Superatoms: Principles, Synthesis and Applications PDF
Preview Superatoms: Principles, Synthesis and Applications
21.9 mm 244 X 170 mm Explore the theory and applications of superatomic clusters and cluster JE Edited by ed assembled materials nait Purusottam (Puru) Jena and Qiang Sun o Superatoms: Principles, Synthesis and Readers will also benefit from the inclusion of: ·r Ss Applications delivers an insightful and u 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 a professionals in chemistry, physics, materials t science, and nanoscience. o m s 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. Cover Design: Wiley Cover Image: © American Chemical Society www.wiley.com 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 © 2022 John Wiley & Sons Ltd All rights reserved. No part of this publication may be reproduced, stored in a retrieval system, or transmitted, in any form or by any means, electronic, mechanical, photocopying, recording or otherwise, except as permitted by law. Advice on how to obtain permission to reuse material from this title is available at http://www.wiley.com/go/permissions. The right of Purusottam (Puru) Jena and Qiang Sun to be identified as the authors of the editorial material in this work has been asserted in accordance with law. Registered Offices John Wiley & Sons, Inc., 111 River Street, Hoboken, NJ 07030, USA John Wiley & Sons, Ltd., The Atrium, Southern Gate, Chichester, West Sussex, PO19 8SQ, UK Editorial Office The Atrium, Southern Gate, Chichester, West Sussex, PO19 8SQ, UK For details of our global editorial offices, customer services, and more information about Wiley products visit us at www.wiley.com. Wiley also publishes its books in a variety of electronic formats and by print- on- demand. Some content that appears in standard print versions of this book may not be available in other formats. Limit of Liability/Disclaimer of Warranty In view of ongoing research, equipment modifications, changes in governmental regulations, and the constant flow of information relating to the use of experimental reagents, equipment, and devices, the reader is urged to review and evaluate the information provided in the package insert or instructions for each chemical, piece of equipment, reagent, or device for, among other things, any changes in the instructions or indication of usage and for added warnings and precautions. While the publisher and authors have used their best efforts in preparing this work, they make no representations or warranties with respect to the accuracy or completeness of the contents of this work and specifically disclaim all warranties, including without limitation any implied warranties of merchantability or fitness for a particular purpose. No warranty may be created or extended by sales representatives, written sales materials, or promotional statements for this work. The fact that an organization, website, or product is referred to in this work as a citation and/or potential source of further information does not mean that the publisher and authors endorse the information or services the organization, website, or product may provide or recommendations it may make. This work is sold with the understanding that the publisher is not engaged in rendering professional services. The advice and strategies contained herein may not be suitable for your situation. You should consult with a specialist where appropriate. Further, readers should be aware that websites listed in this work may have changed or disappeared between when this work was written and when it is read. Neither the publisher nor authors shall be liable for any loss of profit or any other commercial damages, including but not limited to special, incidental, consequential, or other damages. Library of Congress Cataloging- in- Publication data applied for: HB ISBN: 9781119619529 Cover Design: Wiley Cover Image: © American Chemical Society 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
The list of books you might like
