Layered double hydroxides

LAYERED DOUBLE HYDROXIDES: PRESENT AND FUTURE......Page 3
CONTENTS......Page 7
PREFACE......Page 9
REFERENCES......Page 12
PART I: SYNTHESIS, STRUCTURE  AND CHARACTERISATION......Page 13
INTRODUCTION......Page 15
Trivalent metal ratio......Page 16
Metal cations in the layers......Page 17
Structure of the layers......Page 18
Interlamellar anions......Page 19
Interlamellar structure......Page 20
Coprecipitation Method......Page 22
Origin of Interlamellar Anions......Page 23
Experimental Parameters......Page 24
Which Metals ?......Page 26
Which anions ?......Page 27
Which MII/MIII ratio ?......Page 28
Addition rate or aging......Page 29
Induced hydrolysis......Page 30
The [Zn-Cr-Cl] system.......Page 31
POST SYNTHESIS MODIFICATION OF LDHS......Page 33
Anionic exchange......Page 34
Washing and drying process......Page 35
Grafting of anions onto LDH layers......Page 36
Examples: Modification of oxoanions intercalated LDHs.......Page 37
Intercalation of Silicate Species in [Zn-Cr] and [Zn-Al] LDH45......Page 40
[Zn-Cr-SiO4] compound......Page 43
[Zn-Al-SiO4] compound......Page 46
Hybrid LDHs......Page 47
Calcination and reconstruction......Page 48
Redox modifications......Page 49
Delamination process example......Page 50
REFERENCES......Page 52
INTRODUCTION......Page 55
Brucite Layer......Page 56
The Relationship between x and Layer Cell Parameter a......Page 58
 Order-disorder in Isomorphous Cation Distribution......Page 59
Composition of LDHs Interlayers......Page 60
Structural Formulae, Unit Cell Parameters and Nomenclature of Natural LDHs......Page 61
Determination of Unit-cell Parameters......Page 64
Structural Analysis......Page 67
CO3-Bearing LDHs......Page 69
SO4 - Bearing LDHs......Page 70
Ordered Interstratification of Interlayer Anions......Page 71
Mixed-Anion Interlayer Composition......Page 72
POLYTYPE DIVERSITY OF THE LDH COMPOUNDS......Page 74
Two-Layer Polytypes......Page 75
Three-Layer Polytypes......Page 76
Six-Layer Polytypes......Page 78
3D Models......Page 79
XRD Features of LDH Polytypes with Random Cation-Anion Distribution......Page 80
XRD Features of LDH Polytypes with Ordered Cation-Anion Distribution......Page 82
Structural Disorder and Intensity of 10l Superreflections......Page 86
Stacking Faults......Page 89
POLYTYPE DIVERSITY OF EXPERIMENTALLY STUDIED LDHS......Page 93
Polytypes with Interlayer −23CO - Anions......Page 94
SO4-Bearing Polytypes with the Minimum Periodicity C0 = 8.8 Å......Page 95
SO4-Bearing Polytypes with the Minimum Periodicity C0 = 11 Å......Page 96
Polytypism of LDH Containing O−H, C−l, and −24CrO - Anions......Page 98
Multilayer Polytypes with Interstratified Interlayers of Different Composition......Page 99
The Main Crystal Chemical Features of LDH Polytypes......Page 100
Order-Disorder in Cation Distribution Long-Range Order......Page 103
Short-Range Cation Order......Page 107
Coalingite......Page 108
Structures with Vacancy-Containing Brucite-Like Layers......Page 109
LDHs with Silicate Anions in the Interlayers......Page 110
CONCLUSION......Page 111
REFERENCES......Page 112
Computer Modelling as a Technique in Materials Chemistry......Page 115
Background......Page 116
Molecular Dynamics Simulations......Page 117
Model Construction......Page 119
Forcefields......Page 120
Mg3Al-LDHs Containing Carbonate, Nitrate or Chloride......Page 121
MgAl-LDHs Containing Terephthalate......Page 124
MgAl-LDH Containing Carbonate......Page 131
MgAl-LDH Containing (S)-phenylalanine and (S)-tyrosine......Page 132
OTHER LDH SIMULATIONS......Page 135
REFERENCES......Page 137
INTRODUCTION......Page 141
Carbonate-LDHs with Non-transition Metal Cations......Page 142
Removal of Interlayer Water Molecules.......Page 145
Decarbonation and Dehydroxylation.......Page 146
Carbonate-LDHs with Transition Metal Cations in the Layers......Page 149
LDHs with Other Interlayer Inorganic Anions......Page 150
LAYERED DOUBLE HYDROXIDES WITH ORGANIC ANIONS......Page 152
LAYERED DOUBLE HYDROXIDES WITH PERMANENT  INORGANIC ANIONS......Page 154
THE SPECIAL CASE OF REDUCTION......Page 157
REFERENCES......Page 161
INTRODUCTION......Page 167
INFRARED AND RAMAN SPECTROSCOPY......Page 168
INFRARED AND NEAR-INFRARED SPECTROSCOPY......Page 169
INFRARED EMISSION SPECTROSCOPY......Page 170
FACTOR GROUP ANALYSIS......Page 171
Mg/Al-LDH......Page 172
Replacement of Mg by Other di- and Monovalent Metals in M2+/Al-LDH......Page 175
Replacement of Al by Other Trivalent Metals in Mg/M3+-LDH......Page 180
Other Combinations di- and Trivalent Metals in LDHs......Page 181
CO32-......Page 185
NO3-......Page 189
SO42-......Page 191
ClO4-......Page 194
Fe(II)- and Fe(III)- cyano-complexes......Page 195
Vanadates and molybdates......Page 198
Phosphates and Phosphonates......Page 203
Silicates......Page 206
Polyoxometalates......Page 207
SOME SELECTED INTERLAYER AND ADSORBED  ORGANIC COMPLEXES......Page 208
WATER......Page 217
INFRARED EMISSION SPECTROSCOPY DURING THE THERMAL TREATMENT OF LDHS......Page 218
ACKNOWLEDGEMENTS......Page 222
REFERENCES......Page 223
INTRODUCTION......Page 231
NMR Spectra of I=1/2 Nuclei in Solids......Page 232
NMR Spectra of I>1/2 (Quadrupolar) Nuclei in Solids......Page 233
1H......Page 235
2H......Page 237
11B......Page 238
13C......Page 240
27Al......Page 242
29Si......Page 244
35Cl......Page 246
51V......Page 247
77Se......Page 248
EPR STUDIES ON LAYERED DOUBLE HYDROXIDES......Page 249
CONCLUSION......Page 251
REFERENCES......Page 252
INTRODUCTION......Page 255
Cation Ordering in Green Rust and Pyroaurite......Page 256
Redox-manipulated Cation Layers......Page 260
The Interlayer Space: Bonding and Chemistry of Fe-CN Complexes and Mechanical Properties......Page 262
STRUCTURAL CHANGES UPON THERMAL TREATMENT OF LDHS......Page 267
CONCLUSIONS......Page 268
REFERENCES......Page 269
INTRODUCTION......Page 271
HYDROTALCITE AND HYDROTALCITE-LIKE LDHS......Page 272
LAYERED DOUBLE HYDROXIDES WITH  INTERCALATED POLYOXOMETALATES......Page 276
LAYERED DOUBLE HYDROXIDES WITH INTERCALATED HEXACYANOFERRATE COMPLEXES......Page 283
CALCINED LDHS......Page 289
ELECTRON MICROSCOPY......Page 290
ACKNOWLEDGMENTS......Page 293
REFERENCES......Page 294
PART II: APPLICATIONS......Page 297
INTRODUCTION......Page 299
ADSORPTION OF INORGANIC CONTAMINANTS ON HT AND CHT......Page 301
Anionic Species......Page 302
Radiactive Anions......Page 308
Miscellaneous Species......Page 310
Aromatic Anions......Page 311
Pesticides......Page 318
Anionic Surfactants and Dyes......Page 320
Natural Humic Substances......Page 323
Synthesis of OHT......Page 324
Interlayer Structure of OHT......Page 325
Adsorption of Organic Contaminant......Page 328
Adsorption of Inorganic Contaminants......Page 331
REFERENCES......Page 332
INTRODUCTION......Page 337
APPLICATIONS AS CATALYST SUPPORTS......Page 339
INTERMEDIATE OR FINE CHEMICAL SYNTHESIS AND  ORGANIC REACTIONS......Page 343
AIR DECONTAMINATION......Page 350
ADVANCES IN NATURAL GAS CONVERSION......Page 358
PILLARED OR INTERCALATED HT ANIONIC CLAYS......Page 366
CONCLUSIONS......Page 370
REFERENCES......Page 371
INTRODUCTION: HYDROGENATION REACTIONS......Page 381
HYDROGENATION OF UNSATURATED HYDROCARBONS: HYDROGENATION OF ACETYLENE......Page 385
Physico-chemical Characterisation Results......Page 386
Application to selective hydrogenation of acetylene.......Page 390
Influence of the Substitution of Ni by Co or Cu on Ni-Zn-Al Catalysts......Page 395
Influence of the Addition of Co or Cu as Catalytic Modifiers and Cr as Structural Modifier to Ni-Zn-Al Catalysts......Page 400
Study of Ni-Zn-Al-Cr and Ni-Zn-Al-Fe Catalysts......Page 405
Physico-Chemical Characterisation Results......Page 406
Application to selective hydrogenation of acetylene......Page 411
Conclusions......Page 419
Hydrogenation of Acetonitriles and Nitro-Compounds......Page 421
Hydrogenation of Carbonyl Compounds......Page 428
Other Reactions......Page 440
CONCLUDING REMARKS......Page 443
REFERENCES......Page 445
INTRODUCTION......Page 449
PHOTOPHYSICAL AND PHOTOCHEMICAL PROCESSES IN A CONSTRAINED MEDIA......Page 450
SYNTHETIC STRATEGIES TO OBTAIN INTERCALATION COMPOUND AND COMPOSITE LDH-CHROMOPHORES......Page 453
LDH - ANIONIC DYE INTERCALATION COMPOUNDS AND THEIR FLUORESCENCE PROPERTIES......Page 457
LDH INTERCALATES CONTAINING LUMINESCENT INORGANIC COMPLEXES AND THEIR PHOTOPHYSICAL PROPERTIES......Page 463
PORPHYRIN AND PHTALOCYANINE-LDH INTERCALATION COMPOUNDS AND THEIR PHOTO REACTIVITY......Page 464
OTHER LDH-COMPOSITES WITH PHOTOLUMINESCENCE AND NON LINEAR OPTIC PROPERTIES......Page 467
ORGANIC PHOTOCHEMISTRY INSIDE THE LDH  INTERLAYER REGION......Page 468
Antacid and Anti-Pepsin Activity of Hydrotalcite Formulations......Page 472
LDHS IN PHARMACEUTICAL FORMULATIONS AND DRUG RELEASE......Page 474
CONCLUSION......Page 478
REFERENCES......Page 479
INTRODUCTION......Page 483
Oxidation of Fe(0)......Page 484
Oxidation of Fe(II)......Page 485
Reaction of Soluble Fe(II) with Fe(III) Oxides......Page 486
IDENTIFICATION AND CHARACTERIZATION......Page 487
POTENTIOMETRY......Page 490
SOLUBILITY MEASUREMENTS......Page 491
SOLUBILITY AND STABILITY DIAGRAMS......Page 492
Coprecipitation......Page 494
Redox Reactions......Page 495
Oxygen......Page 496
Nitrate and Nitrite......Page 497
Selenium(IV/VI), Chromium(VI) and Other Inorganic Oxidants......Page 500
Organic Oxidants......Page 501
GREEN RUSTS IN NATURAL ENVIRONMENTS......Page 502
REFERENCES......Page 504
INDEX......Page 509