Table Of Content21.9 mm 244 X 170 mm
Explore the theory and applications of superatomic clusters and cluster JE Edited by
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assembled materials nait Purusottam (Puru) Jena and Qiang Sun
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Superatoms: Principles, Synthesis and Readers will also benefit from the inclusion of: ·r
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Applications delivers an insightful and
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exciting exploration of an emerging subfield • A thorough introduction to the rational n
Superatoms
in cluster science, superatomic clusters design of superatoms using electron-
and cluster assembled materials. The book counting rules
presents discussions of the fundamentals of
• Explorations of superhalogens,
superatom chemistry and their application
endohedrally doped superatoms and
in catalysis, energy, materials science, and
assemblies, and magnetic superatoms Principles, Synthesis and Applications
biomedical sciences.
• A practical discussion of atomically
Readers will discover the foundational precise synthesis of chemically
significance of superatoms in science modified superatoms
and technology and learn how they can
• A concise treatment of superatoms as the
serve as the building blocks of tailored
building blocks of 2D materials, as well as
materials, promising to usher in a new era
superatom-based ferroelectrics and cluster-
in materials science. The book covers topics
based materials for energy harvesting
as varied as the thermal and thermoelectric
and storage
properties of cluster-based materials and
clusters for CO activation and conversion,
2 Perfect for academic researchers and
before concluding with an incisive
industrial scientists working in cluster S
discussion of trends and directions likely to
science, energy materials, thermoelectrics, 2D u
dominate the subject of superatoms in the
materials, and CO conversion, Superatoms: p
coming years. 2
Principles, Synthesis and Applications will also e
earn a place in the libraries of interested r
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professionals in chemistry, physics, materials
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science, and nanoscience. o
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Purusottam (Puru) Jena is Distinguished Professor of Physics at Virginia
Commonwealth University, USA. He originated the idea of superatoms
and co-authored the first paper in the field in 1992. He has since published
numerous papers and review articles on superatom clusters as materials
building blocks. He has worked extensively on superhalogens
and superalkalis.
Qiang Sun is Professor at Peking University, China and Visiting Professor
at Virginia Commonwealth University, USA. His research focus is on
nanostructure physics, including 2D materials and clusters, and the physics
of energy materials.
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Cover Image: © American Chemical Society
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Superatoms
Superatoms
Principles, Synthesis and Applications
Edited by
Purusottam (Puru) Jena
Virginia Commonwealth University,
Richmond, VA, USA
Qiang Sun
Peking University,
Beijing, China
This edition first published 2022
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Set in 9.5/12.5pt STIXTwoText by Straive, Pondicherry, India
10 9 8 7 6 5 4 3 2 1
v
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-CountingRules 17
2.2.1 JelliumRule 17
2.2.2 OctetRule 24
2.2.2.1 Superalkalisand Superhalogens 25
2.2.2.2 Superchalcogens 27
2.2.3 18-ElectronRule 29
2.2.4 32-ElectronRule 30
2.2.5 AromaticityRule 31
2.2.6 Wade-MingosRule 34
2.3 StabilizingNegativeIonsUsingMultipleElectron-CountingRules 37
2.3.1 Monoanions 37
2.3.2 Dianions 41
2.3.3 Trianions 43
2.3.4 Tetra-Anionsand Beyond 44
2.4 Conclusions 46
References 46
3 Superhalogens – Enormously Strong Electron Acceptors 53
Piotr Skurski
3.1 SuperhalogenConcept 53
3.1.1 EarlyStudies 53
3.1.2 FurtherResearch(until1999) 55
vi Contents
3.1.3 FirstMeasurementof Gas-PhaseExperimentalElectronDetachment
Energies 57
3.1.4 ThePerformanceof TheoreticalTreatmentsin EstimatingVDEs 58
3.2 AlternativeSuperhalogens 61
3.2.1 NonmetalCentralAtoms 62
3.2.2 NonhalogenLigands 63
3.2.3 BeyondtheMX Formula 66
k+1
3.2.4 Superhalogensas Ligands 68
3.3 PolynuclearSystemsand theSearchfor EAand VDELimits 70
3.3.1 PolynuclearSuperhalogens 71
3.3.2 Searchfor EAand VDELimits 74
3.3.3 MagneticSuperhalogens 76
3.4 Superhalogens’Applicationsata Glance 77
3.5 FinalRemarks 78
Acknowledgements 79
References 79
4 Endohedrally Doped Superatoms and Assemblies 85
Vijay Kumar
4.1 Introduction 85
4.2 MagicClustersand TheirElectronicStability 88
4.3 Discoveryof SiliconFullerenesand OtherPolyhedralForms 89
4.4 EndohedralSuperatomsof Ge,Sn,and Pb 97
4.5 MagneticSuperatoms 101
4.6 EndohedralClustersof Group 11Elements 101
4.7 EndohedralClustersof B,Al,and Ga 104
4.8 HydrogenatedSiliconFullerenes 107
4.9 CompoundSuperatomsand OtherSystems 108
4.10 Assembliesof Superatoms 110
4.11 ConcludingRemarks 117
Acknowledgements 117
References 118
5 Magnetic Superatoms 129
Nicola Gaston
5.1 Introduction 129
5.2 TheArrivalof theMagneticSuperatom 130
5.3 TunableSuperatoms 133
5.4 TheDelocalisationofd-electrons 134
5.5 Prospectsfor NanostructuredMagneticMaterialDesign 137
References 138
6 Atomically Precise Synthesis of Chemically Modified Superatoms 141
Shinjiro Takano and Tatsuya Tsukuda
6.1 Introduction 141
6.1.1 TheConceptof Superatoms 141
Contents vii
6.1.2 ChemicallyModifiedAu/AgSuperatoms 142
6.2 ElectronicStructuresof ChemicallyModifiedSuperatoms 147
6.2.1 SizeEffects 147
6.2.2 CompositionEffects 151
6.2.3 ShapeEffects 153
6.3 AtomicallyPreciseSynthesisof ChemicallyModifiedSuperatoms 160
6.3.1 SizeControl 160
6.3.1.1 Top-downApproach:SizeFocusing 161
6.3.1.2 Bottom-upApproach:SizeConvergence 163
6.3.1.3 TemplateMethod 168
6.3.1.4 KineticControl 168
6.3.2 CompositionControl 169
6.3.2.1 Co-reductionMethod 169
6.3.2.2 AntigalvanicMethod 170
6.3.2.3 Hydride-MediatedTransformation 172
6.3.3 ShapeControl 172
6.3.4 SurfaceControl 174
6.3.4.1 LigandExchange 174
6.3.4.2 Hydrogen-MediatedTransformation 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 FreeElectronModeland theKuboGap 184
7.2.2 ElectronShellStructure 185
7.2.3 Ligand-StabilizedMetalClustersas Superatoms 188
7.2.3.1 CaseStudy:The(Ag (SR) )4−Superatom 188
44 30
7.2.4 Transitionfrom Electronicto AtomicShells 191
7.3 Applications 194
7.3.1 Catalysis 194
7.3.2 Biologicaland MedicalApplications 199
7.3.2.1 CaseStudy:Imagingof Enteroviruses 200
7.3.3 Self-AssemblingClusterMaterialsfrom Superatoms 201
7.3.3.1 CaseStudy:Polymeric1DClusterMaterials 203
7.4 Summaryand Outlook 205
References 206
8 Superatoms as Building Blocks of 2D Materials 209
Zhifeng Liu
8.1 Introduction 209
8.2 Fullerene-assembled2DMaterials 211
8.2.1 C -assembledMonolayer 211
60
8.2.1.1 FreestandingvdWC Monolayer 212
60
viii Contents
8.2.1.2 FreestandingCovalentPolymerizedC Monolayer 213
60
8.2.2 C (n =20,26,32,36)-assembledMonolayers 217
n
8.2.3 FullereneMonolayerson Substrates 220
8.3 Si-basedClusterAssembled2DMaterials 223
8.3.1 V@Si Assembled2DMonolayer 223
12
8.3.1.1 Structureand Stability 223
8.3.1.2 Electronicand FerromagneticProperties 224
8.3.2 OtherTM@Si Assembled2DMonolayers 225
12
8.3.3 Ta@Si Assembled2DMonolayerandThatonSubstrate 226
16
8.4 BinarySemiconductorClusterAssembled2DMaterials 231
8.4.1 Cd Se AssembledSheets 232
6 6
8.4.2 X Y CageClusterAssembledMonolayer 235
12 12
8.5 SimpleandNobleMetalCluster-assembled2DMaterials 236
8.5.1 Mg AssembledMonolayer 236
7
8.5.2 Au andPt AssembledSquareMonolayer 237
9 9
8.6 Zintl-ionCluster-assembled2DMaterials 240
8.6.1 Ge IonClusterMonolayer 240
9
8.6.2 Ti@Au IonClusterMonolayer 241
12
8.7 ChevrelCluster-Assembled2DMaterials 243
8.7.1 Re Se Cluster-basedMonolayer 243
6 8
8.7.2 Co Se Cluster-basedMonolayer 245
6 8
8.8 Summaryand FuturePerspectives 247
References 249
9 Superatom- Based Ferroelectrics 257
Menghao Wu and Puru Jena
9.1 Introduction 257
9.2 OrganicFerroelectrics 258
9.3 HybridOrganic-InorganicPerovskites 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-basedMaterialsfor Moisture-resistantHybridPerovskiteSolar
Cells 283
10.3 Cluster-basedMaterialsfor OptoelectronicDevices 287
10.4 Cluster-basedMaterialsfor Solid-stateElectrolytesin Li-and Na-ion
Batteries 287
10.4.1 Halogen-freeElectrolytes 289
10.4.2 Cluster-basedAntiperovskitesfor Electrolytesin Li-ionBatteries 292
10.4.3 Cluster-basedAntiperovskitesfor Electrolytesin Na-ionBatteries 297
10.5 Cluster-basedMaterialsfor HydrogenStorage 300
