Ordered Porous Solids: Recent Advances and Prospects

Cover Page......Page 1
Copyright Page......Page 2
Contributors......Page 3
A New Family of Mesoporous Oxides-Synthesis, Characterisation and Applications of TUD-1......Page 9
Introduction......Page 10
MCM-41 and FSM-16......Page 11
TUD-1......Page 12
Ti-TUD-1......Page 16
Fe-TUD-1......Page 17
Co- and Cr-TUD-1......Page 20
Cr-TUD-1 as photocatalysts in the gas phase......Page 22
Ce-TUD-1......Page 23
Zr-TUD-1......Page 24
Al2O3-TUD-1 and Al-TUD-1......Page 25
TUD-1 as Potential Drug Carriers......Page 27
Zeolite Beta......Page 28
ITQ-2-Delaminated zeolite......Page 32
Conclusion......Page 34
References......Page 35
Introduction......Page 37
Preparation and Applications of Organoclays......Page 39
Organoclays prepared by grafting of organic moieties......Page 40
Covalent grafting of clays with aminopropyl groups......Page 42
Covalent grafting of clays with miscellaneous functional organic moieties......Page 44
Multifunctional treatment......Page 47
Grafting of functional polymers......Page 48
One step synthesis of organoclays......Page 49
Outlook......Page 51
References......Page 52
A New Family of Mesoporous Oxides-Synthesis, Characterisation and Applications of TUD-1......Page 56
Introduction......Page 57
MCM-41 and FSM-16......Page 58
TUD-1......Page 59
Ti-TUD-1......Page 63
Fe-TUD-1......Page 64
Co- and Cr-TUD-1......Page 67
Cr-TUD-1 as photocatalysts in the gas phase......Page 69
Ce-TUD-1......Page 70
Zr-TUD-1......Page 71
Al2O3-TUD-1 and Al-TUD-1......Page 72
TUD-1 as Potential Drug Carriers......Page 74
Zeolite Beta......Page 75
ITQ-2-Delaminated zeolite......Page 79
Conclusion......Page 81
References......Page 82
Introduction......Page 84
Preparation and Applications of Organoclays......Page 86
Organoclays prepared by grafting of organic moieties......Page 87
Covalent grafting of clays with aminopropyl groups......Page 89
Covalent grafting of clays with miscellaneous functional organic moieties......Page 91
Multifunctional treatment......Page 94
Grafting of functional polymers......Page 95
One step synthesis of organoclays......Page 96
Outlook......Page 98
References......Page 99
Titanium-Based Nanoporous Materials......Page 103
Titanium silicalite-1 (Ti-MFI, TS-1)......Page 104
Comparative evaluation of catalytic activity of Ti[4] titanosilicates......Page 109
Nanoporous Titanosilicates with Ti[6] Coordination......Page 116
Nanoporous Titania......Page 119
Synthesis of Ti-MFI (TS-1)......Page 121
Synthesis of Ti-BEA......Page 122
Synthesis of ETS-10......Page 123
Summary and Outlook......Page 124
References......Page 125
Porous Metal Organic Frameworks: From Synthesis to Applications......Page 128
Introduction......Page 129
Flexible MOFs......Page 132
The reactants......Page 133
Temperature, pressure and pH......Page 134
Heterogeneous reaction medium......Page 135
Thin Films......Page 136
Green-house gases......Page 137
Hydrogen storage......Page 138
Metal nanoparticles......Page 140
Catalytic Applications......Page 141
Magnetism......Page 142
Drug delivery......Page 143
Conclusions......Page 144
References......Page 145
Functionalisation and Structure Characterisation of Porous Silicates and Aluminophosphates......Page 151
Introduction......Page 152
Hydrothermal Conventional and Microwave Synthesis of Nanoporous Silica- and Aluminophosphate-Based Materials......Page 153
Determination of Structure Porosity and Acid Sites in Nanoporous Catalysts......Page 155
X-ray diffraction......Page 156
X-ray absorption spectroscopy......Page 157
Nuclear magnetic resonance spectroscopy......Page 160
Mn-, Fe- and Ti-Functionalised Microporous and Mesoporous Silicates and Aluminophosphates: Case Studies......Page 162
Synthesis and characterisation of MnS-1, MnMCM-41 and MnHMA......Page 163
Fe-modified silicates and aluminophosphates......Page 164
Characterisation of Fe-modified silicate FeTUD-1......Page 165
Ti-modified silicates and aluminophosphates......Page 166
Synthesis and characterisation of (Ti,Al)-Beta/MCM-41, (Ti,Al)-Beta/MCM-48 and Ti-Beta/SBA-15......Page 167
Mesoporous aluminophosphate-based thin films with cubic pore arrangements......Page 169
Acknowledgements......Page 170
References......Page 171
Introduction......Page 177
Nucleation of Zeolites: An Overview and Critical Evaluation......Page 179
Homogeneous nucleation......Page 181
Heterogeneous nucleation......Page 184
Secondary nucleation......Page 187
Nucleation in the gel phase......Page 194
Experimental evidences on the presence of structurally ordered phase in the gel matrix and/or the proposed mechanisms of nucleation......Page 195
Autocatalytic nucleation......Page 210
Nucleation in homogeneous systems (\'clear\' solutions)......Page 217
Nucleation in untemplated homogeneous systems......Page 218
Nucleation in templated homogeneous systems......Page 222
Summary and Outlook......Page 225
References......Page 228
Modern Spectroscopic Methods Applied to Nanoscale Porous Materials......Page 236
Introduction......Page 237
Vibrational Spectroscopy: Fundamentals and Practical Hints......Page 239
Solidification and crystal growth processes......Page 245
Structural characterization of assemblies of microporous nanocrystallites......Page 250
Active centres......Page 252
Guest-host interactions......Page 253
Thin films......Page 254
Synchrotron sources......Page 255
References......Page 256
Computational Modelling of Nanoporous Materials......Page 259
Computational methods......Page 260
Isolated cluster models......Page 262
Hybrid QM/MM models......Page 263
Calculation of the total energy of the system......Page 264
Termination of the QM cluster......Page 265
Treatment of the electrostatic interaction......Page 266
Periodic models......Page 267
Structure and isomorphic substitution of T atoms......Page 268
Bridging hydroxyl groups......Page 269
Extra-framework metal ions and their complexes......Page 270
Basic oxygen centres......Page 276
Zeolite-supported transition metal clusters......Page 277
Adsorption and dissociation of H2......Page 279
Adsorption and dissociation of hydrocarbons......Page 280
Adsorption of chloroform......Page 281
Adsorption of methanol......Page 282
Outlook......Page 283
References......Page 284
Introduction......Page 287
Basic Thermodynamic Conceptsa......Page 288
Dispersion (London) Forces......Page 290
Induced Dipole and Quadrupole-Charge Interactions......Page 295
Dipole-Charge Interactions......Page 300
Interactions of Adsorbed Molecules with Acid Sites......Page 302
Final Remarks......Page 307
References......Page 308
Application of Isotopically Labelled IR Probe Molecules for Characterization of Porous Materials......Page 310
Introduction......Page 311
Brief Background of the Vibrational Spectra of Isotopically Labelled Molecules......Page 312
Chemical Composition and Structure of Surface Species......Page 314
Dicarbonyls......Page 316
Dinitrosyls......Page 322
Tri- and tetracarbonyls......Page 323
Use of D3-Acetonitrile for Determination of Surface Acidity......Page 324
Use of Isotopic Exchange for Changing the Spectral Region......Page 325
References......Page 326
Organically Modified Ordered Mesoporous Siliceous Solids......Page 329
Introduction......Page 330
Post-synthesis grafting method......Page 331
Periodic mesoporous organosilicas......Page 332
Role and nature of organic functional groups......Page 333
Structural and textural characteristics......Page 334
Morphology......Page 337
Catalysis......Page 338
Adsorption......Page 339
Adsorption of metals......Page 340
Adsorption of other pollutants and novel applications......Page 342
Sensors......Page 344
Miscellaneous......Page 345
Outlook and Prospects......Page 346
References......Page 347
Hydrothermal Synthesis of Zeolitic Coatings for Applications in Micro-structured Reactors......Page 355
Micro-structured reactors......Page 356
Influence of synthesis parameters on the properties of zeolitic coatings......Page 357
Effect of Surface Roughness on Coverage......Page 359
Effect of Surface Hydrophobicity on Coverage......Page 361
Effect of heating rate, Si/Al ratio and synthesis temperature......Page 364
Growth model of continuous zeolitic coatings......Page 367
Microwave-Assisted Synthesis of Zeolitic Coatings......Page 369
Bulk chemicals processing......Page 370
Fine chemicals synthesis......Page 373
Acknowledgements......Page 374
References......Page 375
Pure-Silica-Zeolite Low-Dielectric Constant Materials......Page 379
Introduction......Page 380
Alternative low-k materials......Page 381
In situ growth b-oriented pure-silica-zeolite MFI films......Page 382
Spin-on PSZ MFI films......Page 383
Pore characterization......Page 384
Mesoporosity......Page 385
Crystallinity......Page 386
Microporosity......Page 387
Hydrophobicity......Page 390
Mechanical Properties......Page 392
Nanoindentation......Page 394
Mechanical properties of PSZ crystalline films......Page 396
Mechanical properties of zeolite single crystals......Page 397
Pore dimensionality and symmetry......Page 398
Interfacial adhesion studies......Page 399
Tribological properties......Page 400
Future Considerations and Conclusions......Page 401
Acknowledgements......Page 403
References......Page 404
Highly Selective Zeolite Membranes......Page 409
Introduction to Zeolite Membranes......Page 410
Zeolite Membrane Growth Methods......Page 411
Permeation and Gas Transport......Page 412
Zeolite Membrane Modification......Page 414
CO2 sequestration......Page 416
C5-hydrocarbon (HC) separations......Page 417
Xylene separations......Page 418
Reverse osmosis by zeolite membranes......Page 422
Catalytic zeolite membranes......Page 423
Fabrication and Manufacturing......Page 425
Acknowledgement......Page 427
References......Page 428
Abbreviations......Page 431
Introduction......Page 432
Increasing sensor selectivity with nanoporous solids......Page 433
Fabrication and structural properties of porous silicon......Page 436
Optical transducers......Page 438
Electrical transducers......Page 439
Si-Based Microporous Solids: Zeolites and Related Materials......Page 440
Electrochemical/electrical transducers......Page 441
Mass/piezoelectric transducers......Page 443
Optical transducers......Page 445
Mesoporous Silica......Page 447
Ordered Mesoporous Materials: M41S and PMOs Families......Page 448
Optical transducers......Page 450
References......Page 451
Glossary......Page 456
Self-Assembly of Mesoporous Materials......Page 457
Evaporation-Induced Self-Assembly Origins......Page 460
Fundamentals......Page 461
Growth from solution......Page 464
Mesostructured Silicate Systems......Page 465
Mesostructured Non-Silicate Systems......Page 469
Emerging Applications......Page 477
Concluding Remarks......Page 478
References......Page 479
Zeolite Nanocrystals: Hierarchical Assembly and Applications......Page 483
Introduction......Page 484
Hierarchical Assemblies of Zeolite Nanocrystals......Page 485
Removable polymer templates......Page 486
Digestible mesoporous silica templates......Page 487
Biotemplates......Page 489
Others......Page 491
Emerging Applications of Zeolite Nanocrystals......Page 492
Catalytic applications......Page 494
Emerging novel biology-related applications......Page 500
Conclusions and Prospects......Page 506
References......Page 508
Introduction......Page 518
Microporous materials......Page 520
Mesoporous materials......Page 526
Macroporous materials......Page 528
Concluding Remarks......Page 535
References......Page 537
Introduction......Page 541
Dip-coating, slip-casting, and washcoating......Page 543
Spin-coating......Page 545
Zeolite crystals assembly driven by external forces......Page 546
Self-assembly and Langmuir-Blodgett zeolite films......Page 547
Multi-step methods......Page 548
Layer-by-layer deposition......Page 549
Assembly via covalent and ionic linkages......Page 551
Applications of Supported Layers of Preformed Zeolite Crystals......Page 554
Concluding Remarks......Page 556
References......Page 557
Electrochemistry with Micro- and Mesoporous Silicates......Page 560
Introduction......Page 561
Confinement of Microporous Zeolites and Mesoporous Silica Materials onto Electrode Surfaces......Page 562
Electrochemical response of zeolite-modified electrodes......Page 566
Electron transfer mechanisms at zeolite-modified electrodes......Page 571
Electrochemical response of redox probes in mesoporous silica......Page 573
Electrochemistry of mesoporous silica films......Page 575
Applications......Page 577
Preconcentration electroanalysis and permselectivity......Page 578
Electrocatalysis......Page 582
Bioelectrochemistry......Page 584
Indirect amperometric detection......Page 585
Miscellaneous......Page 587
References......Page 589
Nanoparticle Doped Photopolymers for Holographic Applications......Page 595
Introduction......Page 596
Holographic Recording......Page 598
Holographic recording in photopolymers......Page 600
Holographic recording in photopolymerisable nanocomposites......Page 602
Mechanism for the Holographic Redistribution of Nanoparticles......Page 604
Improvement of the dynamic range......Page 605
Improvement of the shrinkage properties......Page 608
Holographic data storage......Page 610
Holographic optical elements......Page 612
Holographic sensors......Page 615
References......Page 619
Inorganic Sulphur Pigments Based on Nanoporous Materials......Page 626
Introduction......Page 627
Styrene......Page 628
Lazurite and natural ultramarine (historical background)......Page 629
Use of synthetic zeolites for the preparation of ultramarine analogues......Page 638
Introduction of radical precursors into zeolite cages during hydrothermal synthesis of zeolites......Page 639
Irradiation of occluded sulphur species......Page 640
Syntheses based on zeolite A......Page 641
Cancrinite......Page 646
Losod......Page 647
Natural zeolites......Page 648
Application of various alkaline cations......Page 649
Ultramarine with non-aluminosilicate matrices......Page 650
Conclusions......Page 652
References......Page 653
Advances in the Use of Carbon Nanomaterials in Catalysis......Page 656
Generalities......Page 657
Synthesis of CNT and CNF......Page 659
Structural and electronic features......Page 660
Mechanical and thermal properties......Page 662
What does a catalyst require?......Page 663
Confinement effect......Page 664
Metal-carbon interactions: Importance of surface functional groups......Page 665
Preparation of nanocarbon decorated with metal nanoparticles......Page 666
Selective hydrogenations: C=C bonds, nitrobenzene......Page 667
CNT as a catalyst itself: The case of oxidative dehydrogenation......Page 669
Grafting of organometallic complexes......Page 670
Problems linked to the use of nanoscopic carbon nanomaterials particles......Page 671
CNF with macroscopic assembly......Page 672
Self-supported MWNT......Page 674
Self-supported CNT via constraint synthesis......Page 675
Aligned CNT patterns......Page 676
Catalytic decomposition of hydrazine......Page 677
Selective oxidation of H2S into elemental sulphur......Page 679
Conclusions......Page 680
References......Page 681
Strong Broslashnsted Acidity in Alumina-Silicates: Influence of Pore Dimension, Steaming and Acid Site Density on Cracking of Alkanes......Page 685
Reacting Species......Page 686
Determining Reaction Constants......Page 687
Cracking of Alkanes Over ZSM5......Page 689
Adsorption of Alkanes in Zeolite Pores......Page 691
Cracking of Alkanes Over Different Zeolites......Page 694
Cracking of Alkanes Over Steamed Zeolites and Amorphous Silica-Alumina......Page 698
Concluding Remarks......Page 699
References......Page 700
Catalysis by Mesoporous Molecular Sieves......Page 703
Introduction to Mesoporous Molecular Sieves......Page 704
Acid-catalyzed reactions......Page 706
Base catalyzed reactions......Page 712
Ti, Zr, Nb, and Sn containing mesoporous materials......Page 713
Transition Metal Oxides Supported on Mesoporous Molecular Sieves......Page 716
Metathesis using MoO3 and Re2O7......Page 717
Grubbs and Schrock catalysts for metathesis......Page 719
C-C bond formation over Pd nanoparticles......Page 720
References......Page 722
Catalytic Phases Embedded in Mesostructured Matrices and their Nanocasts: Effects of Spatial Dimension and Assembling Mode on Activity......Page 727
Introduction......Page 728
Methodology and computational details......Page 731
CP surface area as a function of its assembling mode......Page 733
Conditions for surface area maximization......Page 736
Control of CP Assembling Mode in a Mesostructured Matrix......Page 737
Nanowires (Nanorods)......Page 738
Coating layer......Page 743
Evaluation of CP Assembling Mode in CP/MHM Composites and Their Nanocasts......Page 747
Effect of CPs\' Spatial Dimension and Assembling Mode on Their Catalytic Performance......Page 750
Conclusions......Page 753
References......Page 754
Nanoporous Materials-Catalysts for Green Chemistry......Page 759
Introduction......Page 760
Metrics-Measurement and Comparison of Processes......Page 761
Green Aspects in the Synthesis of Nanoporous Catalysts......Page 763
Diffusion and sorption kinetics......Page 764
Examples of catalytic processes occurring in nanoporous catalysts......Page 765
Towards One-Pot Multistage Syntheses......Page 770
Enzyme Immobilization in Mesoporous Hosts......Page 774
Incorporation of Nanoporous Solids in Flow Reactors......Page 776
Conclusions......Page 778
References......Page 779
The Fascinating Chemistry of Iron- and Copper-Containing Zeolites......Page 783
Introduction......Page 784
The effect of the zeolite matrix......Page 785
The effect of pretreatments at high temperature......Page 786
Dehydroxylation and dealumination of high-silica zeolites......Page 787
The properties of the active sites for benzene oxidation-alpha-sites......Page 790
The role of acidity......Page 793
The Decomposition of N2O by Iron Zeolites......Page 794
The mechanism of N2O decomposition over iron zeolites......Page 795
The autoreduction of Fe3+ to Fe2+......Page 797
Active Oxygen Atoms in Copper Zeolites......Page 798
Copper zeolites for the direct decomposition of NO and N2O......Page 799
The oxidation of methane to methanol......Page 800
Conclusions-Iron Versus Copper Zeolites......Page 801
References......Page 802
B......Page 806
C......Page 807
D......Page 808
F......Page 809
H......Page 810
I......Page 811
M......Page 812
N......Page 814
P......Page 815
R......Page 816
S......Page 817
T......Page 818
Z......Page 819