Nanomaterials Preparation by Thermolysis of Metal Chelates (eBook)

Prof. Igor E. Uflyand, Dr. Sci. (Chem.) is the Head of Chemistry Department, Southern Federal University, Rostov-on-Don, Russia. He was born in 1956. He received his Ph.D. in 1981 after graduating from Rostov State University, Department of Physical and Colloid Chemistry. I.E. Uflyand received his Doctorate in Chemistry in 1996 from the Rostov State University. He received the title of Professor in 1996. The scope of his scientific interest is coordination and organometallic chemistry, metal chelate monomers and polymers on their base, catalysis by metal complexes, and nanomaterials. Prof. Uflyand is the author of over 150 scientific papers, 10 patents and four books. Gulzhian I. Dzhardimalieva, Dr, Sci. (Chem.) is the Head of Laboratory, Institute of Problems of Chemical Physics Russian Academy of Sciences, Chernogolovka, Moscow region, and Professor of Department of Applied Mechanics, Moscow Aviation Institute (National Research University), Russia. She received her Ph.D. in 1987 from the Institute of Chemical Physics, RAS in Moscow, and her Doctorate in Chemistry in 2010 from the Institute of Problems of Chemical Physics RAS in Chernogolovka. The scope of her scientific interest is metal-containing monomers and polymers on their base, macromolecular metal carboxylates, coordination polymers, and metallopolymer nanocomposites. She has been invited researcher of Auburn University, USA (2001), Warsaw Technology University, Poland (2002, 2011), Bremen University, Germany (2007), Turin University, Italy (2008), and Institute of composite and biomedical materials CNR, Neapol, Italy (2011, 2013). G.I. Dzhardimalieva was an issue editor of the Journal of Inorganic and Organometallic Polymers and Materials (2016, vol. 26, 6) and a member of the Organizing Committee of the International Conference on Macromolecular Metal Complexes MMC-17 (Tokyo, Japan, August, 2017). She is the author of about 150 scientific papers and 5 monographs.

Preface 6
Contents 8
About the Authors 12
Abbreviations 14
1 General Introduction 20
References 34
2 General Characteristics of the Methods of Thermolysis of Metal Compounds 43
2.1 Thermogravimetric Methods 45
2.1.1 Volumetric Methods 51
2.1.2 Linear Pyrolysis Method 55
2.1.3 Thermolysis Induced by High-Energy Radiation 57
2.1.4 Spray Pyrolysis 58
2.1.5 Chemical Vapor Deposition 62
2.1.6 Kinetic Approaches to the Investigation of Thermolysis of Metal Chelates 67
References 81
3 Thermolysis of Low Molecular Weight Metal Chelates 88
3.1 Metal Carboxylates 88
3.1.1 Metal Formates 90
3.1.2 Metal Acetates 93
3.1.3 Metal Oleates 101
3.1.4 Other Metal Monocarboxylates 112
3.1.5 Metal Oxalates 114
3.1.6 Metal Malonates 118
3.1.7 Metal Succinates 121
3.1.8 Metal Phthalates 122
3.2 Metal Acetylacetonates 124
3.2.1 Nickel Acetylacetonate 124
3.2.2 Aluminum Acetylacetonate 125
3.2.3 Copper Acetylacetonate 126
3.2.4 Cobalt Acetylacetonates 128
3.2.5 Zirconium Acetylacetonate 128
3.2.6 Zinc Acetylacetonate 129
3.2.7 Manganese Acetylacetonate 129
3.2.8 Iron Acetylacetonates 131
3.2.9 Cadmium Acetylacetonate 134
3.2.10 Gold Acetylacetonate 134
3.2.11 Platinum Acetylacetonate 137
3.2.12 Palladium Acetylacetonate 138
3.2.13 Ruthenium Acetylacetonates 139
3.2.14 Indium Acetylacetonate 142
3.3 Metal Chelates Based on Other O,O-Donor Ligands 144
3.3.1 Metal Salicylaldehydates 144
3.3.2 Metal 2-Hydroxyacetophenone 147
3.3.3 Metal 2-Hydroxy-1-Naphthaldehydates 148
3.3.4 Metal Glycerolates 150
3.3.5 Metal Cupferronates 150
3.4 Metal Chelates with N,N-Containing Ligands 151
3.4.1 2,2?-Diamino-5,5?-Dimethyl-4,4?-Bithiazole 152
3.4.2 2,2?-Bipyridine 155
3.4.3 Ethylenediamine and Related Ligands 157
3.4.4 1,10-Phenanthroline and Related Ligands 162
3.4.5 Aminoiminates 166
3.4.6 Pyridine Carboxamides 168
3.4.7 Dimethylglyoxime 168
3.5 Azomethine Metal Chelates 168
3.5.1 Metal Chelates Based on 2-Hydroxyacetophenonimine 169
3.5.2 Metal Chelates of Salicylaldimine Type 170
3.5.3 Salen Chelates 173
3.5.4 Salphen Chelates 178
3.5.5 Metal Chelates Based on Tridentate Azomethine Ligands 180
3.5.6 Metal Chelates with Other Azomethine Ligands 180
3.6 Metal Chelates with N,O-Donor Ligands 184
3.7 Metal Chelates with S,O-Donor Ligands 188
3.7.1 Metal Chelates with N,S (Se, Te)-Donor Ligands 192
3.8 Metal Dichalcogenides 197
3.9 Mixed-Ligand Metal Chelates 219
3.10 Polynuclear Metal Chelates 225
3.11 Multicomponent Precursors Based on Metal Chelates 234
References 251
4 Thermolysis of Polymeric Metal Chelates 263
4.1 Synthesis of Carbon Nanomaterials 266
4.2 Preparation of Metal and Metal Oxide–Carbon Nanocomposites 271
4.3 Preparation of Metal Oxide Nanomaterials 290
4.3.1 Transition Metal Oxides 292
4.3.1.1 Zinc Oxide 292
4.3.1.2 Cobalt Oxides 301
4.3.1.3 Iron Oxides 304
4.3.1.4 Titanium Oxides 307
4.3.1.5 Manganese Oxides 310
4.3.1.6 Cadmium Oxide 311
4.3.1.7 Copper(II) Oxide 314
4.3.1.8 Nickel Oxide 316
4.3.1.9 Chromium Oxide 317
4.3.1.10 Palladium Oxide 317
4.3.2 Main Group Metal Oxides 317
4.3.3 Rare Earth Metal Oxides 325
4.3.4 Preparation of Metal Nanomaterials 326
4.4 Preparation of Mixed-Oxide Nanocomposites 331
4.5 Preparation of Metal Sulfide Nanomaterials 339
4.6 Preparation of Polymer-Derived Non-oxide Nanocomposites 341
References 352
5 The Conjugate Thermolysis—Thermal Polymerization of Metal Chelate Monomers and Thermolysis of Polymers Formed In Situ 367
5.1 General Characteristics of Metal Chelate Monomers Used in Conjugated Thermolysis 368
5.2 Thermal Polymerization of Metal Chelate Monomers 380
5.3 Overall Scheme of Conjugated Thermolysis 386
5.3.1 Dehydration 389
5.3.2 Polymerization 392
5.3.3 Decarboxylation 394
5.4 The Composition of Gaseous and Solid Products of Conjugated Thermolysis 403
5.4.1 Gaseous and Condensed Products 403
5.4.2 The Composition of the Solid-Phase Products 406
5.5 Kinetic Schemes and Reactions of Thermal Transformation of Metal Chelate Monomers 422
5.5.1 General Kinetic Scheme and Ways of Decomposition of Metal Chelate Monomers 423
5.5.2 Transformation Pathways of Cobalt Acrylate 425
References 434
6 Thermolysis of Metal Chelates in Polymer Matrices 440
References 468
7 Application of Nanomaterials Prepared by Thermolysis of Metal Chelates 474
7.1 Fuel Cells 474
7.2 Supercapacitors 502
7.3 Lithium-Ion Batteries 512
7.4 Nanocatalysis 522
7.4.1 Catalytic Hydrogenation 523
7.4.2 Oxidation Reactions 528
7.4.3 Ullmann-Type Amination Coupling Reaction 531
7.4.4 Suzuki–Miyaura Coupling Reaction 532
7.4.5 Fischer–Tropsch Synthesis 533
7.4.6 Enantioselective Catalysis 533
7.4.7 Photocatalysis 535
References 542
Conclusions and Future Prospects 557
Index 559