24小时热门版块排行榜

返回列表

Pureland

木虫之王 (知名作家)

MN-EPI: 22
应助: 1516 (讲师)
贵宾: 0.015
金币: 135503
散金: 3502
红花: 723
帖子: 6479
在线: 2896.4小时
虫号: 693216
注册: 2009-01-16
专业: 应用高分子化学与物理

[交流] 2014年新著——石墨烯化学（英文版）已有6人参与

De-en Jiang, Zhongfang Chen, "Graphene Chemistry: Theoretical Perspectives"
English | ISBN: 1119942128 | 2014 | 484 pages | PDF | 84 MB

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. Graphene Chemistry: Theoretical Perspectives presents recent exciting developments to correlate graphene’s properties and functions to its structure through state–of–the–art computational studies. This book focuses on the chemistry aspect of the structure–property relationship for many fascinating derivatives of graphene; various properties such as electronic structure, magnetism, and chemical reactivity, as well as potential applications in energy storage, catalysis, and nanoelectronics are covered. The book also includes two chapters with significant experimental portions, demonstrating how deep insights can be obtained by joint experimental and theoretical efforts. Topics covered include: Graphene ribbons: Edges, magnetism, preparation from unzipping, and electronic transport Nanographenes: Properties, reactivity, and synthesis Clar sextet rule in nanographene and graphene nanoribbons Porous graphene, nanomeshes, and graphene–based architecture and assemblies Doped graphene: Theory, synthesis, characterization and applications Mechanisms of graphene growth in chemical vapor deposition Surface adsorption and functionalization of graphene Conversion between graphene and graphene oxide Applications in gas separation, hydrogen storage, and catalysis Graphene Chemistry: Theoretical Perspectives provides a useful overview for computational and theoretical chemists who are active in this field and those who have not studied graphene before. It is also a valuable resource for experimentalist scientists working on graphene and related materials, who will benefit from many concepts and properties discussed here.
Contents
List of Contributors
                        xv 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 + 2 H2m + 4 (na = 1; m = 2, 3, 4 . . . )             117
6.10.2 Bisanthene Series: C8m + 4 H2m + 8 (na = 3; m = 2, 3, 4 . . . )             119
6.10.3 Square and Rectangular Nano-Graphenes: C8m + 4 H2m + 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 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 Lo′ pez-Ur′ıas, 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. Partoens, and 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, and 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, and 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 Gira˜ o, Liangbo Liang, Jonathan Owens, Eduardo Cruz-Silva, Bobby G. Sumpter, and
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-C3 N4 )                                                 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 Moire′ Supported Metal Clusters for Model Catalytic Studies       425
Bradley F. Habenicht, Ye Xu, and Li Liu

18.1 Introduction
                  425
18.2 Graphene Moire′ 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
                              447

English | ISBN: 1119942128 | 2014 | 484 pages | PDF | 84 MB

回复此楼