HANDBOOK OF LESS-COMMON NANOSTRUCTURES Boris I. Kharisov • Oxana Vasilievna Kharissova Ubaldo Ortiz-Mendez CRC Press Taylor &. Francis Croup Boca Raton London NewYork CRC Press is an imprint of the Taylor & Francis Group, an Informa business Contents Abbreviations xix Preface xxiii Acknowledgments xxv Authors xxvii PART I Introduction to Nanostructures Chapter 1 Methods for Obtaining Nanoparticles and Other Nanostructures 3 1.1 General Remarks on Nanoparticle Fabrication 3 1.2 Examples of Several Important Methods for the Synthesis of Nanoobjects 3 1.2.1 Vapor and Plasma-Based Techniques 3 1.2.2 Electrochemical Methods 10 1.2.3 Microwave, Ultrasonic, and UV-Irradiation Techniques 14 1.2.4 High-Pressure Methods 18 1.2.5 Use of Microfluidic Chips 20 1.2.6 Synthesis in Reversed Micelles 21 1.2.7 Hot-Plate Method 21 1.2.8 Other Chemical Routes 22 1.2.9 Biochemical and Self-Assembly Methods 24 1.3 "Green" Aspects of Nanoparticle Synthesis 26 References 27 Chapter 2 Brief Description of Some Classic Nanostructures 31 2.1 Carbon-Based Nanostructures 31 2.1.1 Carbon Nanotubes 31 2.1.2 Fullerenes 34 2.1.3 Nanodiamonds 35 2.1.4 Graphene and Graphane 37 2.2 Conventional Noncarbon Nanostructures 38 2.2.1 Simple and Core-Shell Nanoparticles 38 2.2.2 Nanometals 42 2.2.3 Gallery of Other Conventional Nanostructures 42 References 48 PART II Less-Common Nanostructures Chapter 3 Simple, Linear ID, 2D, and 3D Nanostructures 57 3.1 Nanolines 57 3.2 Nanopencils 61 ix X Contents 3.3 Nanodumbbells 66 3.4 Nanoshuttles 70 3.5 Nanopeapods 73 3.6 Nanopins 77 3.7 Nanochains 79 3.8 Nanobars 87 3.9 Nanowicks 92 3.10 Nanopillars 93 References 96 Chapter 4 Various Prolonged 3D Nanostructures 107 4.1 Nanoarrows 107 4.2 Nanobones 107 4.3 Nanobottles 107 4.4 Nanobricks Ill 4.5 Nanobowlings and Nanonails 113 4.6 Nanocones 115 4.7 Nanospears 120 4.8 Nanospikes 120 References 123 Chapter 5 Circle and Ball-Type Nanostructures 127 5.1 Nanowheels 127 5.2 Nanoeggs 127 5.3 Nanoballs 129 5.4 Nanospheres 133 5.5 Nanograms 136 5.6 Nanorice 139 References 141 Chapter 6 Nanocage-Type Structures 147 6.1 Nanocages, Nanoboxes, and Nanocubes 147 6.2 Nanocapsules 159 References 164 Chapter 7 "Nanovegetation" World 169 7.1 Nanotrees 169 7.1.1 Nanolrees in General 169 7.1.2 Nanopines 176 7.1.3 Nanopalms 179 7.2 Nanoleaves 181 7.3 Nanolbresis 185 7.4 Nanobushes 188 7.5 Nanomush rooms 190 7.6 Nanollowers 193 Contents x' 7.6.1 Nanofiowers in General 193 7.6.1.1 Elemental Nanofiowers (Metals and Carbon) 193 7.6.1.2 Metal Oxide Nanofiowers 195 7.6.1.3 Nanofiowers of Hydroxides and Oxo-Salts 200 7.6.1.4 Sulfide, Selenide, and Telluride Nanofiowers 201 7.6.1.5 Nitride and Phosphide Nanofiowers 203 7.6.1.6 Nanofiowers Formed by Organic and Coordination Compounds 204 7.6.2 Dandelion-Type Nanofiowers 206 7.7 Nanobouquets 211 7.8 Nanodewdrops 213 7.9 Nanoacorns 215 7.10 Nanomulberry 216 7.11 Broccoli-Like Architectures 217 7.12 Nanograsses 218 7.13 Nanokelps 221 7.14 Nanocorns 222 7.15 Nanocactus 222 7.16 Nanospines 224 7.17 Nanosheafs 226 7.18 Nanoonions 232 References 235 Chapter 8 "Nanoanimal" World 251 8.1 Nanolarvae 251 8.2 Nanoworms 251 8.3 Nanosquamae • 261 8.4 Nanourchins 262 References 277 Chapter 9 "Home"-Like Nanostructures 285 9.1 Nanobowls 285 9.2 Nanocups 294 9.3 Nanoplates 298 9.4 Nanoforks 310 9.5 Nanospoons 313 9.6 Nanobrooms 313 9.7 Nanobrushes 317 9.8 Nanocarpets 328 9.9 Nanocombs 332 9.10 Nanofans 338 9.11 Nanospindles 343 9.12 Nanotroughs 356 9.13 Nanowebs 356 9.14 Other Rare "Home" Nanostructures 363 9.14.1 Nanosombrero 363 9.14.2 Nanobowknot 364 9.14.3 Nanowick 365 xii Contents 9.14.4 Eiffel Tower-Like and Nano-New York Nanostructures 365 9.14.5 Nanoladders 366 References 369 Chapter 10 "Nanotechnical" Structures and Devices 383 10.1 Nanosprings/Nanocoils/Nanospirals 383 10.2 Nanoairplanes, Nanopropellers, and Nanowindmills 390 10.3 Nanoboat 392 10.4 Nanosaws 392 10.5 Nanobridges 395 10.6 Nanolhermomelers 399 10.7 Nanotweezers 402 10.8 Nanocars and Nanotrucks 405 10.9 Nanobalances 408 10.10 Nanogrids 409 10.11 Nanomesh 409 10.12 Nanofoams 412 10.13 Nanojunetions 414 10.14 Nanopaper 416 10.15 Nanobatleries 417 10.16 E-Nose and E-Tongue 419 References 421 Chapter 11 Nanostructures Classified as Polyhedra 431 11.1 Nanolriangles 431 I 1.2 Nano.squares and Nanoreclangles 434 11.3 Nanotetrahedra 436 1 1.4 Nanooctahedra 438 11.5 Nanopyramids 443 1 1.6 Nanoicosahedra 447 11.7 Nanododecahedra 450 1 l.X Nanocuboctahcdra 454 11.9 Nanocnbes 455 11.10 Nanoprisms 464 References 467 Chapter 12 Other Rare Nanoslructures 477 12.1 Nanovolcanocs 477 12.2 Nanosponges 477 12.3 Nanostars 480 12.4 Nanoglass Ceramics 485 12.5 Other Nanoobjecls 486 References 488 Contents xiii PART III Selected Intriguing Topics in Nanotechnology Chapter 13 Coordination and Organometallic Nanomaterials 493 13.1 Introduction 493 13.2 Coordination Nanomaterials and Nanocomposites 493 13.2.1 Nanomaterials Based on Nitrogen-Containing Ligands 493 13.2.2 Nanomaterials Based on N,0-Containing Ligands 496 13.2.3 Nanomaterials Based on Oxygen- and/or Sulfur-Containing Ligands 497 13.3 Organometallic Nanomaterials 499 13.4 Nanomaterials Based on Polymers 499 13.5 Coordination Nanomaterials as Precursors 500 References 501 Chapter 14 Application of Ultrasound for Obtaining Nanostructures and Nanomaterials 507 14.1 Metal/Alloy-Containing Nanostructures 508 14.2 Carbon Nanotubes, Graphene, Diamond, and Fullerenes 511 14.3 Oxide- and Hydroxide-Containing Nanostructures 512 14.4 Metal Salts and Complexes 515 14.5 Polymeric and Macrocyclic Nanostructures/Nanocomposites 519 14.6 Applications in Catalysis and Degradation of Toxic Substances 521 14.7 Applications in Drug Delivery and Tumor Treatments 522 References 524 Chapter 15 Inorganic Non-Carbon Nanotubes 533 15.1 Applications of Inorganic Nanotubes 542 References 542 Chapter 16 Soluble Carbon Nanotubes 545 16.1 Functionalization by the Use of Elemental Metals, Inorganics, and Grignard Reagents 546 16.2 Functionalization of CNTs in Strong Acidic Media and with Oxygen-Containing Moieties 547 16.3 Functionalization with Compounds Containing Alkyl and Aromatic Moieties 549 16.4 Functionalization with Aliphatic and Aromatic Amine(Amido)- Containing Moieties 552 16.5 Functionalization with Sulfur-Containing Moieties 553 16.6 Functionalization with Macrocycles 553 16.7 Functionalization with the Use of Biomolecules 554 16.8 Functionalization with the Use of Polymers or Their Precursors 558 16.9 Special Techniques in the Synthesis and Purification of Soluble CNTs 558 16.9.1 Functionalization Using Irradiation or Radionuclides 558 16.9.2 Other Synthesis Methods 563 xjv Contents 16.10 Study of Reactivity and Physicochemical Properties of Soluble CNTs 564 16.10.1 Special Studies of the Reactivity of Soluble CNTs toward Active Oxygen Sources 564 16.10.2 Other Physicochemical Studies 564 16.11 Main Applications of Soluble CNTs 565 References 567 Chapter 17 Graphene 579 17.1 Structure and Properties 579 17.2 Synthesis 584 17.3 Reactivity 587 17.4 Applications 588 References 590 Chapter 18 Nanodiamonds 597 18.1 Synthesis Methods for Nanodiamonds 597 18.1.1 Precursors 597 18.1.2 Hydrothermal Synthesis 598 18.1.3 Ion Bombardment 598 18.1.4 Laser Bombarding 598 18.1.5 Microwave Plasma Chemical Vapor Deposition Techniques 599 18.1.6 Detonation Methods for ND Fabrication 600 18.1.7 Use of Ultrasound 600 18.1.8 Models for Nanodiamond Synthesis 601 18.1.9 Purification of Nanodiamonds 601 18.2 Techniques Applied to Study Structural and Electronic Properties of Nanodiamonds 602 18.3 Some Physical Properties of Nanodiamonds 603 18.4 Chemical Properties and Functionali/ation of Nanodiamonds 605 18.5 Nanodiamond Films and Composite Materials 609 18.6 Applications 611 References 613 Chapter 19 Fulleropyrrolidines 623 19.1 Porphyrin-Containing Fulleropyrrolidines 623 19.2 Fulleropyrrolidines with Sulfur-Containing Groups 624 19.3 Ferrocene-Containing Fulleropyrrolidines 642 19.4 Fulleropyrrolidine Bis- and Tris-Adducts 644 19.5 Enzyme-Containing Fulleropyrrolidines 648 19.6 Polymer-Containing Fulleropyrrolidines 648 19.7 Other Intriguing Fulleropyrrolidines 649 19.8 C7()-Pyrrolidines 655 19.9 Carbon Nanotubes, Functionalized with Pyrrolidines 655 19.10 Applied Techniques to Study Fulleropyrrolidines 657 19.11 Applications 659 Contents xv Appendix A: Selected Modified Methods of Cycloaddition 662 References 663 Chapter 20 Small Fullerenes C20<„<M and Endohedral Metallofullerenes M@C„ 671 20.1 Stability of Fullerenes Lower than C60 and Their Spectral and Electronic Properties 671 20.2 Structures of Small Fullerenes 673 20.3 Electronic Transport, Mechanism, and Growth Studies 674 20.4 Synthesis, Sorption, and Encapsulation 676 20.5 Metal (or X = H, Hal, C, BN)-Small Fullerene Endohedral Complexes 677 References 678 Chapter 21 Nanomesh and Nanohoneycomb Structures 681 References 693 PART IV Nanometals and Nanoalloys Chapter 22 Nanometals 699 22.1 Nanostructured Metals in General 699 22.1.1 Types of Activated Metals 699 22.1.2 Methods for Metal Activation and Applications of Obtained Active Metals 699 22.1.2.1 Physicochemical Methods 699 22.1.2.2 Chemical Methods 708 22.1.2.3 Biological Synthesis 711 References 711 Chapter 23 Activated Micro- and Nanostructured Rieke Metals 721 23.1 History 721 23.2 General Characteristics of Rieke Methods 723 23.2.1 Precautions 723 23.2.2 Reduction Methods of Synthesis 723 23.2.2.1 Method 1 723 23.2.2.2 Method 2 723 23.2.2.3 Method 3 724 23.2.3 Basic Principles of the Synthesis 724 23.2.4 Advantages and Disadvantages of Method of Synthesis of Rieke Metals 725 23.3