Tài liệu Hóa học của tinh thể nano các ô xít. Tổng hợp, tính chất và ứng dụng

Contents
Foreword xiii
Preface . xv
1. Introduction 1
1.1 General . 1
1.2 Preparative Methods 3
1.3 Scope of the Book 5
2. Combustible Solid Precursors toNanocrystallineOxideMaterials 9
2.1 Introduction 9
2.2 Combustible Metal Hydrazine and Metal Hydrazine
Carboxylate Complexes . 11
Part I: Metal Hydrazine Carboxylates: Precursors
to Simple Metal Oxides 14
2.3 Preparation of Metal Formate, Acetate, Oxalate, and Hydrazine
Carboxylates 14
2.3.1 Thermal Analysis and Combustion of Metal
Hydrazine Carboxylates 16
Part II: Single Source Precursors to Mixed Metal Oxides 26
2.4 Mixed Metal Oxides 26
2.4.1 Mixed Metal Acetate and Oxalate Hydrazinates:
Precursors to Cobaltites 27
vii
viii Chemistry of Nanocrystalline Oxide Materials
2.4.2 Mixed Metal Oxalate Hydrazinates: Precursors to
Spinel Ferrites . 27
2.4.3 Mixed Metal Oxalate Hydrates: Precursors
to Metal Titanates . 30
2.5 Mixed Metal Hydrazinium Hydrazine Carboxylates . 30
2.5.1 Mixed Metal Hydrazinium Hydrazine Carboxylates:
Precursors to Nano-Cobaltites and Ferrites 30
2.5.2 Mixed Metal Hydrazinium Hydrazine Carboxylates:
Precursors to Mixed Ferrites 35
2.5.3 Mixed Metal Hydrazinium Hydrazine Carboxylates:
Precursors to Manganites . 37
2.6 Concluding Remarks 38
3. Solution Combustion Synthesis of Oxide Materials 42
3.1 Introduction 42
3.2 Solution Combustion Synthesis (SCS) . 43
3.2.1 Synthesis of Alumina . 45
3.2.2 Mechanism of Aluminum Nitrate—Urea
Combustion Reaction . 46
3.2.3 Thermodynamic Calculation . 48
3.3 Role of Fuels 49
3.4 A Recipe for the Synthesis of Various Classes of Oxides . 53
3.4.1 Recipe for Nanomaterials . 56
3.5 Salient Features of Solution Combustion Method 58
4. Alumina and Related Oxide Materials 61
4.1 Introduction 61
4.2 Alumina and Related Oxide Materials 62
4.3 α-Alumina . 65
4.4 Metal Aluminates (MAl2O4) 68
4.5 Rare Earth Orthoaluminates (LnAlO3) . 73
4.6 Garnets . 74
4.7 Aluminum Borate 78
4.8 Tialite (β-Al2TiO5) . 80
4.9 Aluminum Phosphate 83
Contents ix
4.10 Alumina Composites 84
4.10.1 Al2O3 · SiO2 System: Mullite . 85
4.10.2 Al2O3 · SiO2 System: Cordierite 87
4.10.3 Al2O3 · Si3N4 System: SiAlON 91
4.11 Alumina Nanocomposites 93
4.11.1 Nanocatalysts,Dispersion ofNano-metals (Ag, Au, Pd,
and Pt) in Al2O3 94
4.12 Nanopigments . 99
4.12.1 Cobalt-Based Blue Alumina and Aluminates 99
4.12.2 Chromium-Doped Pink Alumina (Cr3+/Al2O3): Ruby 104
4.12.3 Chromium-Doped Aluminates and Orthoaluminates
(Cr3+/MAl2O4(M = Mg & Zn)) and LaAlO3) 105
4.13 Nanophosphors . 106
4.13.1 Phosphor Materials (Luminescence in Aluminum
Oxide Hosts) . 108
4.14 Concluding Remarks 114
5. Nano-Ceria and Metal-Ion-Substituted Ceria 117
5.1 Introduction 117
5.2 Synthesis and Properties of Nano-Ceria . 119
5.3 Synthesis of Metal-Ion-Substituted Ceria 121
5.4 Characterization of Metal-Ion-Substituted Ceria 124
5.5 Oxygen Storage Materials 132
5.6 Metal-Ion-Substituted Ceria as Nanocatalysts 137
5.6.1 Ce1ưxPdxO2ưδ as a Three-Way Catalyst 141
5.6.2 Ce1ưxPtxO2ưδ . 146
5.6.3 Ce1ưxRhxO2ưδ 147
5.6.4 Bimetal Ionic Catalysts (Ce1ưxPtx/2Rhx/2O2ưδ) . 149
5.7 Concluding Remarks 151
6. Nanocrystalline Fe2O3 and Ferrites 154
6.1 Magnetic Materials . 154
6.2 γ-Fe2O3 156
6.3 Spinel Ferrites (MFe2O4) 158
6.4 Mixed Metal Ferrites 161
x Chemistry of Nanocrystalline Oxide Materials
6.4.1 Li–Zn Ferrites . 161
6.4.2 Mg–Zn Ferrites 165
6.4.3 Ni–Zn Ferrites . 167
6.5 Rare Earth Orthoferrites 170
6.6 Garnets (Ln3Fe5O12) 171
6.7 Barium and Strontium Hexaferrites . 174
6.8 Concluding Remarks 177
7. Nano-Titania and Titanates 179
7.1 Introduction 179
7.2 Nano-TiO2 (Anatase) 182
7.2.1 Synthesis and Properties of Nano-TiO2 (Anatase) . 183
7.3 Photocatalytic Properties of Nano-TiO2 189
7.4 Metal-Ion-Substituted TiO2 197
7.4.1 Synthesis and Photocatalytic Properties of
Ti1ưxMxO2ưδ (M = Ag, Ce, Cu, Fe, V,W, and Zr) 197
7.4.2 Synthesis and Properties of Ti1ưxPdxO2ưδ 199
7.4.3 Catalytic Properties of Ti1ưxPdxO2ưδ . 200
7.5 Titanates for NuclearWaste Immobilization 203
7.5.1 Sintering and Microstructure Studies . 208
7.6 Concluding Remarks 209
8. Zirconia and Related Oxide Materials 212
8.1 Introduction 212
8.2 Zirconia . 213
8.2.1 Preparation and Properties of ZrO2 215
8.3 Stabilized Zirconia . 220
8.3.1 Magnesia-Stabilized Zirconia . 221
8.3.2 Calcia-Stabilized Zirconia . 223
8.3.3 Yttria-Stabilized Zirconia (YSZ) 225
8.3.4 Nickel in Yttria-Stabilized Zirconia (Ni–YSZ) . 227
8.4 Nano-Zirconia Pigments 232
8.5 ZrO2–Al2O3 System: ZTA . 235
8.6 ZrO2–CeO2 System 238
8.7 ZrO2–TiO2 System (ZrTiO4 and Zr5Ti7O24) . 242
Contents xi
8.8 ZrO2–Ln2O3 System: Pyrochlores . 245
8.9 NASICONs . 247
8.9.1 MZr2P3O12(M = Na, K, 1/2 Ca, and 1/4 Zr)
and NbZrP3O12 247
8.9.2 NASICON (Na Superionic Conductor) Materials
(Na1+xZr2P3ưx SixO12) 251
8.10 Concluding Remarks 254
9. Perovskite Oxide Materials 256
9.1 Introduction 256
9.2 Dielectric Materials . 256
9.2.1 MTiO3, MZrO3 (M =Ca, Sr, andBa) 258
9.2.2 Lead-Based Dielectric Materials (PbTiO3, PbZrO3,
PZT, and PLZT) . 259
9.3 Relaxor Materials (PFN, PMN, PNN, and PZN) 265
9.4 Microwave Resonator Materials . 270
9.5 Preparation and Properties of LnMO3 (M = Cr, Mn, Fe,
Co, andNi) . 276
9.6 Preparation and Properties of La1ưx SrxMO3 (M = Mn and Fe) 281
9.7 Concluding Remarks 289
10. Nanocrystalline Oxide Materials for Special Applications 292
10.1 Synthesis and Properties of Simple Oxides . 292
10.2 Metal Silicates 295
10.3 Ceramic Pigments 298
10.3.1 Borate Pigments 299
10.3.2 Metal Chromite Pigments . 302
10.3.3 Silicate Pigments 305
10.3.4 Ceria-Based Pigment—Ce1ưxPrxO2ưδ 308
10.4 Eu3+-Ion-Doped Red Phosphors 313
10.5 Metal Vanadates . 318
10.6 Rare Earth Metal Oxides (La2MO4) 320
10.7 Concluding Remarks 327
xii Chemistry of Nanocrystalline Oxide Materials
Appendix A 330
A.1 Oxidizers (Metal Nitrates) 330
A.1.1 Preparation of Titanyl Nitrate (TiO(NO3)2) 330
A.2 Fuels 331
A.2.1 Carbohydrazide (CH), CH6N4O . 331
A.2.2 Oxalyl Dihydrazide (ODH), C2H6N4O2 . 332
A.2.3 Tetraformal Trisazine (TFTA), C4H16N6O2 332
A.2.4 N, N
-Diformyl Hydrazine (DFH), C2H4N2O2 . 332
A.2.5 Maleic Hydrazide (MH), C4H4N2O2 . 333
A.2.6 Malonic Acid Dihydrazide (MDH), C3H8N4O2 . 333
A.2.7 3-Methyl Pyrazole 5-One (3MP5O), C4H6N2O . 333
A.3 Useful Suggestions . 334
Index 337