Explore the theory and applications of superatomic clusters and cluster assembled materials
Superatoms: Principles, Synthesis and Applications delivers an insightful and exciting exploration of an emerging subfield in cluster science, superatomic clusters and cluster assembled materials. The book presents discussions of the fundamentals of superatom chemistry and their application in catalysis, energy, materials science, and biomedical sciences.
Readers will discover the foundational significance of superatoms in science and technology and learn how they can serve as the building blocks of tailored materials, promising to usher in a new era in materials science. The book covers topics as varied as the thermal and thermoelectric properties of cluster-based materials and clusters for CO2 activation and conversion, before concluding with an incisive discussion of trends and directions likely to dominate the subject of superatoms in the coming years.
Readers will also benefit from the inclusion of:
- A thorough introduction to the rational design of superatoms using electron-counting rules
- Explorations of superhalogens, endohedrally doped superatoms and assemblies, and magnetic superatoms
- A practical discussion of atomically precise synthesis of chemically modified superatoms
- A concise treatment of superatoms as the building blocks of 2D materials, as well as superatom-based ferroelectrics and cluster-based materials for energy harvesting and storage
Perfect for academic researchers and industrial scientists working in cluster science, energy materials, thermoelectrics, 2D materials, and CO2 conversion, Superatoms: Principles, Synthesis and Applications will also earn a place in the libraries of interested professionals in chemistry, physics, materials science, and nanoscience.
Table of Contents
Preface xi
List of Contributors xiii
1 Introduction 1
Puru Jena and Qiang Sun
References 7
2 Rational Design of Superatoms Using Electron-Counting Rules 15
Puru Jena, Hong Fang, and Qiang Sun
2.1 Introduction 15
2.2 Electron-Counting Rules 17
2.2.1 Jellium Rule 17
2.2.2 Octet Rule 24
2.2.2.1 Superalkalis and Superhalogens 25
2.2.2.2 Superchalcogens 27
2.2.3 18-Electron Rule 29
2.2.4 32-Electron Rule 30
2.2.5 Aromaticity Rule 31
2.2.6 Wade-Mingos Rule 34
2.3 Stabilizing Negative Ions Using Multiple Electron-Counting Rules 37
2.3.1 Monoanions 37
2.3.2 Dianions 41
2.3.3 Trianions 43
2.3.4 Tetra-Anions and Beyond 44
2.4 Conclusions 46
References 46
3 Superhalogens - Enormously Strong Electron Acceptors 53
Piotr Skurski
3.1 Superhalogen Concept 53
3.1.1 Early Studies 53
3.1.2 Further Research (until 1999) 55
3.1.3 First Measurement of Gas-Phase Experimental Electron Detachment Energies 57
3.1.4 The Performance of Theoretical Treatments in Estimating VDEs 58
3.2 Alternative Superhalogens 61
3.2.1 Nonmetal Central Atoms 62
3.2.2 Nonhalogen Ligands 63
3.2.3 Beyond the MXk+1 Formula 66
3.2.4 Superhalogens as Ligands 68
3.3 Polynuclear Systems and the Search for EA and VDE Limits 70
3.3.1 Polynuclear Superhalogens 71
3.3.2 Search for EA and VDE Limits 74
3.3.3 Magnetic Superhalogens 76
3.4 Superhalogens’ Applications at a Glance 77
3.5 Final Remarks 78
Acknowledgements 79
References 79
4 Endohedrally Doped Superatoms and Assemblies 85
Vijay Kumar
4.1 Introduction 85
4.2 Magic Clusters and Their Electronic Stability 88
4.3 Discovery of Silicon Fullerenes and Other Polyhedral Forms 89
4.4 Endohedral Superatoms of Ge, Sn, and Pb 97
4.5 Magnetic Superatoms 101
4.6 Endohedral Clusters of Group 11 Elements 101
4.7 Endohedral Clusters of B, Al, and Ga 104
4.8 Hydrogenated Silicon Fullerenes 107
4.9 Compound Superatoms and Other Systems 108
4.10 Assemblies of Superatoms 110
4.11 Concluding Remarks 117
Acknowledgements 117
References 118
5 Magnetic Superatoms 129
Nicola Gaston
5.1 Introduction 129
5.2 The Arrival of the Magnetic Superatom 130
5.3 Tunable Superatoms 133
5.4 The Delocalisation of d-electrons 134
5.5 Prospects for Nanostructured Magnetic Material Design 137
References 138
6 Atomically Precise Synthesis of Chemically Modified Superatoms 141
Shinjiro Takano and Tatsuya Tsukuda
6.1 Introduction 141
6.1.1 The Concept of Superatoms 141
6.1.2 Chemically Modified Au/Ag Superatoms 142
6.2 Electronic Structures of Chemically Modified Superatoms 147
6.2.1 Size Effects 147
6.2.2 Composition Effects 151
6.2.3 Shape Effects 153
6.3 Atomically Precise Synthesis of Chemically Modified Superatoms 160
6.3.1 Size Control 160
6.3.1.1 Top-down Approach: Size Focusing 161
6.3.1.2 Bottom-up Approach: Size Convergence 163
6.3.1.3 Template Method 168
6.3.1.4 Kinetic Control 168
6.3.2 Composition Control 169
6.3.2.1 Co-reduction Method 169
6.3.2.2 Antigalvanic Method 170
6.3.2.3 Hydride-Mediated Transformation 172
6.3.3 Shape Control 172
6.3.4 Surface Control 174
6.3.4.1 Ligand Exchange 174
6.3.4.2 Hydrogen-Mediated Transformation 176
6.4 Summary 176
References 177
7 Atomically Precise Noble Metals in the Nanoscale, Stabilized by Ligands 183
Hannu Häkkinen
7.1 Introduction 183
7.2 Fundamentals 184
7.2.1 Free Electron Model and the Kubo Gap 184
7.2.2 Electron Shell Structure 185
7.2.3 Ligand-Stabilized Metal Clusters as Superatoms 188
7.2.3.1 Case Study: The (Ag44(SR)30)4- Superatom 188
7.2.4 Transition from Electronic to Atomic Shells 191
7.3 Applications 194
7.3.1 Catalysis 194
7.3.2 Biological and Medical Applications 199
7.3.2.1 Case Study: Imaging of Enteroviruses 200
7.3.3 Self-Assembling Cluster Materials from Superatoms 201
7.3.3.1 Case Study: Polymeric 1D Cluster Materials 203
7.4 Summary and Outlook 205
References 206
8 Superatoms as Building Blocks of 2D Materials 209
Zhifeng Liu
8.1 Introduction 209
8.2 Fullerene-Assembled 2D Materials 211
8.2.1 C60-assembled Monolayer 211
8.2.1.1 Freestanding vdWC60 Monolayer 212
8.2.1.2 Freestanding Covalent Polymerized C60 Monolayer 213
8.2.2 Cn (n = 20, 26, 32, 36)-assembled Monolayers 217
8.2.3 Fullerene Monolayers on Substrates 220
8.3 Si-Based Cluster Assembled 2D Materials 223
8.3.1 V@Si12 Assembled 2D Monolayer 223
8.3.1.1 Structure and Stability 223
8.3.1.2 Electronic and Ferromagnetic Properties 224
8.3.2 Other TM@Si12 Assembled 2D Monolayers 225
8.3.3 Ta@Si16 Assembled 2D Monolayer and That on Substrate 226
8.4 Binary Semiconductor Cluster Assembled 2D Materials 231
8.4.1 Cd6Se6 Assembled Sheets 232
8.4.2 X12Y12 Cage Cluster Assembled Monolayer 235
8.5 Simple and Noble Metal Cluster-assembled 2D Materials 236
8.5.1 Mg7 Assembled Monolayer 236
8.5.2 Au9 and Pt9 Assembled Square Monolayer 237
8.6 Zintl-ion Cluster-assembled 2D Materials 240
8.6.1 Ge9 Ion Cluster Monolayer 240
8.6.2 Ti@Au12 Ion Cluster Monolayer 241
8.7 Chevrel Cluster-Assembled 2D Materials 243
8.7.1 Re6Se8 Cluster-based Monolayer 243
8.7.2 Co6Se8 Cluster-based Monolayer 245
8.8 Summary and Future Perspectives 247
References 249
9 Superatom-Based Ferroelectrics 257
Menghao Wu and Puru Jena
9.1 Introduction 257
9.2 Organic Ferroelectrics 258
9.3 Hybrid Organic-Inorganic Perovskites 262
9.4 Supersalts 266
9.5 Conclusion 270
References 270
10 Cluster-based Materials for Energy Harvesting and Storage 277
Puru Jena, Hong Fang, and Qiang Sun
10.1 Introduction 277
10.2 Cluster-Based Materials for Moisture-resistant Hybrid Perovskite Solar Cells 283
10.3 Cluster-Based Materials for Optoelectronic Devices 287
10.4 Cluster-Based Materials for Solid-state Electrolytes in Li-and Na-ion Batteries 287
10.4.1 Halogen-free Electrolytes 289
10.4.2 Cluster-based Antiperovskites for Electrolytes in Li-ion Batteries 292
10.4.3 Cluster-based Antiperovskites for Electrolytes in Na-ion Batteries 297
10.5 Cluster-Based Materials for Hydrogen Storage 300
10.5.1 Hydrogen Interaction Mechanism 300
10.5.2 Intermediate States 303
10.5.3 Catalysts for Lowering the Dehydrogenation Temperature 305
10.6 Clusters Promoting Unusual Reactions 305
10.6.1 Zn in +III Oxidation State 307
10.6.2 Covalent Binding of Noble Gas Atoms 307
10.7 Conclusions 310
References 311
11 Thermal and Thermoelectric Properties of Cluster-based Materials 317
Tingwei Li, Qiang Sun, and Puru Jena
11.1 Introduction 317
11.2 Basic Theory 318
11.2.1 Thermoelectric Effect 318
11.2.2 Material Performance 319
11.2.3 Tuning ZT by Carrier Concentration 320
11.2.4 Tuning ZT by Electronic Structure 321
11.2.4.1 Carrier Effective Mass, m* 321
11.2.4.2 Carrier Mobility 322
11.3 Low Lattice Thermal Conductivity of Cluster-based Materials 323
11.3.1 Crystal Complexity of Cluster-based Materials 324
11.3.2 Chemical Bond Hierarchy in Cluster-based Materials 325
11.3.3 Structural Disorder in Cluster-based Materials 326
11.3.4 Orientational Disorder in Cluster-based Materials 327
11.3.4.1 Co6E8(PEt3)6 and [Co6E8(PEt3)6][C60]2 328
11.3.4.2 Fullerene Assembled Films 329
11.4 Thermoelectric Properties of some Selected Cluster-based Materials 330
11.4.1 Mo6 and Mo9 Cluster-based Selenides 330
11.4.1.1 Crystal Structures 330
11.4.1.2 Electronic Structures 331
11.4.1.3 Thermal Properties 332
11.4.1.4 Thermoelectric Figure of Merit ZT 334
11.4.2 Boron-based Cluster Materials 334
11.4.2.1 Crystal Structures 335
11.4.2.2 Thermoelectric Properties 335
11.4.3 Silver-based Cluster Materials 338
11.5 Conclusion 341
References 342
12 Clusters for CO2 Activation and Conversion 349
Haoming Shen, Qiang Sun, and Puru Jena
12.1 Introduction 349
12.2 Superalkali Catalysts 351
12.2.1 Li-based Superalkalis for CO2 Activation 351
12.2.2 Supported or Embedded Superalkalis for CO2 Capture 358
12.3 Al-Based Clusters for CO2 Capture 359
12.4 Ligand-Protected Au25 Clusters for CO2 Conversion 361
12.5 M@Ag24 Clusters for CO2 Conversion 364
12.6 Cu-Based Clusters for CO2 Conversion 367
12.7 Metal Encapsulated Silicon Nanocages for CO2 Conversion 370
12.8 Summary and Perspectives 370
References 372
13 Conclusions and Future Outlook 375
Puru Jena and Qiang Sun
Index 379
