Graphene chemistry : theoretical perspectives

 Content: Preface xix Acknowledgements xxi  1 Introduction 1  De-en Jiang and Zhongfang Chen   2 Intrinsic Magnetism in Edge-Reconstructed Zigzag Graphene Nanoribbons 9  Zexing Qu and Chungen Liu   2.1 Methodology 10  2.1.1 Effective Valence Bond Model 10  2.1.2 Density Matrix Renormalization Group Method 11  2.1.3 Density Functional Theory Calculations 12  2.2 Polyacene 12  2.3 Polyazulene 14  2.4 Edge-Reconstructed Graphene 17  2.4.1 Energy Gap 17  2.4.2 Frontier Molecular Orbitals 18  2.4.3 Projected Density of States 19  2.4.4 Spin Density in the Triplet State 20  2.5 Conclusion 22  Acknowledgments 23  References 23  3 Understanding Aromaticity of Graphene and Graphene Nanoribbons by the Clar Sextet Rule 29  Dihua Wu, Xingfa Gao, Zhen Zhou, and Zhongfang Chen   3.1 Introduction 29  3.1.1 Aromaticity and Clar Theory 30  3.1.2 Previous Studies of Carbon Nanotubes 33  3.2 Armchair Graphene Nanoribbons 34  3.2.1 The Clar Structure of Armchair Graphene Nanoribbons 34  3.2.2 Aromaticity of Armchair Graphene Nanoribbons and Band Gap Periodicity 37  3.3 Zigzag Graphene Nanoribbons 40  3.3.1 Clar Formulas of Zigzag Graphene Nanoribbons 40  3.3.2 Reactivity of Zigzag Graphene Nanoribbons 40  3.4 Aromaticity of Graphene 42  3.5 Perspectives 44  Acknowledgements 45  References 45  4 Physical Properties of Graphene Nanoribbons: Insights from First-Principles Studies 51  Dana Krepel and Oded Hod   4.1 Introduction 51  4.2 Electronic Properties of Graphene Nanoribbons 53  4.2.1 Zigzag Graphene Nanoribbons 53  4.2.2 Armchair Graphene Nanoribbons 56  4.2.3 Graphene Nanoribbons with Finite Length 58  4.2.4 Surface Chemical Adsorption 60  4.3 Mechanical and Electromechanical Properties of GNRs 63  4.4 Summary 66  Acknowledgements 66  References 66  5 Cutting Graphitic Materials: A Promising Way to Prepare Graphene Nanoribbons 79  Wenhua Zhang and Zhenyu Li   5.1 Introduction 79  5.2 Oxidative Cutting of Graphene Sheets 80  5.2.1 Cutting Mechanisms 80  5.2.2 Controllable Cutting 83  5.3 Unzipping Carbon Nanotubes 85  5.3.1 Unzipping Mechanisms Based on Atomic Oxygen 86  5.3.2 Unzipping Mechanisms Based on Oxygen Pairs 88  5.4 Beyond Oxidative Cutting 91  5.4.1 Metal Nanoparticle Catalyzed Cutting 92  5.4.2 Cutting by Fluorination 95  5.5 Summary 96  References 96  6 Properties of Nanographenes 101  Michael R. Philpott   6.1 Introduction 101  6.2 Synthesis 103  6.3 Computation 103  6.4 Geometry of Zigzag-Edged Hexangulenes 104  6.5 Geometry of Armchair-Edged Hexangulenes 107  6.6 Geometry of Zigzag-Edged Triangulenes 110  6.7 Magnetism of Zigzag-Edged Hexangulenes 112  6.8 Magnetism of Zigzag-Edged Triangulenes 114  6.9 Chimeric Magnetism 115  6.10 Magnetism of Oligocenes, Bisanthene-Homologs, Squares and Rectangles 117  6.10.1 Oligocene Series: C4m+2H2m+4 (na = 1; m = 2, 3, 4 ...) 117  6.10.2 Bisanthene Series: C8m+4H2m+8 (na = 3; m = 2, 3, 4 ...) 119  6.10.3 Square and Rectangular Nano-Graphenes: C8m+4H2m+8 (m = 2, 3, 4 ...) 122  6.11 Concluding Remarks 122  Acknowledgment 123  References 124  7 Porous Graphene and Nanomeshes 129  Yan Jiao, Marlies Hankel, Aijun Du, and Sean C. Smith   7.1 Introduction 129  7.1.1 Graphene-Based Nanomeshes 130  7.1.2 Graphene-Like Polymers 130  7.1.3 Other Relevant Subjects 131  7.1.3.1 Isotope Separation 131  7.1.3.2 Van der Waals Correction for Density Functional Theory 132  7.1.3.3 Potential Energy Surfaces for Hindered Molecular Motions Within the Narrow Pores 133  7.2 Transition State Theory 134  7.2.1 A Brief Introduction of the Idea 134  7.2.2 Evaluating the Partition Functions: The Well-Separated "Reactant" State 136  7.2.3 Evaluating Partition Functions: The Fully Coupled 4D TS Calculation 137  7.2.4 Evaluating Partition Functions: Harmonic Approximation for the TS Derived Directly from Density Functional Theory Calculations 138  7.3 Gas and Isotope Separation 139  7.3.1 Gas Separation and Storage by Porous Graphene 139  7.3.1.1 Porous Graphene for Hydrogen Purification and Storage 139  7.3.1.2 Porous Graphene for Isotope Separation 140  7.3.2 Nitrogen Functionalized Porous Graphene for Hydrogen Purification/Storage and Isotope Separation 140  7.3.2.1 Introduction 140  7.3.2.2 NPG and its Asymmetrically Doped Version for D2/H2 Separation -- A Case Study 141  7.3.3 Graphdiyne for Hydrogen Purification 144  7.4 Conclusion and Perspectives 147  Acknowledgement 147  References 147  8 Graphene-Based Architecture and Assemblies 153  Hongyan Guo, Rui Liu, Xiao Cheng Zeng, and Xiaojun Wu   8.1 Introduction 153  8.2 Fullerene Polymers 154  8.3 Carbon Nanotube Superarchitecture 156  8.4 Graphene Superarchitectures 160  8.5 C60/Carbon Nanotube/Graphene Hybrid Superarchitectures 163  8.5.1 Nanopeapods 163  8.5.2 Carbon Nanobuds 165  8.5.3 Graphene Nanobuds 168  8.5.4 Nanosieves and Nanofunnels 169  8.6 Boron-Nitride Nanotubes and Monolayer Superarchitectures 171  8.7 Conclusion 173  Acknowledgments 173  References 174  9 Doped Graphene: Theory, Synthesis, Characterization, and Applications 183  Florentino Lopez-Uryas, Ruitao Lv, Humberto Terrones, and Mauricio Terrones   9.1 Introduction 183  9.2 Substitutional Doping of Graphene Sheets 184  9.3 Substitutional Doping of Graphene Nanoribbons 194  9.4 Synthesis and Characterization Techniques of Doped Graphene 196  9.5 Applications of Doped Graphene Sheets and Nanoribbons 200  9.6 Future Work 201  Acknowledgments 202  References 202  10 Adsorption of Molecules on Graphene 209  O. Leenaerts B. and Partoens F. M. Peeters   10.1 Introduction 209  10.2 Physisorption versus Chemisorption 210  10.3 General Aspects of Adsorption of Molecules on Graphene 212  10.4 Various Ways of Doping Graphene with Molecules 215  10.4.1 Open-Shell Adsorbates 215  10.4.2 Inert Adsorbates 217  10.4.3 Electrochemical Surface Transfer Doping 220  10.5 Enhancing the Graphene-Molecule Interaction 221  10.5.1 Substitutional Doping 221  10.5.2 Adatoms and Adlayers 222  10.5.3 Edges and Defects 224  10.5.4 External Electric Fields 224  10.5.5 Surface Bending 225  10.6 Conclusion 226  References 226  11 Surface Functionalization of Graphene 233  Maria Peressi   11.1 Introduction 233  11.2 Functionalized Graphene: Properties and Challenges 236  11.3 Theoretical Approach 237  11.4 Interaction of Graphene with Specific Atoms and Functional Groups 238  11.4.1 Interaction with Hydrogen 238  11.4.2 Interaction with Oxygen 240  11.4.3 Interaction with Hydroxyl Groups 241  11.4.4 Interaction with Other Atoms, Molecules, and Functional Groups 245  11.5 Surface Functionalization of Graphene Nanoribbons 247  11.6 Conclusions 248  References 249  12 Mechanisms of Graphene Chemical Vapor Deposition (CVD) Growth 255  Xiuyun Zhang, Qinghong Yuan, Haibo Shu, Feng Ding   12.1 Background 255  12.1.1 Graphene and Defects in Graphene 255  12.1.2 Comparison of Methods of Graphene Synthesis 257  12.1.3 Graphene Chemical Vapor Deposition (CVD) Growth 257  12.1.3.1 The Status of Graphene CVD Growth 257  12.1.3.2 Phenomenological Mechanism 260  12.1.3.3 Challenges in Graphene CVD Growth 260  12.2 The Initial Nucleation Stage of Graphene CVD Growth 261  12.2.1 C Precursors on Catalyst Surfaces 262  12.2.2 The sp C Chain on Catalyst Surfaces 262  12.2.3 The sp2 Graphene Islands 263  12.2.4 The Magic Sized sp2 Carbon Clusters 264  12.2.5 Nucleation of Graphene on Terrace versus Near Step 266  12.3 Continuous Growth of Graphene 271  12.3.1 The Upright Standing Graphene Formation on Catalyst Surfaces 271  12.3.2 Edge Reconstructions on Metal Surfaces 273  12.3.3 Growth Rate of Graphene and Shape Determination 275  12.3.4 Nonlinear Growth of Graphene on Ru and Ir Surfaces 276  12.4 Graphene Orientation Determination in CVD Growth 278  12.5 Summary and Perspectives 280  References 282  13 From Graphene to Graphene Oxide and Back 291  Xingfa Gao, Yuliang Zhao, Zhongfang Chen   13.1 Introduction 291  13.2 From Graphene to Graphene Oxide 292  13.2.1 Modeling Using Cluster Models 292  13.2.1.1 Oxidative Etching of Armchair Edges 292  13.2.1.2 Oxidative Etching of Zigzag Edges 293  13.2.1.3 Linear Oxidative Unzipping 294  13.2.1.4 Spins upon Linear Oxidative Unzipping 296  13.3 Modeling Using PBC Models 297  13.3.1 Oxidative Creation of Vacancy Defects 297  13.3.2 Oxidative Etching of Vacancy Defects 298  13.3.3 Linear Oxidative Unzipping 299  13.3.4 Linear Oxidative Cutting 300  13.4 From Graphene Oxide back to Graphene 302  13.4.1 Modeling Using Cluster Models 302  13.4.1.1 Cluster Models for Graphene Oxide 302  13.4.1.2 Hydrazine De-Epoxidation 302  13.4.1.3 Thermal De-Hydroxylation 307  13.4.1.4 Thermal De-Carbonylation and De-Carboxylation 308  13.4.1.5 Temperature Effect on De-Epoxidation and De-Hydroxylation 309  13.4.1.6 Residual Groups of Graphene Oxide Reduced by Hydrazine and Heat 311  13.4.2 Modeling Using Periodic Boundary Conditions 312  13.4.2.1 Hydrazine De-Epoxidation 312  13.4.2.2 Thermal De-Epoxidation 313  13.5 Concluding Remarks 314  Acknowledgement 314  References 314  14 Electronic Transport in Graphitic Carbon Nanoribbons 319  Eduardo Costa Gir??ao, Liangbo Liang, Jonathan Owens, Eduardo Cruz-Silva, Bobby G. Sumpter, Vincent Meunier   14.1 Introduction 319  14.2 Theoretical Background 320  14.2.1 Electronic Structure 320  14.2.1.1 Density Functional Theory 320  14.2.1.2 Semi-Empirical Methods 320  14.2.2 Electronic Transport at the Nanoscale 322  14.3 From Graphene to Ribbons 324  14.3.1 Graphene 324  14.3.2 Graphene Nanoribbons 325  14.4 Graphene Nanoribbon Synthesis and Processing 329  14.5 Tailoring GNR's Electronic Properties 330  14.5.1 Defect-Based Modifications of the Electronic Properties 331  14.5.1.1 Non-Hexagonal Rings 331  14.5.1.2 Edge and Bulk Disorder 332  14.5.2 Electronic Properties of Chemically Doped Graphene Nanoribbons 332  14.5.2.1 Substitutional Doping of Graphene Nanoribbons 332  14.5.2.2 Chemical Functionalization of Graphene Nanoribbons 333  14.5.3 GNR Assemblies 334  14.5.3.1 Nanowiggles 334  14.5.3.2 Antidots and Junctions 335  14.5.3.3 GNR Rings 335  14.5.3.4 GNR Stacking 336  14.6 Thermoelectric Properties of Graphene-Based Materials 336  14.6.1 Thermoelectricity 336  14.6.2 Thermoelectricity in Carbon 336  14.7 Conclusions 338  Acknowledgements 339  References 339  15 Graphene-Based Materials as Nanocatalysts 347  Fengyu Li and Zhongfang Chen   15.1 Introduction 347  15.2 Electrocatalysts 347  15.2.1 N-Graphene 348  15.2.2 N-Graphene-NP Nanocomposites 350  15.2.3 Non-Pt Metal on the Porphyrin-Like Subunits in Graphene 351  15.2.4 Graphyne 352  15.3 Photocatalysts 353  15.3.1 TiO2-Graphene Nanocomposite 353  15.3.2 Graphitic Carbon Nitrides (g-C3N4) 355  15.4 CO Oxidation 356  15.4.1 Metal-Embedded Graphene 357  15.4.2 Metal-Graphene Oxide 358  15.4.3 Metal-Graphene under Mechanical Strain 359  15.4.4 Metal-Embedded Graphene under an External Electric Field 360  15.4.5 Porphyrin-Like Fe/N/C Nanomaterials 361  15.4.6 Si-Embedded Graphene 361  15.4.7 Experimental Aspects 361  15.5 Others 362  15.5.1 Propene Epoxidation 362  15.5.2 Nitromethane Combustion 362  15.6 Conclusion 363  Acknowledgements 364  References 364  16 Hydrogen Storage in Graphene 371  Yafei Li and Zhongfang Chen   16.1 Introduction 371  16.2 Hydrogen Storage in Molecule Form 373  16.2.1 Hydrogen Storage in Graphene Sheets 373  16.2.2 Hydrogen Storage in Metal Decorated Graphene 374  16.2.2.1 Lithium Decorated Graphene 375  16.2.2.2 Calcium Decorated Graphene 376  16.2.2.3 Transition Metal Decorated Graphene 377  16.2.3 Hydrogen Storage in Graphene Networks 377  16.2.3.1 Covalently Bonded Graphene 378  16.2.4 Notes to Computational Methods 381  16.3 Hydrogen Storage in Atomic Form 382  16.3.1 Graphane 382  16.3.2 Chemical Storage of Hydrogen by Spillover 383  16.4 Conclusion 386  Acknowledgements 386  References 386  17 Linking Theory to Reactivity and Properties of Nanographenes 393  Qun Ye, Zhe Sun, Chunyan Chi, and Jishan Wu   17.1 Introduction 393  17.2 Nanographenes with Only Armchair Edges 394  17.3 Nanographenes with Both Armchair and Zigzag Edges 397  17.3.1 Structure of Rylenes 398  17.3.2 Chemistry at the Armchair Edges of Rylenes 398  17.3.3 Anthenes and Periacenes 402  17.4 Nanographene with Only Zigzag Edges 405  17.4.1 Phenalenyl-Based Open-Shell Systems 406  17.5 Quinoidal Nanographenes 411  17.5.1 Bis(Phenalenyls) 412  17.5.2 Zethrenes 414  17.5.3 Indenofluorenes 417  17.6 Conclusion 417  References 418  18 Graphene Moir'e Supported Metal Clusters for Model Catalysis Studies 425  Bradley F. Habenicht, Ye Xu, and Li Liu   18.1 Introduction 425  18.2 Graphene Moir'e on Ru(0001) 426  18.3 Metal Cluster Formation on g/Ru(0001) 430  18.4 Two-dimensional Au Islands on g/Ru(0001) and its Catalytic Activity 434  18.5 Summary 440  Acknowledgments 441  References 441  Index
 Abstract:             
              What are the chemical aspects of graphene as a novel 2D material and how do they relate to the molecular structure?  This book addresses these important questions from a theoretical and computational standpoint.                 Read more...