635.2.3.1 Determination of Mass Fraction 1635.2.3.2 Wetting and Interaction with Solvents 1665.2.3.3 Specific Surface Area and Pore Size 1685.2.4 Solid-State Transport Characterization of Layered Hybrids 1695.2.4.1 Junction Characterization in Layered Hybrids 1715.2.5 Interfacial Studies by Electrochemical Impedance Spectroscopy Methods 1755.2.6 Advanced Interfacial Studies in ALD-Hybrid Test Systems 1775.2.6.1 Residual Strain 1775.2.6.2 Evidence of an Interfacial Ti—O—C Bond 1795.2.6.3 Electronic Structure of the Ti—O—C Interface 1805.3 EDLC Introducing Pseudocapacitive Reactions 1825.4 Capacitive Deionization 1855.5 Battery Electrodes 1895.6 Conclusions and Perspective 193References 1946 Advanced Materials Designed with Nanodiamonds: Synthesis and Applications 201Jean-Charles Arnault6.1 Introduction 2016.2 Synthesis of Isolated Objects from ND 2036.2.1 ND Grafted with Molecules 2036.2.1.1 Electrostatic Grafting 2036.2.1.2 Chemical Grafting 2066.2.2 Nanodiamonds as Templates 2096.2.2.1 Decoration by Atoms or Clusters 2096.2.2.2 Core Shells with Diamond Core 2126.3 Decoration of Particles by ND, Core Shells with Diamond Shell 2156.3.1 Nanodiamonds to Decorate or to Graft to NP 2156.3.1.1 Emulsion 2156.3.1.2 Decoration of Nanoparticles with ND 2166.3.1.3 Decoration of Carbon Nanostructures by ND 2176.3.2 Silica/Diamond Core Shells 2186.4 Conclusion and Perspectives 219References 2207 Chemical Functionalization of Nanodiamond for Nanobiomedicine 229Naoki Komatsu7.1 Introduction 2297.2 ND for Fluorescent Cell Labeling 2297.2.1 Fluorophore-Immobilized ND 2297.2.1.1 Synthesis 2297.2.1.2 Cell Labeling 2317.2.2 ND with Intrinsic Fluorescence 2327.2.2.1 Synthesis 2327.2.2.2 Cell Labeling 2337.3 ND for MRI 2357.3.1 Synthesis 2357.3.2 MRI Relaxivity 2387.4 ND for Gene Delivery 2387.4.1 Synthesis 2387.4.2 Gene Delivery 2397.5 ND for Drug Delivery 2417.5.1 Synthesis 2417.5.2 Drug Delivery 2437.6 Concluding Remarks 244Acknowledgments 245References 2458 Nanocarbon Aerogels and Aerographite 247Hubert Beisch and Bodo Fiedler8.1 Introduction 2478.2 Fabrication 2478.2.1 Non-template Based and Template Based Methods 2488.2.1.1 Non-template Based Synthesis 2488.2.1.2 Template Based Synthesis 2498.2.2 Template Based Synthesis of Aerographite and Globugraphite 2498.2.2.1 Fabrication of Porous Ceramic Templates 2498.2.2.2 CVD Synthesis 2508.3 Morphology 2538.3.1 Tetrapodal Networks 2538.3.2 Globular Foam Structures with Hierarchical Pore Morphology 2548.3.3 ReticularMorphology 2558.3.4 Carbon Hybrids 2568.4 Properties 2588.4.1 Density 2588.4.2 Electrical and Electrochemical Properties 2598.4.2.1 Electrical Conductivity 2598.4.2.2 Electrochemical Performance 2628.5 Modifications 2678.5.1 Metal and Metal Oxide Hybrids 2678.5.2 Thermal Treatment (Annealing) 2678.6 Conclusion 2708.6.1 Summary 2708.6.2 Outlook 271References 2719 Optoelectronic Properties of Nanocarbons and Nanocarbon Films 275Cameron J. Shearer, LePing Yu and Joseph G. Shapter9.1 Introduction 2759.2 Nanocarbons 2769.2.1 Graphene and Derivatives 2769.2.1.1 Pristine Graphene via Micromechanical Exfoliation 2769.2.1.2 Reduced Graphene/Graphite Oxide 2789.2.1.3 Graphene from Chemical Vapor Deposition 2789.2.2 Carbon Nanotubes 2799.2.2.1 SWCNT Chirality 2809.3 Fundamentals of Optical and Electronic Properties of Nanocarbons 2809.3.1 Electronic Properties 2809.3.1.1 Graphene 2809.3.1.2 Carbon Nanotubes 2829.3.2 Optical Properties 2849.3.2.1 Graphene 2849.3.2.2 Carbon Nanotubes 2849.4 Optoelectronic Properties of Nanocarbon Films 2879.4.1 The Figure of Merit (FOM) of Optoelectronic Devices 2879.4.2 Techniques to Maximize FOM 2879.5 Summary and Outlook 289References 290Index 295