Complex-shaped Metal Nanoparticles Bottom-Up Syntheses and Applications
, by Sau, Tapan K.; Rogach, Andrey L.
- ISBN: 9783527330775 | 3527330771
- Cover: Hardcover
- Copyright: 8/7/2012
Covering all important aspects and techniques of preparation and characterization of nanoparticles with controlled morphology and architecture, this book provides a sound overview, from the basics right up to recent developments. Renowned research scientists from all over the world present our existing knowledge of the field, covering theory and modeling, synthesis, characterization and properties of these novel nanomaterials. By emphasizing the underlying concepts and principles in detail, the book enables researchers to fully recognize and exploit the application potential of complex-shaped nanoparticles, thus laying down the state-of-the art but also inspiring further research.
Tapan K. Sau is an associate professor at the International Institute of Information Technology, Hyderabad, India. After his PhD in chemistry, obtained from the Indian Institute of Technology in Kharagpur, he had worked as a postdoctoral fellow at the University of South Carolina-Columbia and Clarkson University, USA, and as an assistant professor at the Panjab University in Chandigarh, India. From 2007 to 2009 he was an Alexander-von-Humboldt Research Fellow at the Ludwig-Maximilians-Universität, München, Germany. His research interests are in synthesis, spectroscopy and applications of colloidal metal nanocrystals. He has authored over 50 publications including patents and book chapters.
Andrey L. Rogach is chair professor at the Department of Physics and Materials Science of City University of Hong Kong. After his PhD in chemistry, obtained from the Belarusian State University in Minsk, he had worked as a research scientist at the University of Hamburg, Germany (1995-2002), and as a lead staff scientist at the Photonics and Optoelectronics group of the Ludwig-Maximilians-Universität Munich, Germany (2002-2009), where he completed his habilitation in experimental physics. His research is focused on synthesis, assembly, optical spectroscopy and applications of colloidal semiconductor and metal nanocrystals, which has been extensively (over 12,000) times cited.
Andrey L. Rogach is chair professor at the Department of Physics and Materials Science of City University of Hong Kong. After his PhD in chemistry, obtained from the Belarusian State University in Minsk, he had worked as a research scientist at the University of Hamburg, Germany (1995-2002), and as a lead staff scientist at the Photonics and Optoelectronics group of the Ludwig-Maximilians-Universität Munich, Germany (2002-2009), where he completed his habilitation in experimental physics. His research is focused on synthesis, assembly, optical spectroscopy and applications of colloidal semiconductor and metal nanocrystals, which has been extensively (over 12,000) times cited.
Foreword VII
Preface XVII
List of Contributors XIX
Metal Nanoparticles of Complex Morphologies: A General Introduction 1
References 5
1 Colloidal Synthesis of Noble Metal Nanoparticles of Complex Morphologies 7
Tapan K. Sau and Andrey L. Rogach
1.1 Introduction 7
1.2 Classification of Noble Metal Nanoparticles 8
1.3 Synthesis Methodologies 9
1.3.1 Chemical Reduction Method 9
1.3.1.1 Spatially Confined Medium/Template Approach 10
1.3.1.2 Preformed Seed-Mediated Synthesis 15
1.3.1.3 High-Temperature Reduction Method 19
1.3.2 Chemical Transformation Method 19
1.3.2.1 Galvanic Displacement Method 19
1.3.2.2 Etching Method 21
1.3.3 Electrochemical Synthesis 22
1.3.4 Photochemical Method 23
1.3.5 Biosynthesis 24
1.3.6 Postpreparation Separation 25
1.4 Characterization 25
1.5 Thermodynamic–Kinetic Factors and Particle Morphology 29
1.5.1 Nucleation and Growth 29
1.5.1.1 Homogeneous and Heterogeneous Nucleations 29
1.5.1.2 Defects in Seed Crystal 37
1.5.1.3 Growth of Seed Crystal 41
1.5.2 Reaction Parameters 43
1.5.2.1 Reactants and Their Concentrations 43
1.5.2.2 Additives/Impurities 48
1.5.2.3 Solvent, pH, and Temperature 50
1.6 Mechanisms of Morphology Evolution 51
1.6.1 One-Dimensional Nanoparticle Formation 52
1.6.1.1 Nanorod Formation 52
1.6.1.2 Nanobipyramid Formation 57
1.6.2 Two-Dimensional Nanoparticle Formation 57
1.6.3 Three-Dimensional Polyhedral Shape Evolution 62
1.6.4 Epitaxial/Core–Shell/Heterodimer/Overgrowth Mechanism 64
1.6.5 Branched Nanoparticle Formation 67
1.6.6 Hollow/Porous Nanoparticle Formation 70
1.7 Conclusions and Outlook 72
References 73
2 Controlling Morphology in Noble Metal Nanoparticles via Templating Approach 91
Chun-Hua Cui and Shu-Hong Yu
2.1 Introduction 91
2.2 Galvanic Replacement Method 92
2.2.1 Synthesis of Quasi-Zero-Dimensional Nanoparticles 93
2.2.2 Synthesis of One-Dimensional Nanostructures 97
2.3 Hard Template-Directed Method 99
2.3.1 Porous Membrane Template-Directed Method 100
2.3.2 Pattern Template-Directed Method 104
2.4 Soft Template-Directed Method 106
2.4.1 Micelle Template-Directed Synthesis 106
2.4.2 Selective Adsorption-Directed Synthesis 109
2.5 Conclusions and Outlook 112
References 113
3 Shape-Controlled Synthesis of Metal Nanoparticles of High Surface Energy and Their Applications in Electrocatalysis 117
Na Tian, Yu-Hua Wen, Zhi-You Zhou, and Shi-Gang Sun
3.1 Introduction 117
3.2 Fundamentals and Background 119
3.2.1 Thermodynamics of Crystallization: Principles and Rules 119
3.2.1.1 Equilibrium Shape of a Crystal 119
3.2.1.2 Nucleation 120
3.2.1.3 Three-Dimensional Growth of a Crystal on Substrate 122
3.2.1.4 Two-Dimensional Nuclei Theory 124
3.2.2 Correlation of the Shape of Crystal and Its Surface Structure 125
3.3 Progress in Shape-Controlled Synthesis of Metal Nanoparticles of High Surface Energy and Their Applications 127
3.3.1 Electrochemistry Route 128
3.3.1.1 Pt and Pd Nanoparticles 128
3.3.1.2 Fe Nanoparticles 137
3.3.2 Wet Chemistry Route 137
3.3.2.1 Au Nanoparticles 139
3.3.2.2 Pd and Pd–Au Nanoparticles 141
3.3.2.3 Pt Nanoparticles 144
3.4 Theoretical Simulations of Structural Transformation and Stability of Metal Nanoparticles with High Surface Energy 148
3.4.1 Brief Description of Theoretical Calculation Methods 148
3.4.1.1 First-Principles Methods 148
3.4.1.2 Molecular Dynamics Methods 149
3.4.1.3 Predictions and Limitations of Theoretical Calculations 149
3.4.2 Theoretical Study of Metal Nanoparticles of High Surface Energy 150
3.4.2.1 Pt Nanoparticles 151
3.4.2.2 Pd Nanoparticles 153
3.4.2.3 Au Nanoparticles 155
3.4.2.4 Fe Nanoparticles 157
3.5 Conclusions 160
References 162
4 Shape-Controlled Synthesis of Copper Nanoparticles 167
Wen-Yin Ko and Kuan-Jiuh Lin
4.1 Introduction 167
4.1.1 Zero-Dimensional Nanostructures 167
4.1.2 One-Dimensional Nanostructures 168
4.1.3 Two-Dimensional Nanostructures 169
4.1.4 Complex (3D) Nanostructures 170
4.2 Metallic Copper 172
4.2.1 Significance and Challenges 172
4.2.2 Shape Control of Cu Nanoparticles 172
4.3 Electrodeposition Method for Growth of Cu Nanoparticles of Different Shapes 174
4.3.1 Synthesis and Growth Mechanism of Tetrahedral Metallic Cu 174
4.3.1.1 Synthesis 174
4.3.1.2 Growth Mechanism 177
4.3.2 Synthesis of Cu Nanoparticles of Cubic and Multipod Shapes 179
4.4 Conclusions 179
References 181
5 Size- and Shape-Variant Magnetic Metal and Metal Oxide Nanoparticles: Synthesis and Properties 183
Kristen Stojak, Hariharan Srikanth, Pritish Mukherjee, Manh-Huong Phan, and Nguyen T. K. Thanh
5.1 Introduction 183
5.2 Synthesis of Size- and Shape-Variant Ferrite Nanoparticles 184
5.2.1 Thermal Decomposition 184
5.2.1.1 Surface Functionalization 185
5.2.1.2 Size and Shape Variance 187
5.2.2 Chemical Coprecipitation 189
5.2.3 Solvothermal Technique 191
5.2.4 Microemulsion Technique 192
5.3 Other Magnetic Nanoparticles: Synthesis, Size Variance, and Shape Variance 194
5.4 Magnetism in Ferrite Nanoparticles 196
5.4.1 Crystal Structure and Spin Configuration 196
5.4.2 Critical Size and Superparamagnetism 197
5.4.3 Size-Dependent Magnetic Properties 198
5.4.3.1 Static Magnetic Properties 198
5.4.3.2 Dynamic Magnetic Properties 203
5.4.4 Shape-Dependent Magnetic Properties 205
5.5 Magnetic Nanoparticles for Biomedical Applications 207
5.5.1 Targeted Drug Delivery 207
5.5.2 Hyperthermia 208
5.5.3 MRI Contrast Enhancement 208
5.6 Concluding Remarks and Future Directions 210
References 212
6 Structural Aspects of Anisotropic Metal Nanoparticle Growth: Experiment and Theory 215
Tulio C.R. Rocha, Herbert Winnischofer, and Daniela Zanchet
6.1 Introduction 215
6.2 Atomic Packing on Metal NPs 217
6.3 Structural Aspects in the Anisotropic Growth: The Silver Halide Model 221
6.4 Experimental Requisites to Produce Anisotropic NPs 226
6.5 Concluding Remarks 234
References 235
7 Colloids, Nanocrystals, and Surface Nanostructures of Uniform Size and Shape: Modeling of Nucleation and Growth in Solution Synthesis 239
Vladimir Privman
7.1 Introduction 239
7.2 Burst Nucleation Model for Nanoparticle Growth 242
7.3 Colloid Synthesis by Fast Growth 247
7.4 Improved Models for Two-Stage Colloid Growth 251
7.5 Particle Shape Selection in Solution Synthesis 254
7.6 Applications for Control of Morphology in Surface Structure Formation 261
7.7 Summary 263
References 264
8 Modeling Nanomorphology in Noble Metal Particles: Thermodynamic Cartography 269
Amanda S. Barnard
8.1 Introduction 269
8.2 Ab Initio Simulation of Small Gold Nanoclusters 271
8.3 Ab Initio Simulation of Gold Nanoparticles 272
8.4 Thermodynamic Cartography 276
8.4.1 Size-Dependent Melting 281
8.4.2 Mapping the Morphology of Nanogold 282
8.5 Gold Nanorods and Dimensional Anisotropy 285
8.5.1 Preferred Shape and Termination Geometry 286
8.5.2 Aspect Ratio and Dependence on Temperature 289
8.5.3 Twinning in Gold Nanorods 291
8.6 Comparison with Platinum and Inclusion of Surface Defects 294
8.7 Conclusions 298
References 300
9 Platinum and Palladium Nanocrystals: Soft Chemistry Approach to Shape Control from Individual Particles to Their Self-Assembled Superlattices 305
Christophe Petit, Caroline Salzemann, and Arnaud Demortiere
9.1 Introduction 305
9.2 Influence of the Chemical Environment on the NC Shape 306
9.2.1 How the Capping Agents Tune the Shape and the Size of Metal NCs: A Comparison of Two-Liquid Synthesis Methods 306
9.2.1.1 Effect of the Capping Agent on the Shape of Platinum NCs 308
9.2.1.2 Effect of the Capping Agent on the Size of Platinum NCs 310
9.2.1.3 Effect of the Capping Agent on the Size and Shape of Palladium NCs Made in Reverse Micelles 312
9.2.2 Role of the Strength of the Capping Agent–Metal Bond 315
9.2.3 Role of the Gas Dissolved in a Solvent 318
9.3 Synthesis of Platinum Nanocubes 321
9.4 Supercrystals Self-Assembled from Nonspherical NCs 323
9.5 Conclusions 333
References 335
10 Ordered and Nonordered Porous Superstructures from Metal Nanoparticles 339
Anne-Kristin Herrmann, Nadja C. Bigall, Lehui Lu, and Alexander Eychmüller
10.1 Introduction 339
10.2 Metallic Porous Superstructures 341
10.2.1 Ordered Porous Metallic Nanostructures 341
10.2.1.1 Preparation 342
10.2.1.2 Applications in Catalysis and as SERS Substrates 345
10.2.2 Nonordered Porous Superstructures on Biotemplates 347
10.2.3 Freestanding Nonordered Porous Superstructures 351
10.3 Summary and Outlook 355
References 355
11 Localized Surface Plasmons of Multifaceted Metal Nanoparticles 361
Cecilia Noguez and Ana L. González
11.1 Introduction 361
11.2 Light Absorption and Scattering by Metal NPs 363
11.2.1 Light Absorption Mechanisms 366
11.2.2 Surface Plasmon Resonances 367
11.2.3 Dielectric Function of Metal NPs 368
11.3 Spectral Representation Formalism 371
11.3.1 General Trends of SPRs of Metal NPs in Vacuum 373
11.3.2 General Trends of SPRs of Metal NPs in a Host Medium 374
11.4 Spherical and Spheroidal NPs 375
11.4.1 Nanospheres 375
11.4.2 Nanospheroids 378
11.4.3 Multishell NPs 379
11.5 Discrete Dipole Approximation 380
11.6 SPRs in Multifaceted Morphologies 383
11.6.1 Cubic Morphology 383
11.6.2 Decahedral Morphology 385
11.6.3 Elongated NPs with Complex Morphologies 388
11.7 Summary 390
References 391
12 Fluorophore–Metal Nanoparticle Interactions and Their Applications in Biosensing 395
Thomas A. Klar and Jochen Feldmann
12.1 Introduction 395
12.2 Fluorescence Decay Rates in the Vicinity of Metal Nanostructures 395
12.2.1 Physical Concept 395
12.2.2 Oligonucleotide Sensing 401
12.2.3 Protein Sensors 404
12.2.3.1 Unspecific Protein Sensors 405
12.2.3.2 Immunoassays 405
12.2.3.3 Aptamer-Based Sensing 407
12.2.4 Sensing Small Molecules (Haptens) 409
12.2.5 Ion Sensing 411
12.2.6 Fluorescence Enhancement Sensors 411
12.3 Shaping of Fluorescence Spectra by Metallic Nanostructures 412
12.4 Shaping of Extinction Spectra by Strong Coupling 417
12.4.1 Physical Concept 417
12.4.2 Biosensor Applications 419
12.5 Specific Issues on the Interaction of Fluorophores with Complex-Shaped Metallic Nanoparticles 419
12.5.1 Spectral Tunability 420
12.5.2 Encoding 421
References 422
13 Surface-Enhanced Raman Scattering Using Complex-Shaped Metal Nanostructures 429
Frank Jäckel and Jochen Feldmann
13.1 Introduction 429
13.2 Basics 430
13.2.1 Raman Scattering 430
13.2.2 Surface-Enhanced Raman Scattering 431
13.3 Modeling 435
13.4 SERS Substrate Preparation 437
13.5 Fundamental Studies 439
13.5.1 Morphology Dependence 439
13.5.2 SERS with Single Particles 441
13.5.3 Single-Molecule SERS 443
13.5.4 Enhancement Mechanism 444
13.6 Applications 447
13.7 Conclusions and Outlook 448
References 449
14 Photothermal Effect of Plasmonic Nanoparticles and Related Bioapplications 455
Alexander O. Govorov, Zhiyuan Fan, and Alexander B. Neiman
14.1 Introduction 455
14.2 Theory of the Photothermal Effect for Single Nanoparticles and for Nanoparticle Clusters 458
14.2.1 Plasmonic Model 459
14.2.2 Mie Theory for a Single Spherical Nanoparticle 460
14.2.3 Effective Medium Approaches for the Dielectric Function and for the Thermal Conductivity of a Nanoparticle Cluster 462
14.2.4 Optically Generated Temperature 462
14.2.5 Mie Theory for Nanoparticles and Clusters 463
14.2.5.1 Small Spherical Nanoparticles and Clusters 463
14.2.5.2 Large Clusters 464
14.3 Physical Examples and Applications 467
14.3.1 Melting of the Matrix 467
14.3.2 Heating from a Collection of Nanoparticles: Heat Accumulation Effect 468
14.4 Application to Biological Cells: Control of Voltage Cellular Dynamics with Photothermal Actuation 471
14.5 Summary 474
References 474
15 Metal Nanoparticles in Biomedical Applications 477
Jun Hui Soh and Zhiqiang Gao
15.1 Introduction 477
15.2 Biosensing and Diagnostics 478
15.2.1 Localized Surface Plasmon Resonance Detection 479
15.2.2 Colorimetric Detection 482
15.2.3 Surface-Enhanced Raman Scattering Detection 487
15.2.4 Electrochemical and Electrical Detection 491
15.2.5 Magnetic Resonance-Based Detection 495
15.3 Therapeutic Applications 498
15.3.1 Applications in Tissue Engineering 499
15.3.2 Application in Drug Delivery 501
15.3.3 Cancer Therapy 504
15.4 Bioimaging 508
15.5 Conclusions and Outlook 513
References 515
16 Anisotropic Nanoparticles for Efficient Thermoelectric Devices 521
Nguyen T. Mai, Derrick Mott, and Shinya Maenosono
16.1 Introduction 521
16.2 Chemical Synthesis Methods of Complex-Shaped TE NPs 523
16.2.1 Thermal Decomposition Method 523
16.2.2 Hydrothermal Method 523
16.2.3 Solvent-Based Reduction Method 523
16.2.4 Important Factors in the Synthesis Toward Complex-Shaped TE NPs 524
16.3 One-Dimensional TE NPs 525
16.3.1 Pb–(Te, Se) System 525
16.3.2 (Bi, Sb)–(Te, Se) System 528
16.4 Two-Dimensional TE NPs 531
16.4.1 Pb–(Te, Se) System 531
16.4.2 (Bi, Sb)–(Te, Se) System 531
16.5 Other Complex-Shaped TE NPs 535
16.6 Properties of Complex-Shaped TE NPs 538
16.7 Conclusions and Future Outlook 540
References 541
Index 545
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