Inorganic Nanosheets and Nanosheet-Based Materials: Fundamentals and Applications of Two-Dimensional Systems

Preface......Page 6
Contents......Page 8
Fundamental Aspects of Inorganic Nanosheets......Page 10
 1.1 Introduction—What Are Inorganic Nanosheets?......Page 11
 1.2 Inorganic Nanosheets and Chemistry of Nanomaterials......Page 13
 1.3 Intercalation Chemistry and Nanosheets......Page 14
  1.4.2 Progress in Intercalation Chemistry......Page 16
  1.4.3 Development of Nanosheet Chemistry......Page 19
 1.5 Classification and Preparation of Exfoliated Nanosheets......Page 20
  1.5.1 Nanosheets of Ion-Exchangeable Layered Solids......Page 21
  1.5.2 Nanosheets of Non-ion-Exchangeable Layered Solids......Page 22
 1.6 Nanosheet-Based Nanostructures......Page 25
 1.7 Application of the Nanosheets to Advanced Materials......Page 27
  1.7.1 Applications of Single Nanosheets......Page 28
  1.7.2 Applications of Two-Dimensional Nanospaces......Page 29
  1.7.3 Applications Based on Thinness of the Nanosheets......Page 30
  1.7.4 Applications Based on the High Surface Area of the Nanosheets......Page 32
  1.7.5 Applications of Colloidally Dispersed State of the Nanosheets......Page 33
 1.8 Outlook......Page 34
 References......Page 35
 2.1 Introduction......Page 40
  2.2.1 General......Page 41
  2.2.2 Smectites......Page 42
  2.3.1 Casting......Page 45
  2.3.2 Spin Coating......Page 46
  2.3.3 Layer-by-Layer (LbL) Assembling......Page 47
  2.3.4 Langmuir–Blodgett (LB) and Langmuir–Schaefer (LS) Technique......Page 48
  2.4.1 Alkylammonium Cations......Page 50
  2.4.2 Cationic Organic Dyes......Page 51
  2.4.3 Cationic Inorganic Dyes......Page 56
 2.5 Organization of Clay Mineral Layers......Page 57
 References......Page 59
 3.1 Introduction......Page 61
  3.2.1 Cation-Exchangeable Layered Solids......Page 62
  3.2.2 Exfoliation......Page 63
  3.3.1 Osmotic Swelling......Page 64
  3.3.3 Effects of the Exfoliating Reagent and Temperature......Page 66
  3.3.4 Nanosheet Size......Page 69
  3.4.1 Titanates......Page 70
  3.4.2 Niobates and Tantalates......Page 72
  3.4.3 Perovskite-Type Titanates, Niobates, and Tantalates......Page 74
   3.4.4.1 Manganates......Page 75
   3.4.4.3 Ruthenates......Page 76
  3.4.5 Silicates......Page 77
  3.4.6 Metal Phosphates......Page 78
  3.4.7 Other Cation-Exchangeable and Related Materials......Page 80
  3.5.1 Layered Double Hydroxides (LDHs)......Page 81
  3.5.2 Layered Hydroxide Salts......Page 84
 3.6 Assembly of the Nanosheets......Page 85
   3.6.1.1 Porous Solids......Page 86
   3.6.1.2 Cast Films......Page 87
   3.6.1.3 Transformation to Nanoscrolls......Page 90
   3.6.2.1 Electrostatic LbL Assemblies......Page 91
   3.6.2.3 Nanosheet Monolayer Films as Substrates for Crystal Growth......Page 93
  3.6.3 Assemblies of the Nanosheets in the Colloidal State......Page 95
 3.7 Summary and Outlook......Page 97
 References......Page 98
  4.1.1 Bulk Form of Graphene and Related Layered Materials......Page 107
  4.1.2 Graphene Isolation and the Following Researches......Page 108
  4.2.1 Structure and Mechanical Properties......Page 109
  4.2.2 Electronic State and Electrical Properties......Page 111
  4.3.1 Mechanical Exfoliation......Page 113
  4.3.2 Chemical Exfoliation......Page 114
  4.3.3 Decomposition of SiC......Page 115
   4.3.4.1 Precipitation......Page 116
   4.3.4.2 Surface Reaction......Page 117
   4.3.4.3 Other Methods Related to CVD......Page 118
 4.4 Functionalization......Page 119
  4.4.1 Covalent Functionalization......Page 120
  4.4.2 Non-covalent Functionalization......Page 121
  4.4.3 Heteroatom Doping......Page 122
  4.4.4 Graphene Nanoribbon and Graphene Quantum Dot......Page 124
 4.5 Related Materials......Page 125
  4.5.1 Silicene, Germanene, Stannene, Phosphorene......Page 126
  4.5.2 Hexagonal Boron Nitride and Transition Metal Dichalcogenide......Page 128
  4.5.3 Heterostructures......Page 129
 References......Page 131
5 Chalcogenide Nanosheets: Optical Signatures of Many-Body Effects and Electronic Band Structure......Page 139
 5.1 Introduction......Page 140
  5.2.1 Crystal Structure......Page 142
  5.2.2 Preparation......Page 143
  5.2.3 Energy Band Structure......Page 144
  5.2.4 Optical Signatures of Band Structure......Page 146
  5.2.5 Optical Signatures of Excitons......Page 150
 5.3 Other Layered Chalcogenides......Page 156
  5.3.1 Sn-Based Monochalcogenides......Page 157
  5.3.2 Ga-Based Monochalocogenides......Page 158
  5.3.3 Re-Based Dichalcogenides......Page 159
  5.3.4 Trichalcogenides......Page 160
 References......Page 161
 6.1 Introduction......Page 169
 6.2 Electrostatic Interactions......Page 170
 6.3 Other Driving Forces for the Intercalation......Page 180
 6.4 Guest–Guest Interactions......Page 183
 6.5 Summary and Future Perspectives......Page 187
 References......Page 188
 7.1 Introduction......Page 193
  7.2.1 Clay; A Hybrid of Silicate Layers with Water......Page 194
  7.2.2 Alloys; Good Examples of Ideal Hybrids......Page 195
 7.3 Intercalation Reaction of Sheet Silicates with Organic Compounds......Page 196
 7.4 Nylon-Clay Mineral Hybrids (NCH) by Toyota R&D Lab......Page 198
 7.5 Exfoliation Process for Clay-Polymer Nanocomposites (CPNs)......Page 200
 7.6 Polymer Processing and Optimization of Properties for CPNs......Page 201
 7.7 Progress in the Development of New Hybrids......Page 203
 References......Page 205
 8.1 Introduction......Page 207
 8.2 Classical Theory of Colloids Applicable for Nanosheets......Page 208
 8.3 Liquid Crystal Phases of Nanosheet Colloids......Page 210
  8.3.1 Layered Phosphates......Page 212
  8.3.2 Layered Transition Metal Oxides......Page 216
  8.3.3 Layered Clay Minerals......Page 219
  8.3.4 Graphene and Grapheme Oxide......Page 222
  8.3.5 Other Related Materials......Page 224
  8.4.1 Onsager Theory......Page 225
  8.4.2 Other Theories......Page 228
 8.5 Orientational Control Under External Fields......Page 229
   8.5.1.1 Electric Birefringence......Page 230
   8.5.1.2 Electrorheological Behavior......Page 231
   8.5.1.3 Electric Alignment of the Nanosheets in the LC State......Page 233
  8.5.2 Orientation Under Magnetic Fields......Page 235
  8.5.3 Orientation by Shear Forces......Page 237
  8.5.4 Hierarchical Macroscopic Structures of Nanosheet LCs Under Dual External Fields......Page 238
  8.5.5 Orientation at the Interfaces......Page 239
  8.5.6 Immobilization of Aligned Nanosheet Structures......Page 241
  8.6.1 Phase Separation in Multicomponent Colloids......Page 244
  8.6.2 Phase Separation of Binary Nanosheet Colloids......Page 246
  8.6.3 Photochemical Applications of Niobate–Clay Binary Nanosheet Colloids......Page 249
 8.7 Rheological Properties......Page 251
  8.7.1 Theory and Models......Page 252
  8.7.2 Colloid Structure and Rheology......Page 254
  8.7.3 Control of the Rheological Properties of the Nanosheet Colloids......Page 257
 8.8 Summary and Outlook......Page 259
 References......Page 260
Functions and Applications of the Inorganic Nanosheets......Page 267
 9.1 Introduction......Page 268
  9.2.1 Cation Exchange......Page 269
  9.2.2 Anion Exchange......Page 272
  9.3.1 Carbon Dioxides......Page 273
  9.4.1 Organic Modification with Ionic Species......Page 277
  9.4.2 Pillared-Layered Materials......Page 279
  9.4.3 Grafting......Page 284
  9.4.4 Inorganic Modification......Page 285
  9.4.6 Stimuli Responsive Adsorbents......Page 287
 9.5 Adsorption of Polymers......Page 291
 9.6 Adsorption of Nanoparticles......Page 293
 9.7 Morphosynthesis of Layered Solids for System Design......Page 294
 9.8 Summary and Future Perspectives......Page 299
 References......Page 300
 10.1 Introduction......Page 307
 10.2 Sensing Gas Molecules......Page 308
 10.3 Sensing Dissolved Molecules......Page 313
 References......Page 315
 11.2 Requirements as Electrode Materials......Page 319
 11.3 Fabrication of Thin-Film Electrodes......Page 320
 11.4 Pseudo-capacitive Properties of Exfoliated Oxide Nanosheet Electrodes......Page 321
  11.4.1 Pseudo-capacitive Properties of RuO2 Nanosheet Electrodes......Page 322
  11.4.2 Pseudo-capacitive Properties of MnOx and CoOx Nanosheet Electrodes......Page 326
 11.5 Oxide Nanosheets for Rechargeable Batteries......Page 328
 References......Page 330
 12.1 Introduction......Page 334
  12.2.1 Structure of GO......Page 335
  12.2.2 Electric Conduction of GO......Page 337
  12.2.3 Proton Conduction of GO......Page 338
  12.3.1 Fuel Cells......Page 340
  12.3.2 Supercapacitors......Page 342
  12.3.3 Other Devices......Page 344
 References......Page 345
 13.1 Introduction......Page 350
 13.2 Electronic Properties of 2D Oxide Nanosheets......Page 351
 13.3 Electronic Devices Based on 2D Oxide Nanosheets......Page 354
 13.4 Conclusion and Outlook......Page 357
 References......Page 358
 14.1 Introduction......Page 360
 14.2 Conversion of Photoenergy into Chemical Energy......Page 361
 14.3 Conversion of Photoenergy into Electrical Energy......Page 362
 14.4 Conversion of Photoenergy into Mechanical Energy......Page 363
  14.5.1 Theory of Förster Resonance Energy Transfer......Page 364
  14.5.2 Nonphotofunctional Nanosheets as FRET Reaction Fields for Organic Guests......Page 365
  14.5.3 Photofunctional Nanosheets as FRET Donor/Acceptors......Page 368
 References......Page 371
 15.1 Introduction......Page 375
 15.2 Properties of Nanosheet-Based Hybrids......Page 377
 15.3 Photofunctional Applications of Nanosheet-Based Hybrids......Page 378
  15.3.1 Photocatalytic Degradation of Toxic Organic Pollutants......Page 379
  15.3.2 Photocatalytic Water Splitting and CO2 Reduction......Page 384
  15.3.3 Solar Cells......Page 388
  15.3.4 Photoluminescence......Page 389
 15.4 Conclusions and Outlook......Page 391
 References......Page 393
 16.1 Introduction......Page 397
 16.2 Charge Transfer Promoters......Page 398
 16.3 Molecular Recognition......Page 402
 16.4 Others......Page 406
 References......Page 408
 17.1 Band Structures of Nanosheets......Page 410
 17.2 Nanosheet pn-Junction......Page 411
 References......Page 417
18 Hybrids with Functional Dyes......Page 420
 18.1 Introduction......Page 421
  18.1.1 Basic Features of the Hybrids with Photoactive Dyes......Page 422
 18.2 Surface and Structural Parameters of Inorganic Nanolayered Compounds......Page 423
  18.3.1 Colloids......Page 424
  18.3.2 Surface Modification of Inorganic Nanoparticles......Page 425
  18.3.3 Hybrids with Neutral, Insoluble, and Hydrophobic Dyes......Page 426
  18.3.4 Sol–Gel Processes and Covalently Attached Dye Molecules......Page 428
  18.3.5 Thin Solid Films......Page 429
  18.4.1 Metachromasy and Dye Molecular Aggregation......Page 432
  18.4.2 Molecular Aggregation and Photoactivity......Page 434
  18.4.3 Effect of Layer Charge......Page 435
  18.4.4 J-Aggregates......Page 436
  18.4.5 Reduction of Dye Molecular Aggregation by Using Surfactants......Page 437
  18.4.6 Molecular Aggregation in Other Systems......Page 438
  18.5.1 Optical Anisotropy and Dye Molecular Orientation......Page 439
  18.5.2 Structural Changes and Photochromic Properties......Page 441
  18.5.4 Resonance Energy Transfer......Page 443
  18.5.5 Dye Reactions and Photosensitization......Page 445
  18.6.1 Sensors......Page 447
  18.6.2 Hybrids with Natural Dyes......Page 448
  18.6.3 Hybrids Used in Biology, Medicine, and Agriculture......Page 449
  18.6.4 Polymer Nanocomposites and Other Applications......Page 450
 Acknowledgments......Page 451
 References......Page 452
 19.1 Nanosheets and Nanosheet-Based Materials for Optoelectronic Applications......Page 467
 19.2 Fabrication of Low Light-Scattering Nanosheet Materials......Page 468
   19.2.1.1 Langmuir–Blodgett-Based Technique......Page 469
   19.2.1.2 Filtration-Based Technique......Page 470
  19.2.2 Index Matching by Composition......Page 472
 19.3 Nanosheet-Based Optical Material......Page 474
  19.3.2 Buildup and Nonlinear Optical Property of Multi-quantum Well Structure......Page 475
  19.3.4 Nanosheet–Organic Compound Hybrid Materials for Wavelength Conversion......Page 476
  19.3.5 Nanosheet–Organic Compound Hybrids with Efficient Two-Photon Absorption Properties......Page 477
 References......Page 479
 20.1 Introduction......Page 482
 20.2 Structural Studies on the Chiral Crystal of Kaolinite......Page 483
  20.3.1 Spectroscopic Studies on the Adsorption of Metal Complexes by a Smectite Clay......Page 484
  20.3.2 Theoretical Studies of Racemic Adsorption and Its Significance for Chiral Recognition......Page 488
  20.4.2 Clay Column Chromatography for Optical Resolution......Page 489
   20.4.3.1 Asymmetric Syntheses......Page 491
   20.4.3.2 Chiral Ru(II) Metal Complexes on a Clay Surface......Page 492
   20.4.3.3 Ir(III) Complexes Applied as a Luminescent Modifier on a Clay Surface......Page 494
  20.4.4 Construction of Clay Nano-Sheet Films for Gas Sensing......Page 495
 20.5 Summary and Future Development......Page 496
 References......Page 497
 21.1 Introduction......Page 500
 21.3 Application of PNCs......Page 504
  21.4.1 PP/Clay Nanocomposites......Page 505
  21.4.2 PE/Clay Nanocomposites......Page 509
  21.4.3 Polyvinyl Chloride (PVC)/Nanoclay Nanocomposites......Page 510
   21.4.5.1 Polyethylene Terephthalate (PET)/Clay Nanocomposites......Page 511
   21.4.5.2 Ethyl(vinyl alcohol) (EVOH)/Nanoclay Nanocomposites......Page 512
  21.4.6 Nylon/Clay Nanocomposites......Page 514
  21.4.8 Acetal/Clay Nanocomposites......Page 515
  21.4.10 Biopolymer/Clay Nanocomposites......Page 516
 21.5 Future of Clay-Based Polymer Nanocomposites......Page 517
 References......Page 518
 22.1 Accumulation of Man-Made Materials in the Environment......Page 521
 22.2 Man-Made Materials that Are Replacing Natural Materials that Were Used by Humans for Millennia: Transformations of Immense Proportions on a Global Scale......Page 522
 22.3 Molecules to Materials to Devices (MMD): How Nature Does It?......Page 524
 22.4 Basics of Protein Chemical Modification as a General Strategy for Biological Material Synthesis by Rational Methods......Page 526
 22.5 Synthesis, Characterization, and Evaluation of Protein Fluorescent Nanoparticles......Page 529
  22.5.1 Nanoparticles of Controlled Size from Bovine Serum Albumin......Page 531
  22.5.2 Characterization of Nanoparticles and Labeling with FITC......Page 532
  22.5.3 Nanoparticle Synthesis from Other Proteins and Enzymes......Page 534
  22.5.4 Live Cell Imaging with Protein Fluorescent Nanoparticles......Page 535
  22.5.6 Comparisons of GlowDots with Quantum Dots......Page 537
 References......Page 539