Polyoxometalate Chemistry

1st Edition, Volume 69 - February 17, 2017
Editors: Rudi van Eldik, Lee Cronin
Language: English
Hardback ISBN:
9 7 8 - 0 - 1 2 - 8 1 1 1 0 5 - 5
eBook ISBN:
9 7 8 - 0 - 1 2 - 8 1 1 1 0 6 - 2

Polyoxometalate Chemistry continues a long-running series that describes recent advances in scientific research, in particular, in the field of inorganic chemistry. Several h… Read more

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Polyoxometalate Chemistry continues a long-running series that describes recent advances in scientific research, in particular, in the field of inorganic chemistry. Several highly regarded experts, mostly from academia, contribute on specific topics. The current issue focuses on recent advances in the development and application of polyoxometalate complexes in areas such as solution chemistry, self-organization, solar fuels, non-aqueous chemistry, spintronics, nanoscience and catalysis.

Chapter One: Exploring Self-Assembly and the Self-Organization of Nanoscale Inorganic Polyoxometalate Clusters

Abstract
1 Introduction to Polyoxometalate Chemistry
2 From Serendipity to Directed Assembly
3 Synthetic Methodologies
4 POM-Based Supramolecular Structures
5 From Self-Assembled to Self-Organizing Cluster Systems
6 Conclusions

Chapter Two: Supramolecular Structures Formation of Polyoxometalates in Solution Driven by Counterion–Macroion Interaction

Abstract
1 Introduction
2 Self-Assembly of POM Macroions Into “Blackberries”
3 Counterion-Mediated Self-Assembly of POM Macroions
4 The Kinetic Properties and Lag Phase of POM Assembly
5 POM–Counterion Ion Pairing in Solution
6 Dynamic of Alkali Counterions in POM Solution
7 Cation Transportation Through Blackberry “Membrane”
8 Selective Permeability of Uranyl Peroxide Nanocage
9 Self-Recognition Behaviors During Their Self-Assembly
10 Simulation Studies on Self-Assembly of POM Macroions
11 Conclusions
Acknowledgments

Chapter Three: Electron Transfer–Oxygen Transfer Reactions and Beyond With Polyoxometalates

Abstract
1 Mechanisms for the Aerobic Oxidation of Organic Compounds
2 The H₅PV₂Mo₁₀O₄₀ Polyoxometalate and Electron Transfer Oxidations
3 The First Example of Electron Transfer–Oxygen Transfer Catalyzed by H₅PV₂Mo₁₀O₄₀
4 Oxidation of Sulfides
5 Oxidation of Primary and Vicinal Alcohols
6 Oxidation of via Activation of C–H Bonds Revisited
7 Insertion of Oxygen Into a Carbon–Metal Bond
8 The Structure of H₅PV₂Mo₁₀O₄₀ During the Catalytic Reaction
9 Conclusions
Acknowledgments

Chapter Four: Oxygen–Isotope Exchange and Metastable Dissociation in Oxides

Abstract
1 Introduction
2 Broad Reactivity Trends for Dissolving Materials and Glasses
3 Acid–Base Chemistry and Reactivity in Niobates
4 The Transition to a Partly Detached Structure in MAl₁₂ Cations
5 Metastable Intermediates
6 Conclusions
Acknowledgments

Chapter Five: Polyoxometalate Multielectron Catalysts in Solar Fuel Production

Abstract
1 Introduction
2 Definitions
3 Water Splitting Overview
4 Water Oxidation Catalysts
5 Water Reduction Catalysts
6 Immobilization of Polyoxometalate WOCs
7 Assessment of Catalytic Activity
8 Stability in POM Catalytic Systems
9 Conclusions
Acknowledgments

Chapter Six: [Co₉(H₂O)₆(OH)₃(HPO₄)₂(PW₉O₃₄)₃]¹⁶⁻: A Highly Efficient Catalyst for Water Oxidation

Abstract
1 Introduction
2 Homogeneous Electrocatalytic Water Oxidation Activity of Co₉
3 Characterization of the Catalytic Activity of Co₉ With NaClO
4 Stability and Solution Speciation Under Catalytic Water Oxidation Conditions
5 Heterogeneous WOC With Modified Co₉/Carbon Paste Electrodes
6 Conclusions

Chapter Seven: Polyoxometalate-Functionalized Nanocarbon Materials for Energy Conversion, Energy Storage, and Sensor Systems

Abstract
1 Introduction
2 Synthesis of the POM/Nanocarbon Composites
3 Applications of the POM/Nanocarbon Composites
4 Conclusions

Chapter Eight: Design of Magnetic Polyoxometalates for Molecular Spintronics and as Spin Qubits

Abstract
1 Introduction
2 Relevant Precedent Studies of POMs in Molecular Magnetism
3 Relevance of POMs in Molecular Spintronics
4 Recent Advances on the Use of POMs for Quantum Computing
5 Concluding Remarks
Acknowledgments

Chapter Nine: Perspectives for Polyoxometalates in Single-Molecule Electronics and Spintronics

Abstract
1 Introduction
2 Basics of Molecular Spin Electronics
3 Material Requirements for Molecular Spintronics
4 Advantages of Magnetic Polyoxometalates
5 Polyoxometalates in Redox-Based Resistive Switching
6 Conclusions
Acknowledgments

Chapter Ten: Nonaqueous Polyoxometalate Synthesis for Systematic Studies of Hydrolysis, Protonation, and Reduction

Abstract
1 Introduction
2 Synthesis of Lindqvist-Type Heterometalates
3 Synthesis of Keggin-Type Heterometalates
4 Protonolysis of M–OR Bonds and Condensation
5 Synthesis and Reactivity of Chlorido {ClMW₅} Lindqvist Anions
6 Studies of {MW₅} Lindqvist Anion Protonation
7 Ligand Behavior of [(μ-O)(TiW₅O₁₈)₂]⁶⁻
8 Reductive Transformations
9 Summary
Acknowledgments

Rudi van Eldik

Rudi van Eldik was born in Amsterdam (The Netherlands) in 1945 and grew up in Johannesburg (South Africa). He received his chemistry education and DSc degree at the former Potchefstroom University (SA), followed by post-doctoral work at the State University of New York at Buffalo (USA) and the University of Frankfurt (Germany). After completing his Habilitation in Physical Chemistry at the University of Frankfurt in 1982, he was appointed as Professor of Inorganic Chemistry at the Private University of Witten/Herdecke in 1987. In 1994 he became Professor of Inorganic and Analytical Chemistry at the University of Erlangen-Nürnberg, from where he retired in 2010. At present he is Professor of Inorganic Chemistry at the Jagiellonian University in Krakow, Poland, and Visiting Professor of Inorganic Chemistry at the N. Copernicus University in Torun, Poland. His research interests cover the elucidation of inorganic and bioinorganic reaction mechanisms, with special emphasis on the application of high pressure thermodynamic and kinetic techniques. In recent years his research team also focused on the application of low-temperature rapid-scan techniques to identify and study reactive intermediates in catalytic cycles, and on mechanistic studies in ionic liquids. He is Editor of the series Advances in Inorganic Chemistry since 2003. He serves on the Editorial Boards of several chemistry journals. He is the author of over 880 research papers and review articles in international journals and supervised 80 PhD students. He has received honorary doctoral degrees from the former Potchefstroom University, SA (1997), Kragujevac University, Serbia (2006), Jagiellonian University, Krakow, Poland (2010), University of Pretoria, SA (2010), and Ivanovo State University of Chemistry and Technology, Russia (2012). He has developed a promotion activity for chemistry and related experimental sciences in the form of chemistry edutainment presentations during the period 1995-2010. In 2009 he was awarded the Federal Cross of Merit (‘Bundesverdienstkreuz’) by the Federal President of Germany, and the Inorganic Mechanisms Award by the Royal Society of Chemistry (London). His hobbies include music, hiking, jogging, cycling and motor-biking. He is the father of two and grandfather of four children.

Affiliations and expertise

University of Erlangen-Nurnberg, Germany; Professor of Inorganic Chemistry, Jagiellonian University in Krakow, Poland

Lee Cronin

Affiliations and expertise

University of Glasgow, Glasgow, UK

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Polyoxometalate Chemistry

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Rudi van Eldik

Lee Cronin