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ÊéÃûFunctionalized Inorganic Fluorides
×÷ÕßALAIN TRESSAUD
Research Director CNRS (Emeritus), ICMCB¨CCNRS,
Bordeaux University, France
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Ò³Êý617
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ISBN: 978-0-470-74050-7 (Cloth
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1 Sol-Gel Synthesis of Nano-Scaled Metal Fluorides ¨C Mechanism and
Properties 1
Erhard Kemnitz, Gudrun Scholz and Stephan Ru¡§diger
1.1 Introduction 1
1.1.1 Sol-Gel Syntheses of Oxides ¨C An Intensively Studied and
Widely Used Process 1
1.1.2 Sol-Gel Syntheses of Metal Fluorides ¨C Overview of
Methods 2
1.2 Fluorolytic Sol-Gel Synthesis 4
1.2.1 Mechanism and Properties 5
1.2.2 Insight into Mechanism by Analytical Methods 8
1.2.3 Exploring Properties 27
1.2.4 Possible Fields of Application 29
References 35
2 Microwave-Assisted Route Towards Fluorinated Nanomaterials 39
Damien Dambournet, Alain Demourgues and Alain Tressaud
2.1 Introduction 39
2.2 Introduction to Microwave Synthesis 40
2.2.1 A Brief History 40
2.2.2 Mechanisms to Generate Heat 40
2.2.3 Advantages of Microwave Synthesis 41
2.2.4 Examples of Microwave Experiments 41
2.3 Preparation of Nanosized Metal Fluorides 42
2.3.1 Aluminium-based Fluoride Materials 42
2.3.2 Microwave-assisted Synthesis of Transition Metal
Oxy-Hydroxy-Fluorides
2.4 Concluding Remarks 64
Acknowledgements 64
References 65
3 High Surface Area Metal Fluorides as Catalysts 69
Erhard Kemnitz and Stephan Ru¡§diger
3.1 Introduction 69
3.2 High Surface Area Aluminium Fluoride as Catalyst 71
3.3 Host-Guest Metal Fluoride Systems 74
3.4 Hydroxy(oxo)fluorides as Bi-acidic Catalysts 78
3.5 Oxidation Catalysis 84
3.6 Metal Fluoride Supported Noble Metal Catalysts 88
3.6.1 Hydrodechlorination of Monochlorodifluoromethane 90
3.6.2 Hydrodechlorination of Dichloroacetic Acid (DCA) 94
3.6.3 Suzuki Coupling 95
References 97
4 Investigation of Surface Acidity using a Range of Probe Molecules 101
Alexandre Vimont, Marco Daturi and John M. Winfield
4.1 Introduction 101
4.1.1 Setting the Scene: Metal Fluorides versus Metal Oxides 102
4.1.2 Some Examples of the Application of FTIR Spectroscopy to
the Study of Surface Acidity in Metal Oxides 103
4.1.3 A Preview 107
4.2 Characterization of Acidity on a Surface: Contrasts with Molecular
Fluorides 108
4.2.1 Molecular Brønsted and Molecular Lewis Acids 108
4.2.2 A Possible Benchmark for Solid Metal Fluoride, Lewis
Acids: Aluminium Chlorofluoride 109
4.3 Experimental Methodology 110
4.3.1 FTIR Spectroscopy 110
4.3.2 Characteristic Reactions and the Detection of Adsorbed
Species by a Radiotracer Method 112
4.4 Experimental Studies of Surface Acidity 117
4.4.1 Using FTIR Spectroscopy 118
4.4.2 Using HCl as a Probe with Detection via [36Cl]-Labelling 123
4.4.3 Metal Fluoride Surfaces that Contain Surface Hydroxyl
Groups: Aluminium Hydroxy Fluorides with the Hexagonal
Tungsten Bronze Structure 129
4.4.4 Possible Geometries for HCl Adsorbed at Metal Fluoride
Surfaces: Relation to Oxide and Oxyfluoride Surfaces 135
4.5 Conclusions 136
References 137ÓйØÄÉÃׯæÊ飡£¡£¡£¡£¡£¡£¡£¡£¡£¡£¡£¡£¡
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