Preface ...................................................... XIII
List of Contributors ........................................... XV
1 An Introduction to Craphene ................................ 1
Konstantinos Spyrou and Petra Rudolf
1.1 Brief History of Graphite .................................. 1
1.2 Graphene and Graphene Oxide ................................ 2
1.2.1 Preparation of Graphene from Graphene Oxide ......... 3
1.2.2 Isolation of Pristine Graphene Monolayers ........... 5
1.2.3 Large Scale Production of GO by Langmuir-Blodgett
Methods ............................................. 6
1.2.4 Other Methods of Graphene Production ................ 6
1.3 Characterization of Graphene ............................... 9
1.3.1 Microscopic Observation ............................. 9
1.3.2 Raman Spectroscopy ................................. 11
1.3.3 Thermogravimetric Analysis ......................... 12
1.3.4 Optical Properties of Graphene ..................... 13
1.3.5 X-Ray Diffraction Pattern .......................... 17
References ................................................ 28
2 Covalent Attachment of Organic Functional Groups on
Pristine Graphene ......................................... 21
Vasilios Georgakilas
2.1 Introduction .............................................. 21
2.2 Cycloaddition Reactions ................................... 22
2.2.1 1,3-Dipolar Cycloaddition of Azomethine Ylide ...... 22
2.2.1.1 Through a Substituted Aldehyde Pathway .... 24
2.2.1.2 Through Substituted a Amino Acid Pathway .. 27
2.2.2 Cycloaddition by Zwitterionic Intermediate ......... 28
2.2.3 Diels-Alder Cycloaddition .......................... 29
2.2.4 Nitrene Addition ................................... 30
2.2.5 Carbene Addition ................................... 35
2.2.6 Aryne Addition ..................................... 36
2.2.7 Bingel Type Cycloaddition .......................... 37
2.3 Addition of Free Radicals ................................. 39
2.3.1 Diazonium Salt Reaction ............................ 39
2.3.2 Other Radical Additions ............................ 42
2.4 Nucleophilic Addition ..................................... 46
2.5 Electrophilic Addition on Graphene ........................ 46
2.6 Organometallic Chemistry of Graphene ...................... 48
2.7 Post Functionalization Reactions .......................... 50
2.8 Conclusion ................................................ 55
References ................................................ 56
3 Addition of Organic Groups through Reactions with Oxygen
Species of Graphene Oxide ................................. 59
Vasilios Georgakilas
3.1 Introduction .............................................. 59
3.1.1 Graphene/Polymer Nanocomposites .................... 60
3.2 The Role of Carboxylic Acids of GO ........................ 61
3.2.1 Organic Functionalization through Amide Bond
Formation .......................................... 61
3.2.1.1 Lipophilic Derivatives .................... 61
3.2.1.2 Hydrophilic - Biocompatible Derivatives ... 62
3.2.1.3 Addition of Chromophores .................. 64
3.2.1.4 Polymer Graphene Composite ................ 69
3.2.2 Esterification of GO ............................... 71
3.2.3 Functionalization of GO through Heterocyclic Ring
Formation .......................................... 75
3.3 The Role of Hydroxyl Groups of GO ......................... 77
3.4 Miscellaneous Additions ................................... 78
3.4.1 Reaction of Carboxylic Acid and Hydroxyl Groups
with Isocyanate Derivatives ........................ 78
3.4.2 Reaction of Epoxides with Carboxylic Acids or
Hydroxyl Groups .................................... 78
3.4.3 Interaction of Ammonia with Carboxylic Acids and
Epoxides of GO ..................................... 80
3.4.4 Enrichment of GO in Carboxylic Acids ............... 81
3.4.5 Addition of Gallium-Phthalocyanine (Ga-Pc) to GO
through Ga-O Covalent Bond ......................... 82
3.5 The Role of Epoxide Groups of GO .......................... 83
3.5.1 Nucleophilic Addition of Amine to Epoxides ......... 83
3.5.2 Addition of Chromophores ........................... 85
3.5.3 Addition of Polymers ............................... 86
3.6 Post Functionalization of GO .............................. 87
3.6.1 Post Functionalization of Organically Modified GO
via Click Chemistry ................................ 87
3.6.2 Counter Anion Exchange ............................. 89
3.7 Conclusions ............................................... 90
References ................................................ 92
4 Chemical Functionalization of Graphene for Biomedical
Applications .............................................. 95
Cinzia Spinato, Cécilia Ménard-Moyon, and Alberto Bianco
4.1 Introduction .............................................. 95
4.2 Covalent Functionalization of Graphene Nanomaterials ...... 97
4.2.1 Synthesis of GO and rGO ............................ 99
4.2.1.1 Synthesis of Graphene Oxide ............... 99
4.2.1.2 Reduction of Graphene Oxide ............... 99
4.2.2 Functionalization of Graphene Oxide with
Polymers .......................................... 100
4.2.2.1 PEGylated-GO Conjugates .................. 100
4.2.2.2 Covalent Linkage of Biopolymers .......... 103
4.2.3 Tethering of Antibodies ........................... 105
4.2.4 Attachment of Nucleic Acids ....................... 106
4.2.5 Grafting of Peptides and Enzymes .................. 108
4.2.6 Attachment of Other Organic Molecules and
Biomolecules ...................................... 108
4.3 Non-covalent Functionalization of Graphene ............... 110
4.3.1 Adsorption via π-Stacking ......................... 110
4.3.1.1 Adsorption of Drugs ...................... 111
4.3.1.2 Adsorption of Pyrene Derivatives ......... 111
4.3.1.3 Non-covalent Interactions with Nucleic
Acids and Aptamers ....................... 113
4.3.1.4 Immobilization of Enzymes, Proteins,
and Other Macromolecules ................. 116
4.3.2 Electrostatic and Hydrophobic Interactions ........ 116
4.3.2.1 Coating with Polymers and Biopolymers .... 116
4.3.2.2 Deposition of Nanoparticles .............. 119
4.3.2.3 Adsorption of Quantum Dots ............... 121
4.4 Graphene-Based Conjugates Prepared by a Combination of
Covalent and Non-covalent Functionalization .............. 121
4.4.1 Polymer- and Biopolymer-Grafted Graphene
Nanomaterials Used as Nanocarriers ................ 121
4.4.1.1 Polymer-Functionalized GO for Drug
Delivery ................................. 122
4.4.1.2 Polymer-Functionalized GO for Gene
Delivery ................................. 123
4.4.1.3 Chitosan-Functionalized GO ............... 125
4.4.2 GO Functionalized with Targeting Ligands and
Antibodies ........................................ 125
4.4.2.1 Folic Acid-Conjugated GO ................. 125
4.4.2.2 Antibody-Functionalized GO for
Radioimaging and Biosensing .............. 127
4.5 Conclusions .............................................. 129
Acknowledgments .......................................... 130
References ............................................... 130
5 Immobilization of Enzymes and other Biomolecules on
Graphene ................................................. 139
Ioannis V. Pavlidis, Michaela Patila, Angeliki С. Polydera,
Dimitrios Goumis, and Haralampos Stamatis
5.1 Introduction ............................................. 139
5.2 Immobilization Approaches ................................ 141
5.3 Applications of Immobilized Biomolecules ................. 145
5.3.1 Biosensors ........................................ 145
5.3.1.1 Glucose Oxidase-Based Biosensors ......... 146
5.3.1.2 Horseradish Peroxidase-Based Biosensors .. 150
5.3.1.3 Tyrosinase-Based Biosensors .............. 151
5.3.1.4 Cytochrome c-Based Biosensors ............ 152
5.3.1.5 Other Protein/Enzyme Biosensors .......... 152
5.3.1.6 DNA Sensors .............................. 152
5.3.1.7 Immunosensors and Aptasensors ............ 154
5.3.2 Biocatalysis ...................................... 155
5.3.3 Biofuel Cells ..................................... 159
5.3.4 Drug and Gene Delivery ............................ 161
5.4 Interactions between Enzymes and Nanomaterials ........... 162
Conclusions .............................................. 165
Abbreviations ............................................ 165
References ............................................... 166
6 Halogenated Craphenes: Emerging Family of Two-
Dimensional Materials .................................... 173
Kasibhatta Kumara Ramanatha Datta and Radek Zbořil
6.1 Introduction ............................................. 173
6.2 Synthesis of Halogenated Graphenes ....................... 174
6.2.1 Fluorographene .................................... 175
6.2.1.1 Mechanical or Chemical Exfoliation -
from Graphite Fluoride to
Fluorographene ........................... 175
6.2.1.2 Fluorination of Graphene - from
Graphene to Fluorographene ............... 175
6.2.2 Nonstoichiometric Fluorinated Graphene and
Fluorinated Graphene Oxide ........................ 175
6.2.3 Other Halogenated Graphenes ....................... 178
6.3 Characterization of Halogenated Graphenes ................ 179
6.3.1 Fluorographene .................................... 179
6.3.2 Partially Fluorinated and Halogenated Graphenes ... 183
6.4 Chemistry, Properties, and Applications of
Fluorographene and Fluorinated Graphenes ................. 184
6.5 Chemistry and Properties of Chlorinated and Brominated
Graphenes ................................................ 190
6.6 Other Interesting Properties of Halogenated Graphenes
and Their Applications ................................... 190
6.7 Halogenated Graphene-Graphene Heterostructures -
Patterned Halogenation ................................... 193
6.8 Conclusion and Future Prospects .......................... 295
References ............................................... 295
7 Noncovalent Functionalization of Graphene ................ 199
Kingsley Christian Kemp, Yeonchoo Cho, Vimlesh Chandra,
and Kwang Soo Kim
7.1 Noncovalent Functionalization of Graphene - Theoretical
Background ............................................... 199
7.1.1 Insight into the π-Interaction of Benzene ......... 200
7.1.2 Adsorption on Graphene ............................ 201
7.2 Graphene-Ligand Noncovalent Interactions - Experiment .... 202
7.2.1 Polycyclic Molecules .............................. 202
7.2.2 Biomolecules ...................................... 205
7.2.3 Polymers .......................................... 207
7.2.4 Other Molecules ................................... 210
7.3 Conclusions .............................................. 213
References ............................................... 213
8 Immobilization of Metal and Metal Oxide Nanoparticles
on Graphene .............................................. 219
German Y. Vвez, Armando Encinas, and Mildred Quintana
8.1 Introduction ............................................. 219
8.2 Graphene Production ...................................... 219
8.2.1 Graphene Oxide (GO) ............................... 220
8.2.2 Functionalized Graphene (ƒ-Graphene) .............. 220
8.2.3 Graphene Growth on Metal Surfaces ................. 220
8.2.4 Micromechanical Cleavage of Graphite .............. 221
8.3 Graphene Functionalized with Metal Nanoparticles
(M-NPs) .................................................. 221
8.3.1 GO-Reducing Approach .............................. 221
8.3.1.1 Reduction Assisted by Sonication ......... 222
8.3.2 Anchoring NPs on ƒ-Graphene ....................... 223
8.3.2.1 Controlling Size of NPs .................. 226
8.3.3 Applications of M-NPs/Graphene Nanohybrids ........ 227
8.3.3.1 Optoelectronic Devices ................... 227
8.3.3.2 Applications in Catalysis ................ 229
8.3.3.3 Applications in Biology .................. 232
8.4 Graphene Functionalized with Metal Oxide Nanoparticles ... 233
8.4.1 Lithium Batteries ................................. 233
8.4.2 Optical Properties ................................ 236
8.4.2.1 Water Splitting .......................... 237
8.4.2.2 ƒ-Graphene-POM ........................... 238
8.4.3 Photocatalytic Reduction of GO .................... 238
8.5 Graphene Functionalized with Magnetic NPs ................ 242
8.5.1 Magnetic Properties ............................... 243
8.5.2 Applications of GO-Mag NPs ........................ 246
8.5.2.1 Magnetic Separation of Metals and
Pollutants with GO-Mag NPs ............... 247
8.5.2.2 Biomedical Applications of GO-Mag NPs .... 248
8.6 Conclusions .............................................. 252
References ............................................... 252
9 Functionalization of Graphene by other Carbon
Nanostructures ........................................... 255
Vasilios Georgakilas
9.1 Introduction ............................................. 255
9.2 Graphene-C60 Nanocomposites .............................. 255
9.2.1 Covalent Bonding of C60 on GO ..................... 256
9.2.2 Deposition of C60 on Graphene ..................... 256
9.3 Graphene-CNT Hybrid Nanostructures ....................... 262
9.3.1 Graphene-CNT Composites by Simple Mixing .......... 264
9.3.2 Graphene-CNTs Hybrid Nanostructures by Direct
Development of CNTs on Graphene Surface ........... 272
9.4 Graphene-Carbon Nanospheres .............................. 274
9.5 Graphene-Carbon Nitride Dots Hybrid Nanocomposite ........ 277
9.6 Conclusions .............................................. 279
References ............................................... 280
10 Doping of Graphene by Nitrogen, Boron, and Other
Elements ................................................. 283
Achutharao Govindaraj and C.N.R. Rao
10.1 Introduction ............................................. 283
10.2 Nitrogen-Doped Graphene .................................. 284
10.2.1 DC Arcing ......................................... 284
10.2.2 Heating with Ammonia, Hydrazine, and Other
Reagents .......................................... 287
10.2.3 Chemical Functionalization Route .................. 288
10.2.4 Solvothermal Synthesis ............................ 289
10.2.5 Chemical Vapor Deposition and Pyrolysis ........... 293
10.2.6 Pyrolysis Methods ................................. 300
10.2.7 Other Methods ..................................... 306
10.3 Boron Doping ............................................. 320
10.3.1 Mechanical Exfoliation ............................ 321
10.3.2 Thermal Annealing ................................. 321
10.3.3 Chemical Vapor Deposition ......................... 323
10.3.4 Other Methods ..................................... 326
10.4 BN Doping in Graphene .................................... 329
10.5 Doping with Other Elements ............................... 334
10.6 Properties and Applications .............................. 339
References ............................................... 352
11 Layer-by-Layer Assembly of Graphene-Based Hybrid
Materials ................................................ 359
Antonios Kouloumpis, Panagiota Zygouri, Konstantinos
Dimos, and Dimitrios Gournis
11.1 Introduction ............................................. 359
11.2 LbL Graphene-Based Hybrid Films .......................... 360
11.2.1 Hybrid Thin Films for Electronics ................. 360
11.2.2 Hybrid Thin Films as Sensors ...................... 375
11.2.3 Hybrid Films for Other Applications ............... 383
11.3 Graphene-Based Hybrids through the Langmuir-Blodgett
Approach ................................................. 385
11.3.1 Monolayers of Graphene Oxide ...................... 385
11.3.2 Nanocomposite Films ............................... 389
11.3.3 Applications and Properties of LB Thin Films ...... 390
11.4 Conclusions .............................................. 397
References ............................................... 397
Index ......................................................... 401
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