Recent Advances in the Science and Technology of Zeolites and Related Materials (eBook)

Cover 1
Table of Contents 5
Silicalite-1 Crystals with Modified Morphology:HRTEM Imaging and Synthesis of B-Oriented Films 7
Abstract 7
Introduction 7
Experimental Section 8
Synthesis and Characterization of Modified MFI Crystals 8
Membrane Preparation and Xylene Isomer Separation 8
Results and Discussion 9
Conclusions 13
References 14
Microcrystal X-Ray Diffraction and NMR Studies of Thermal Expansion Properties of Pure Silica Zeolites FER and a Comparison with IFR 15
Abstract 15
Introduction 15
Results and Discussion 16
Concluding Remarks 19
Acknowledgement 19
References 19
HAS 17 O NMR Been Established as a Spectroscopic Tool for Zeolite Characterization? 20
Abstract 20
Introduction 20
Experimental 21
Results and Discussion 21
Acknowledgements 25
References 26
A Reinvestigation of the Disorder in Zeolite UTD-1 27
Abstract 27
Introduction 27
Description of Zeolite UTD-1 as an Array of Tubular Pores 28
Periodic Building Units 28
Connectivity of the Periodic Building Units 29
Simulation of XRD Patterns of Faulted Structures 31
Comparison with the Disorder in ZSM-48 and SSZ-31 32
Summary and Conclusions 33
Acknowledgements 33
References 34
Technique Integration Applied to Structure Solution: The Case of UZM-5. Details of the Structure, Faulting and Templating 35
Abstract 35
Introduction 35
Experimental Methods 35
Results 36
X-ray Diffraction 36
IR Spectroscopy 36
McBain Adsorption 36
Transmission Electron Microscopy 36
Structure Solution by Model Building 38
Rietveld Refinement of PXRD 40
Faulting in UZM-5 40
Discussion 42
Acknowledgments 43
References 43
Surface Structure Determination of Zeolites 44
Abstract 44
Introduction 44
Methodology 45
Results and Discussion 46
Conclusion 50
References 50
Characterization of Delaminated Zeolites by 129Xe NMR with Laser- Hyperpolarized Xenon 51
Abstract 51
Introduction 51
Experimental Section 52
Materials 52
Apparatus and Procedure 52
Results and Discussion 52
MCM-22 and ITQ-2 52
Ferrierite and ITQ-6 54
Conclusions 58
References 58
Elucidating the Dealumination Mechanism of Zeolite H-Y by Solid-State NMR Spectroscopy 59
Abstract 59
Introduction 59
Experimental Section 59
Results and Discussion 59
References 60
Stability upon Thermal Treatment of Coked Zeolite Beta 61
Abstract 61
Introduction 61
Experimental 62
Materials 62
Characterization 62
Results and Discussion 62
Characterization of not Impregnated Zeolite Beta 62
Structural Characterization 63
Spectroscopic Characterization 66
Conclusions 68
References 68
Characterisation and Evaluation of Hypothetical Zeolite Frameworks 69
Abstract 69
Introduction 69
Method 69
Results 70
Hypothetical Silica Polymorphs 70
AlPO4 vs. Silica Polymorphs 71
Three Trinodal Zeolites with D4R and Low Framework Density 73
Conclusions 75
Acknowledgements 76
References 76
Similarities between Atomic Properties in Dense and Open Aluminophosphate Sieves 77
Abstract 77
Introduction 77
Computational Details and Experimental Part 78
Geometry Optimizations 78
AlPO4-14 Sieve 78
AlPO4-15 Sieve 80
Comparison of the HBs in the AlPO4-14 and AlPO4-15 Sieves 80
Charge Distribution and Electron Density 81
Charge Distributions 81
Comparison of the ED at the Bond CP Positions of the H...O and Al-O Bond Types 81
Multipolar Representation of the ED in the TMC and Calcined ALPOs 82
Conclusions 83
Acknowledgements 83
References 84
Solid State NMR Studies of the Hydration of Molecular Sieve AlPO-36 85
Abstract 85
Introduction 85
Experimental 85
Results and Discussion 86
27Al MAS Single Pulse Spectra 86
As-synthesized Material 86
Calcined-dried Material 86
Calcined-rehydrated Material 87
31 P MAS Single-pulse Spectra 87
As-synthesized Material 87
Calcined-dried Material 87
Calcined-rehydrated Material 87
27Al MQMAS NMR Experiments 87
As-synthesized Material 87
Calcined-dried Material 87
Calcined-rehydrated Material 88
27Al/31P MAS INEPT Experiments 89
As-synthesized Material 89
Calcined-dried Material 89
Calcined-rehydrated Material 91
Conclusions 91
Acknowledgement 92
References 92
The Standardization of Zeolite-Type Crystal Structures 93
Abstract 93
Introduction 93
Systematics of Zeolite-Type Crystal Structures 94
Current Standardization Procedures 94
The Standardization of Zeolite-Type Structures 94
Example:ABW-Type Frameworks 97
Conclusion 99
References 99
Crystal-Chemical Comparisons of Zeolites based on Standardized Crystal Structure Data 101
Abstract 101
Introduction 101
Group-Subgroup Relationships 101
CHA-Type Frameworks 101
CAN-Type Frameworks 102
FAU-Type Frameworks 102
HEU-Type Frameworks 104
LEV-Type Frameworks 105
Chemical Compositions 106
Conclusion 106
References 107
Topological and Geometrical Characterization of Zeotypes with a Free Software Code Called Zeotsites: The Case Study of Germanium Location in Octadecasil 108
Abstract 108
Introduction 108
Computational Methodology 108
Bonds, Angles, and Coordination Sequences 108
Vertex Symbols 109
Case Study:Germanium Location in Octadecasil 109
Conclusions 112
References 112
The Structure of Subcolloidal Zeolite Precursor Nanoparticles 114
Abstract 114
Introduction 114
Experimental 115
29Si NMR Spectroscopy 115
Small Angle Neutron Scattering 116
Simulations 116
Results 117
Solution 29Si NMR 117
Small Angle Neutron Scattering 118
Kratky Plots 118
Pair Distance Distribution Function 118
Conclusions 120
References 120
Synthesis and Structure of ECR-40: An Ordered SAPO having the MEI Framework 121
Abstract 121
Introduction 121
Experimental Section 122
Results and Discussion 122
Conclusion 128
References 128
3D Computer Simulation of Zeolite a Crystal Growth 129
Abstract 129
Introduction 129
3D Simulation Methodology 130
Results and Discussion 132
Conclusions 134
References 135
The Investigation of Beta Polymorphs by 19F Nuclear Magnetic Resonance 136
Abstract 136
Introduction 136
Experimental 137
Materials 137
Techniques 138
Results and Discussion 138
Conclusions 141
Acknowledgements 141
References 141
Similarities between the Clathrasil Framework Types DOH, DDR, MEP and MTN 142
Abstract 142
Introduction 142
Alternative Description of the Clathrasils using Periodic Building Units 144
Periodic Building Units (PerBU1 and PerBU2) 144
Stacking Sequences of the Periodic Building Units 145
Stacking Sequences of PerBU1's 145
Stacking Sequences of "Extended" PerBU1's 147
Stacking Sequence of the Orthogonal (Extended) PerBU2's 148
References 149
Ordered Intergrowths of ETS-10 150
Abstract 150
Defects in ETS-10 150
Procedure for the Quantification of Defects and Stacking Disorder in ETS-10 from HREM Images 151
Stacking of Double-pores 153
New Structure Type (CMM-5) 156
Conclusions 157
References 157
Measuring the Silion Fluoride Bond Distance in Zeolites 160
Abstract 160
Introduction 160
Experimental Section 161
Solid-State NMR 161
Calculations 161
Results and Discussion 161
Fast Spinning 29Si Spectra 162
Measurement of Si-F Distance by MAS NMR 162
Conclusions 164
Acknowledgement 164
References 164
Stability of Framework Aluminum in the New Zeolite UZM-5 165
Abstract 165
Introduction 165
Calcinations to Remove Template in UZM-5 166
Air Calcination Followed by Aqueous NH4 + Exchange 166
NH3 Calcinations 167
Cation Exchange Forms 168
Dealumination of Zeolites from Repetitve Calcinations 168
Framework Al 169
Zeolite Crystallinity 169
Analysis 170
Summary 171
Experimental 171
Acknowledgments 172
References 172
Synthesis, Characterization, and Applications of the New Zeolite UZM-5 173
Abstract 173
Introduction 173
Experimental 173
Synthesis 173
UZM-5 TMA 173
UZM-5 TMA/Na 173
UZM-5 P 174
UZM-5 P2 174
Characterization 174
Microreactor Testing 175
Results and Discussion 175
Morphological Differences 175
Physical/Chemical Properties 177
Microreactor Testing 179
Heptene 179
Meta-xylene 180
Conclusions 180
References 181
Structure and Ion Exchange Properties of the Natural Zeolites Edingtonite and Goosecreekite 182
Abstract 182
Introduction 182
Experimental Section 183
Results and Discussion 184
EDI Structures 184
GOO Structures 185
Thermal Decomposition of EDI and GOO 186
Thermogravimetric-differential Thermal Analysis 186
In Situ Variable Temperature Powder X-ray Diffraction 187
Concluding Remarks 189
References 189
Investigation of Cancrinite Structures by Powder Neutron Diffraction 190
Abstract 190
Introduction 190
Experimental 191
Structure Analysis and Results 191
Ordered Cancrinite, [Na8(CO3).(D2O)n] [AlSiO4]6-CAN 191
Disordered Cancrinite [Na8_y(CO3)1-y/2.(D2O)n] [AlSiO4]6- CAN/SOD 193
Variable Temperature Studies 193
Discussion of the Cancrinite Structures 194
Ordered Cancrinite, [Na8(CO3).(D2O)n] [AlSiO4]6- CAN 194
Disordered Cancrinite [Na8-y(CO3)1-y/2.(D2O)n] [AlSiO4]6- CAN/SOD 194
Thermal Decomposition of Ordered and Disordered Cancrinites 194
Conclusions 196
Acknowledgement 196
References 196
Novel Synthesis and Characterization of Vanadium Aluminosilicates with BEA Structure 197
Abstract 197
Introduction 197
Experimental 198
Materials 198
Synthesis 198
Characterization 198
Results and Discussion 198
Hydrothermal Synthesis 198
Physicochemical Properties 200
Morphology 200
Framework IR Vibration 200
Electroparamagnetic Property 201
DRS Property 201
Conclusion 202
Acknowledgement 202
References 202
The Pore Size Analysis of Mesoporous Films by Krypton Adsorption 204
Abstract 204
Introduction 204
Experimental Section 205
Results and Discussions 205
Conclusion 208
References 209
IR Spectra of Zeolites Recorded at Liquid Helium Temperature 210
Abstract 210
Introduction 210
Experimental 211
Results and Discussion 211
The Effect of Temperature, Si/Al Ratio and Water Content on IR Bands of Framework Vibrations of Zeolites 211
The Effect of Zeolite Structure on Low Temperature IR Spectra of Zeolites 213
Conclusions 215
Acknowledgment 215
References 215
Is the Intensity of OH IR Stretching Bands a Measure of the Bronsted Acidity Strength of Zeolite? 216
Abstract 216
Introduction 216
Experimental 217
Results and Discussion 217
Conclusion 219
References 220
An Improved 1H NMR Spectra Interpretation of B and Al Zeolites with Dipolar Methods 221
Abstract 221
Introduction 221
Experimental Section 222
Results and Discussion 222
Conclusions 224
References 225
The Effect of Chemical Composition and Structure on XPS Binding Energies in Zeolites 226
Abstract 226
Introduction 226
Experimental 227
Results and Discussion 228
Conclusions 232
Acknowledgement 233
References 233
A Pair Distribution Function Analysis for Zeolite Beta 234
Abstract 234
Introduction 234
Experimental Section 236
Results and Discussion 236
Structure Refinement 237
Conclusions 239
References 240
Quantification of Electric-Field Gradients in the Supercage of HY, Steam-Dealuminated Y and Lanthanum-Exchanged Y Zeolites by 129Xe and 131Xe NMR of ... 241
Abstract 241
Introduction 241
Experimental 242
Results and Discussion 243
Conclusion 245
References 246
A Soft X-Ray EXAFS Study of the Local Structure of Tetrahedral Aluminium in Zeolites 247
Abstract 247
Introduction 247
Experimental 248
Results and Discussion 248
Acknowledgements 251
References 251
Investigations of the Mechanism of Dealumination of Zeolite Y by Steam: Tuned Mesopore Formation Versus the Si/Al Ratio 252
Abstract 252
Introduction 252
Experimental 253
Results and Discussion 253
Determination of the Si/Al Ratios 253
Pore Size Architecture 255
Conclusion 257
Acknowledgement 258
References 258
Structural Evolution of Calcium or Lanthanum-exchanged(NH4)2SiF6-Dealuminated Y Zeolite after Various Chemical Treatments 259
Abstract 259
Introduction 259
Experimental 260
Sample Preparation 260
Dealumination of (NH4)Y(LZY64) Zeolite by (NH4)2sif6. 260
Cacl2 or La(NO3)3 Exchange of Zeolite YD 260
Acid-base Treatment 260
Spectroscopy 260
X-ray Diffraction: < /h3~>
29Si NMR Spectra 260
27Al NMR Spectra 260
Results and Discussion 260
Sample Characterization 260
Structural Evolution of the Samples after Acid-base Treatment 261
YD Zeolite 261
CaYD Zeolite 263
LaYD Zeolite 263
29Si and 27Al NMR Study 263
CaYD Zeolite 263
LaYD Zeolite 264
Conclusion 265
References 265
The Stability of H-MCM-22 Under Severe Thermal Conditions 267
Abstract 267
Introduction 267
Experimental 268
Results and Discussion 268
Conclusions 271
Acknowledgements 271
References 271
Kinetic Study of LiAlSio4 Formation from Li-Exchanged Zeolite a by Time-Resolved Synchrotron Powder Diffraction 272
Abstract 272
Introduction 272
Experimental Section 273
Material 273
Time Resolved Powder Diffraction Experiment 273
Used Methods for the Phase Calculations 273
Results and Discussion 273
Conclusion 278
References 278
Si Atoms in SAPO-31: A Computational Study 280
Abstract 280
Introduction 280
Computational Details 281
Results and Discussion 282
Pure AIPO-31 282
Isolated Si-H+ Substitution 282
Silicon Islands 284
Conclusions 286
Acknowledgement 286
References 286
Modelling Mesoporous Materials with Analytical Functions 289
Abstract 289
Introduction 289
Experimental 289
References 296
Deriving Pore Size Distributions of Solids with both Micro- and Mesopores from Comparison Plots 297
Abstract 297
Introduction 297
Experimentals 298
Results and Discussion 298
t- plot and the Curve of Accumulating Pore Volume 298
Empirical Relation between t and Pore Diameter D 300
Procedures to Derive Quantitative PSD 300
Conclusions 303
Acknowledgment 303
References 303
Exploring the Internal Structure of Mesoporous Powders and Thin Films by Continuous Flow Laser-Enhanced 129Xe NMR 305
Abstract 305
Introduction 305
Experimental 305
Materials 305
Optical Pumping Setup 306
NMR 306
Results and Discussion 306
129Xe Chemical Shift 306
Variable Pressure Experiments for MCM-41 and SBA-15 Samples 306
Variable-temperature 129Xe NMR Spectra for MCM-41 and SBA-15 Samples 307
Mesoporous Silica Film 309
Conclusion 311
References 311
Characterization of AlPO- and SAPO-based Mesostructured Materials by Solid-State NMR 312
Abstract 312
Introduction 312
Experimental 312
Results and Discussion 312
SAPO-based Mesoporous Molecular Sieve 312
AlPO-based Mesostructured Lamellar Material 316
Summary 318
Acknowledgements 318
References 318
Pore Wall Structure Modeling of MCM-41 Type Silica using Molecular Dynamics Simulation 319
Abstract 319
Introduction 319
Methodologies 320
Molecular Dynamics Simulation Methods 320
Modeling Methods for MCM-41 Type Silica 320
Pore Structure Analysis 321
MD Simulation of Other Silica 321
Results and Discussion 321
Conclusion 325
References 325
In Situ FTIR Study of the Thermal Treatment on Boron Containing Mesoporous Molecular Sieve MCM-41 326
Abstract 326
Introduction 326
Experimental Section 326
B-MCM-41 Synthesis 326
In Situ DRIFTS Monitoring 327
Results and Discussion 327
Conclusion 330
Acknowledgement 330
References 330
FTIR Study of Fe-doped MCM-41 Mesoporous Molecular Sieves 331
Abstract 331
Introduction 331
Experimental 331
Results and Discussion 332
Texture and Structure Study 332
FTIR Study 333
NO Adsorption on Non Modified Materials (MCM-41, AlMCM-41, NbMCM-41) 333
NO Adsorption on Fe-doped Silicate MCM-41 Materials 334
NO Adsorption on Fe-doped Niobium-containing MCM-41 334
NO Adsorption on Fe-doped Aluminium Containing MCM-41 335
Conclusions 337
Acknowledgments 337
References 338
The Surface Acidity of Mesoporous Silicoaluminophosphates:A FTIR Study 339
Abstract 339
Introduction 339
Experimental Section 339
Results and Discussion 340
Conclusion 344
Acknowledgements 344
References 344
Design and Control of Acidic Strength in Ordered Mesoporous Aluminosilicates by Using Preformed Zeolite Precursors 348
Abstract 348
Introduction 348
Experimental 348
Results 349
X-ray Diffraction 349
Isotherms for N2 349
NH3-TPD 349
Discussion 352
References 352
Spectroscopic Evidence of SBA-15 Mesoporous Solids Functionalization 354
Abstract 354
Introduction 354
Experimental Section 354
Results and Discussion 355
Conclusion 359
References 359
An Inherent Macroperiodic Assembly or an Artificial Beauty? 360
Abstract 360
Introduction 360
Experimental Section 361
Results and Discussion 361
References 365
Differences between Isolated Silanols in All-Silica ITQ-2 and MCM-41 367
Abstract 367
Introduction 367
Experimental 368
Results and Discussion 368
H-bonding with Probes: Acidity of Silanols 368
Optical Isotherms and Equilibrium Constants 369
Conclusions 372
References 372
Characterization of the Superacidit Y in Zeolite Y by 27Al MAS and 1H/27 Al Trapdor NMR and FTIR:Correlation with Catalytic Activity 374
Abstract 374
Introduction 374
Experimental 375
Materials 375
IR Experiments 375
NMR Experiments 375
Catalytic Tests 375
Results and Discussion 376
Characterization Results 376
27Al MAS and 1H/27Al TRAPDOR NMR Results 376
IR Measurements 377
Catalytic Results 379
Discussion and Conclusion 380
Acknowledgements 380
References 380
Studies on Physicochemical and Catalytic Properties of Borosilicate Zeolites 382
Abstract 382
Introduction 382
Experimental Section 382
Results and Discussion 383
Physicochemical Characterization of Starting Materials: B-SSZ-33, SiOH-SSZ-33 and Si- SSZ-33 383
Physicochemical Characterization of Pt/B-SSZ-33, Pt/SiOH-SSZ-33 and Pt/Si-SSZ-33 386
Catalytic Characterization of Pt/B-SSZ-33, Pt/SiOH-SSZ-33 and Pt/Si-SSZ-33 388
Summary 389
Acknowledgements 389
References 389
Cation Dynamics in Zeolites Studied by MAS-NMR 390
Abstract 390
Experimental Section 390
Results and Discussion 390
Chromate Cancrinite 390
Carbonate Cancrinite 392
Sulfate Cancrinite 393
Conclusions 393
References 394
Dielectric Relaxation Spectroscopy:The Location and De-trapping Energy of Extra-Framework Cations in Zeolites 395
Abstract 395
Introduction 395
Dielectric Relaxation 396
Experimental 396
Materials 396
Experiments 397
Modelling 397
Results and Discussion 397
Conclusion 401
References 401
ESR and ESEEM Study of Silver Clusters in SAPO-17 and SAPO-35 Molecular Sieves 403
Abstract 403
Introduction 403
Experimental 404
Results 404
Discussion 408
Conclusions 409
References 410
Disproporationation of Two Elements, Sulfur and Iodine, upon Sorption into Fully Dehydrated Fully cd2+ -Exchanged Zeolite X 411
Abstract 411
Introduction 411
Experimental Section 411
Results and Discussion 415
References 416
A Quantum Chemical Study of the Interaction of Carbonyls with H-ZSM-5 Zeolite 417
Abstract 417
Introduction 417
Methods 418
Results and Discussion 419
Comparisons of Quantum Cluster with ONIOM Models 419
The Interactions of Acetone and Acetaldehyde with the H-ZSM5 Zeolite 420
Conclusions 422
Acknowledgments 422
References 423
The Interaction of Co and No with Co Sites in CoZSM-5 Zeolite.FTIR, EPR and Theoretical Studies 424
Abstract 424
Introduction 424
Materials and Methods 425
Results and Discussion 425
Transformations Due to the Thermal Activation 425
Structure of Bare Cobalt Sites 427
Interaction of CoZSM-5 with CO 427
Formation of Nitrosyl Adducts with CoZSM-5 429
Conclusions 431
Acknowledgments 432
References 432
Adsorption of Methanol on MCM-36 Derivatives with Strong Acid and Base Sites 433
Abstract 433
Introduction 433
Experimental 434
Results and Discussion 434
Infrared Spectra of Activated Materials 434
Interaction of Methanol with the Zeolitic Bronsted Acid Sites on MCM-22 435
Adsorption of Methanol on (Mixed) Oxide Pillared MCM-36 Materials 436
Reaction of Methanol on Al2O3-MCM-36 437
Thermal Decomposition of Adsorbed Methanol Species 438
Conclusions 439
Acknowledgements 439
References 439
Computational Studies of Hydration in Na+ -Mordenite Zeolites 441
Abstract 441
Introduction 441
Computational Methodology 442
Interatomic Potential 442
Energy Minimisation Procedure 443
Molecular Dynamics Simulation 443
Results and Discussions 443
Conclusion 446
Acknowledgments 446
References 446
Characterization the Bacisity of Calcium-Modified NaZSM-5 Zeolites 447
Abstract 447
Introduction 447
Experimental 447
Results and Discussion 448
Conclusion 454
Acknowledgements 454
References 454
Isomerization of K(CO)+ and K(OC)+ Carbonyls Formed upon CO Adsorption on the Faujasite-Type K-Y Zeolite 455
Abstract 455
Introduction 455
Experimental 456
Results and Discussion 456
Acknowledgements 459
References 459
Motions of K+ Ion in Zeolite L 461
Abstract 461
Introduction 461
Experimental 461
Results and Analyses 462
Discussion 466
Acknowledgements 467
References 467
Color Modification of Ultramarine Analogs Prepared from Zeolites 468
Abstract 468
Introduction 468
Experimental 469
Results and Discussion 469
Conclusions 475
References 475
In Situ Characterisation by Anomalous X-Ray Diffraction of the Cationic Distribution of Dehydrated SrRbX Zeolite 476
Abstract 476
Introduction 476
Experimental Section 477
Results and Discussion 480
Conclusion 482
References 483
Evidence of a Solvent Screen Effect Affecting the Redox Properties of Co(II) Ions in CoApO-37, CoAPO-40 and CoIST-2(AEN), by Cyclic Voltammetry 484
Abstract 484
Introduction 484
Experimental 485
Samples 485
Cyclic Voltamperommetric Measurements 485
Results and Discussion 486
Theoretical Expectations for the Stability of P-(OH)-Co(II) Species in Different Pore Structures 486
Comparative Electrochemical Behavior of CoAPO-37, CoAPO-40 and CoIST-2 486
Conclusions 488
Acknowledgments 489
References 489
The IR Studies of the Status of Cu+ Ions in CuZSM-5 CuBeta and in CuMCM-41 490
Abstract 490
Introduction 490
Experimental 491
Results and Discussion 491
Electron Donor Properties of Cu+ and Activation of Adsorbed Molecule 491
TPD-IR Studies of the Heterogeneity of Cu+ Sites in Zeolites 492
Reduction and Oxidation of Cu+ in Zeolites 493
Acknowledgment 495
References 495
Copper Clusters in Zeolites 496
Abstract 496
Introduction 496
Zeolite Characterization 497
Theoretical Background 499
Calculation of Geometry 500
Calculation of Absorption Bands and Comparison with Experiment 502
Conclusions 502
Acknowledgements 503
References 503
The Reduction of Copper in Porous Matrices 505
Abstract 505
Introduction 505
Experimental 505
Results 506
Discussion 512
Conclusions 512
Acknowledgements 512
References 512
An Infrared and Solid-State NMR Study of the H2S Adsorption on Basic Zeolite 514
Abstract 514
Introduction 514
Experimental 515
Samples 515
IR Study 515
NMR Study 515
Results 516
IR Spectroscopy 516
Proton (1H) MAS NMR 517
Discussions and Conclusions 519
References 520
Room Temperature Interaction of Co with Alkali-Metal Cations in M-ZSM-5 Zeolites as Studied by Joint FT-IR Spectroscopy and Microcalorimetry 521
Abstract 521
Introduction 521
Experimental Section 521
Results and Discussion 522
Conclusions 526
References 527
IR X-Ray and Thermal Studies on Zeolite-13X and its Mn(II) and Zn(II) Exchange and Adsobed Derivatives 528
Abstract 528
Introduction 528
Experimental Methodology 528
Results and Discussion 528
Conclusion 534
References 534
Stabilization and Magnetic Property of Mononuclear Zn+ Species in SAPO-CHA 535
Abstract 535
Introduction 535
Experimental 536
Results and Discussion 536
The Magnetic Susceptibility of the Mononuclear Univalent Zinc 538
The Stabilization of Mononuclear Zn+ Cations in SAPO-CHA 539
The Interaction between the Mononuclear Zn+ Cations and NH3 540
Conclusion 541
Acknowledgments 541
References 541
Deposition of Platinum into Beta-Zeolite 543
Abstract 543
Introduction 543
Experimental Section 544
Results and Discussion 545
Conclusions 548
Acknowledgements 548
References 548
XAFS Investigation of Nanoparticles Supported on Faujasite: Effect of Hydrogen Chemisorption on the Atomic Structure 549
Abstract 549
Introduction 549
Experimental Section 550
Sample Preparation 550
Sample Characterization 550
X-ray Absorption Fine Structure 550
Results and Discussion 550
Conclusion 554
Acknowledgement 555
References 555
Water Relaxation Behavior Inside the Pores and Cages of Some Molecular Sieves 556
Abstract 556
Introduction 556
Experimental 557
Results and Discussions 558
Faujasite 558
Nanoporous Molecular Sieves 559
Discussion 560
Conclusions 562
Acknowledgements 563
References 563
2D-IR Pressure Jump Spectroscopy for the Study of Adsorbed Species on Zeolites (2D-PJAS-IR) 565
Abstract 565
Introduction 565
Experimental Part 565
Results and Discussion 565
Pressure Jump Spectroscopy of Adsorbed Species (PJAS) 565
Gas Phase Acetic Acid: Monomer and Dimer in Equilibrium 567
Study of Adsorbed Acetonitrile on Mordenite 567
Conclusion 570
Acknowledgements 570
References 570
Effect of Hydration Levels and Pressure on Zeolite Structure 572
Abstract 572
Introduction 572
Methodology 573
Results and Discussion 573
The Structure of Scolecite and Natrolite 574
The Dehydration of Scolecite and Natrolite 574
Pressure Induced Overhydration of Natrolite 576
Dehydration of Laumontite 577
Conclusions 579
References 579
Investigation of Conformational Changes of Simple 1-Butene Sorbed in Zeolites by Proton HR MAS NMR Spectroscopy 581
Abstract 581
Introduction: Aim and Scope 581
Experimental 581
1H NMR Chemical Shift:Dynamic of Adsorption 582
2D1H NOESY NMR 584
Homonuclear and Hetronuclear Cross-Relaxation 584
Conclusions 585
References 585
Mobility of Benzene Molecules in NaEMT and KL Zeolitc Nanostructures Studied by 2H NMR Technique 586
Abstract 586
Introduction 586
Experimental 586
Materials and XRD Data Collection 586
Data Treatment 587
Results and Discussion 587
Motion of Benzene in KL Zeolite 588
Motion of Benzene in Naemt Zeolite 589
Conclusions 591
Acknowledgements 591
References 591
Double Interaction between Ammonia and NaY Zeolite and Migration of Na+ upon Adsorption of Ammonia Evidenced by Neutron Diffraction 592
Abstract 592
Introduction 592
Experimental Section 593
Starting Samples 593
Adsorption of d3-ammonia on the Dehydrated Sample 593
Neutron Data Collection and Refinement Details 593
Results and Discussion 593
Conclusions 597
Acknowledgements 597
References 597
An Accelerated Quantum Molecular Dynamics Study of NH3 Interaction with the Bronsted Acid in Periodic Zeolite Models 598
Abstract 598
Introduction 598
Models and Computational Details 599
Results and Discussion 599
References 602
Nuclear Magnetic Resonance Investigation on the Adsorption of Pyrrole over Alkali-Exchanged Zeolites X 604
Abstract 604
Introduction 604
Experimental 605
Materials 605
Solid State NMR 605
Results and Discussion 605
1H MAS NMR: The Validity of Pyrrole as an NMR Probe Molecule 605
23Na MAS NMR of Zeolite NaX 606
23Na and 133Cs MAS NMR of Zeolite CsNaX: The Selective Adsorption of Pyrrole 608
Conclusions 610
Acknowledgements 610
References 610
Experimental and Theoretical Investigations of the Structure and Synthesis of Inorganic-Organic Hybrid Solids 612
Abstract 612
Introduction 612
Methodology 612
Density Functional Theory (DFT) 612
Monte Carlo - Simulated Annealing 613
Results and Discussion 613
The Structure and Synthesis of AlMePO-Alpha and AlMePO-Beta 613
The Structure of Aluminium Benzylphosphonate II (AlBzPO-II) 615
The Synthesis of Zinc Carboxylates Structures 617
Conclusion 618
References 618
Comparison of the Thermal Stability of Ru Cationic Complexes in BEA and Y Zeolites 619
Abstract 619
Introduction 619
Experimental Section 619
Materials 619
Characterizations 620
Results 620
UV-visible Study of the [Ru(NH3)6]3+ Exchange Solution 620
Influence of the Drying Temperature on the Characteristics of the Ru Species 621
Decomposition of the Ru Complexes during Reduction and Ru° Dispersion 623
Conclusion 624
Acknowledgments 625
References 625
Monitoring the Intracrystalline Distribution of Guest Molecules in Zeolites 626
Abstract 626
Introduction 626
Experimental 626
Results and Discussion 627
Methanol in CrAPO-5: Equilibrium with the Vapour Phase 627
Methanol in CrAPO-5: Uptake Kinetics 628
Water in CrAPO-5 and SAPO-5: Equilibrium with the Vapour Phase 629
Methanol in Ferrierite: Uptake Kinetics 629
Conclusion 630
Acknowledgement 631
References 631
Investigation of Adsorption Hysteresis in Microporous Materials 632
Abstract 632
Introduction 632
Experimental and Computer Simulation Procedures 632
Results and Discussion 633
Conclusions 638
References 638
Structural and Dynamic Properties of Confined Water in Model Porous Materials (Alpo4-5, Mcm-41) 639
Abstract 639
Introduction 639
Experimental Section 641
Results and Discussion 641
Water Sorption in the Mesopores of the MCM-41 Sample 641
Finite Size Effects and Diffractogram Modifications 643
Water Sorption in the Micropores of the AIPO4-5 Zeolite 643
Confined Water Properties in the Mesoporous and Microporous Confinement Range 645
Conclusion 646
References 646
The Energetical Contribution of Gas/Liquid Interfaces during Mesopores Filling Processes:A Thermodynamical Study 647
Abstract 647
Introduction 647
Experimental 647
Results 648
Conclusion 651
References 651
Adsorption of Toluene over Faujasite Zeolite Investigated by the Combined Quantum Mechanics/Molecular Mechanics Method 652
Abstract 652
Introduction 652
Method 653
Results and Discussion 653
Structures of Faujasite Zeolite Models 653
Interactions of Toluene with Faujasite Zeolites 655
Conclusions 656
Acknowledgments 656
References 656
1H and 13C NMR Studies of Long Chain Hydrocarbons Adsorbed on MCM-41 and Zeolite Nax 658
Abstract 658
Introduction 658
Experimental 659
Sample Preparation 659
NMR Measurements 659
Results and Discussions 659
Conclusions 664
References 664
Molecular Spring or Bumper: A New Application for Hydrophobic Zeolitic Materials 665
Abstract 665
Introduction 665
Experimental 667
Synthesis and Characterization 667
Compressibility Tests 667
Results and Discussion 667
Characteristics of the Zeolite Samples 667
The Silicalite-1 (F) Sample 667
The Decadodecasil 3R Sample 668
The Zeolite Beta (F) Sample 668
Pressure-Volume Isotherms 670
Conclusion 672
Acknowledgments 672
References 672
Hydrogen Storage and Diffusion in 6-Ring Clathrasils 673
Abstract 673
Introduction 673
Theory 674
Results 675
Discussion 676
Conclusion 678
References 678
Structure and Energetics of Nitrous Oxide and Methane Adsorption on the Fe-ZSM-5 Zeolite: ONIOM and Density Functional Studies 679
Abstract 679
Introduction 679
Methods 680
Results and Discussion 681
Structures of the Alpha-site [Fe(II)O+/ZSM-5-] 681
Structures of the Alpha-oxygen Loaded Site [Fe(III)O2+/ZSM-5-] 681
Adsorption of Nitrous Oxide on the Alpha-site 681
Adsorption of Methane on the Alpha-oxygen Loaded Site 682
Conclusions 682
Acknowledgments 683
References 683
Molecular Simulation for Adsorption of Chlorinated Hydrocarbon in Y-Type Zeolites 684
Abstract 684
Introduction 684
Experimental 684
Gravimetric Method 684
Chromatographic Method [1] 685
Simulation 686
Models 686
Results and Discussion 688
The System of PQ-USY 688
The System of USY6.18 688
Molecular Dynamics (MD) Method 689
Conclusions 691
Nomenclature 692
References 692
Adsorption of Bulky Nitrosamines on Zeolite with Small Pore Size 693
Abstract 693
Introduction 693
Experimental 693
Results and Discussion 694
The Structure of Nitrosamine and the Analysis of the Adsorption Model 694
The Actual Adsorption of NHMI and NNN on the Zeolites with Small Pore Size 695
Conclusion 699
Acknowledgements 700
References 700
Sorption of Volatile Organic Compounds on Zeolites with Microwave Irradiation 701
Abstract 701
Introduction 701
Experimental 701
Results 702
Adsorption and Desorption of Pure Products with and without Microwave Irradiation 702
Chlorobenzene 702
Adsorption of Cyclohexane and Methanol 703
Desorption of Cyclohexane and Methanol 704
Adsorption and Desorption of Mixtures 704
Methanol/Cyclohexane 704
Chlorobenzene/Cydohexane 705
Discussion and Conclusion 705
Acknowledgement 706
References 706
Co-Template Impact on Structure of AFI Type Crystals: An Adsorption Study 707
Abstract 707
Introduction 707
Experimental 708
Results and Discussion 708
Materials 708
Adsorption of Nitrogen 708
Adsorption of Benzene 710
Adsorption of Water 710
Conclusions 714
Acknowledgements 714
References 714
Removal of Uranyl Carbonate Complex using Zeolites and MCM-41/ZSM-5 Composite 715
Abstract 715
Introduction 715
Experimental 716
Result and Discussion 716
Applied Zeolites 716
Applied MCM-41/ZSM-5 718
Acknowledgment 719
References 720
Evaluation of Iron Modified Zeolites for Removal of Arsenic from Drinking Water 723
Abstract 723
Introduction 723
Materials and Methods 724
Results and Discussion 724
Conclusion 729
Acknowledgements 729
References 730
Removal of Metal-Complex Dyestuffs by Croatian Clinoptilolite 731
Abstract 731
Introduction 731
Experimental Section 732
Samples 732
Sample Characterization 732
Treatment Procedure of the Clinoptilolite 732
General Procedures 732
Results and Discussion 733
Conclusions 736
References 737
Vitrification of CsA and CsX Zeolites 738
Abstract 738
Introduction 738
Experimental 738
Results and Discussion 739
Conclusion 742
References 742
Alkali Cations Exchange in MCM-22 743
Abstract 743
Introduction 743
Experimental 744
Materials 744
Equilibrium Studies 744
Treatment of Data 744
Structure Refinements 745
Results and Discussion 745
Ion Exchange Isotherms 745
Thermodynamic Treatment of Data 746
Structure Refinement 747
Conclusion 750
References 750
Ion Exchange Equilibria in a Synthetic Merlinoite 751
Abstract 751
Introduction 751
Materials and Methods 752
Materials and their Characterization 752
Cation Exchange Capacity 752
Ion Exchange Runs 753
Analytical Procedures 753
Computation of the Thermodynamic Parameters 753
Results 754
Merlinoite Characterization 754
Ion Exchange Equilibria 755
Thermodynamic Parameters 756
Discussion 757
Conclusion 757
References 758
Ionic Exchange and Thermal Characterisation of Different Cation Exchanged forms of ETS-4 760
Abstract 760
Introduction 760
Experimental 760
Results and Discussion 760
Thermal Characterization 762
Ionic Exchange in Equilibrium Conditions 763
Application of Different Exchanged Cationic forms of ETS-4 for the Removal of Ammonium 764
Characterization of NH4-ETS-4 764
Conclusion 765
Acknowledgements 765
References 765
Modelling of n-Hexane and 3-Methylpentane Permeation through a Silicalite-1 Membrane 766
Abstract 766
Introduction 766
Modelling 767
Single-component Permeation 767
Binary Mixture Permeation 768
Experimental 769
Results and Discussion 769
Single-component Permeation 769
Binary Mixture Permeation 771
Conclusion 773
References 773
Chromatographic Liquid Phase Separation of n-Alkane Mixtures using Zeolites 775
Abstract 775
Introduction 775
Experimental 775
Results and Discussion 776
Conclusions 780
Acknowledgements 780
References 780
Long-Chain Paraffins Adsorption over 5A Zeolites 781
Abstract 781
Introduction 781
Experimental Section 782
Materials 782
Procedure for Gravimetric Runs 782
XRD Experiments 782
Results and Discussion 783
Variation of the Calcium Exchange Ratio 783
Thermal Treatment Effect 785
Conclusion 787
Acknowledgement 787
References 787
Enantioselective Adsorption of Hydrobenzoin on Zeolite Beta 788
Abstract 788
Introduction 788
Experimental 789
Results and Discussion 790
Conclusion 791
References 791
Sorption Equilibria of Nitrogen and Oxygen on Li,RE-LSX Zeolite for Oxygen PVSA Processes 792
Abstract 792
Introduction 792
Experimental 792
Sorption Experiments 792
Mathematical Experiments 793
Sorbents and their Characterization 793
Results and Discussion 796
Sorption-thermodynamic Data 796
Li,RELSX Structures for Simulation 797
Simulation Results and Discussion with Other Characterization Data 797
Conclusions 800
Acknowledgments 800
References 800
Time Resolved Multicomponent Sorption of Linear and Branched Alkane Isomers on Zeolites, using NIR Spectroscopy 802
Abstract 802
Introduction 802
Experimental Section 803
Results and Discussion 804
Single Component Isotherms 804
Near Infrared Spectroscopy 804
Conclusions 808
Acknowledgements 808
References 808
SMB: Mono-Methyl Paraffin Separation 809
Abstract 809
Introduction 809
MMP Sorbex TM Development 809
Silicalite Adsorbent 809
Molecular Simulation 810
Pulse Test 810
Sorbex Pilot Plant Demonstration 813
Conclusion 813
References 813
Molecular Siting in the Liquid-Phase Adsorption of Alkane and Aromatic Mixtures in MFI Zeolites:An Experimental and Molecular Modeling Study 814
Abstract 814
Introduction 814
Methods 815
Thermodynamic Equilibrium 815
Mixtures of Aromatics 815
Mixtures of Alkanes 816
Experiments for Mixtures of Alkanes 816
Results 816
Conclusions 821
Acknowledgments 821
References 821
Chromatographic Adsorption Measurement of Chlorinated Organics on High Silica Zeolite 822
Abstract 822
Introduction 822
Experimental Procedure and Conditions and Method of Analysis 822
Result 824
Adsorption Equilibrium Constant 826
Axial Dispersion 826
Diffusion in Macropore 827
Diffusion in Micropore 827
Discussion 828
Conclusion 828
Notation 829
References 829
Solvent Recovery by PSA with High Silica Zeolite:An Experimental and a Simulation Study 832
Abstract 832
Introduction 832
Experimental 832
Adsorption Equilibria 832
PSA Experimental Procedure 833
Results 834
Result for EX20P 835
Result for PQ-USY 835
Comparison of PQ-USY with EX20P 836
Breakthrough Curves and Simulation 836
PSA Simulation 837
Discussion 837
Prediction of the Adsorption in the Adsorption Bed 837
Toward Optimization 839
Non Isothermal Effect 839
Conclusion 840
References 840
Adsorption Removal of the Mixed Organic Solvent Stream by High Silica Zeolite 841
Abstract 841
Introduction 841
Experimental 841
Adsorbent 841
Experimental Procedure 841
Molecular Simulation 842
Result and Discussion 842
Breakthrough Curves 842
Adsorption Equilibria 842
Stop and Go Method 843
Molecular Simulation 846
Conclusion 847
References 848
Continuous Separation of Amino Acids from Aqueous Solution in a Flow-Type Adsorber by Molecular Sieve Adsorbents 849
Abstract 849
Introduction 849
Experimental Section 849
Adsorbent Preparation and Characterization 849
Batch Adsorption of Amino Acids 850
Continuous Adsorption of Amino Acids 850
Results and Discussion 851
Conclusions 854
Acknowledgements 855
References 855
The Application of Zeolite/FAC Composites in Protein Separation 856
Abstract 856
Introduction 856
Experimental Section 857
Preparation of the ZSM-5/FAC 857
Immobilization of Transitional Metal Ions 857
Protein Separation Process 857
Results and Discussion 858
Preparation and Characterization of ZSM-5/FAC Composites 858
Protein Separation 860
Conclusion 861
Acknowledgements 861
References 862
Reduction of Hydrocarbon Emission from Engine Exhaust using Zeolitic Adsorbers 863
Abstract 863
Introduction 863
Experimental 864
Adsorbent Materials 864
Equilibrium Adsorption Measurements 865
Dynamic Adsorption Measurements 865
Results and Discussion 866
Adsorption Measurements with Single Hydrocarbons or Artificial Mixtures 866
Adsorption Measurements in Real Condition with Engine Exhaust Gas 867
Conclusions 868
Acknowledgments 868
References 868
Mass Transfer Processes during Sorption and Diffusion of Aromatic Molecules on Medium Pore Zeolites 870
Abstract 870
Introduction 870
Experimental 871
Sample 871
Experimental Setup 871
Principle IR Spectroscopic Method Applied 871
Sample Preparation, Activation 872
Data Analysis 872
Results 872
Discussion 874
Conclusions 876
Acknowledgments 876
References 876
Diffusion of n-Hexane into the Etched ZSM-5 Crystals 878
Abstract 878
Introduction 878
Experimental 879
Results and Discussion 879
Conclusions 884
Acknowledgements 884
References 884
Diffusivities of Co2 and N2 in Silicalite, Comparison between Quasi-Elastic Neutron Scattering and Molecular Simulations 885
Abstract 885
Introduction 885
Quasi-elastic Neutron Scattering Experiments 885
Molecular Dynamics Simulations 886
Results and Discussion 887
Acknowledgments 890
References 890
Development of Thermodynamically Consistent, Experiment-Based Molecular Models of Diffusion through Thin Microporous Membranes 891
Abstract 891
Introduction 891
Capturing Equilibrium Diffusion Behavior Via Lattice Models 892
Thermodynamic Consistency of Hybrid Molecular-Based and Experiment-Based Models 893
Factorial Design Approaches to Experimental Parameterization of Lattice Monte Carlo Models 895
Effects of Thermodynamic Inconsistency on Equilibrium Solutions 896
Modeling Transport through Very Thin Membranes 896
Conclusions 897
References 897
Mobility of Nitrogen in Li, RE-LSX Zeolite Beads 899
Abstract 899
Introduction 899
Experimental 899
Frequency-response Technique 899
Piezometric Sorption-kinetic Technique 900
Sorbent 900
Results and Discussion 901
Nitrogen Mobility in Li,RE-LSX Beads 901
Identification of Mass-transfer Mechanism by FR Technique 901
Effective and Macropore Diffiisivities 901
Temperature Dependencies of Effective and Macropore Diffusivities 902
Concentration Dependence of Effective Time Constants 903
Overall Uptake-rate Constants for Nitrogen 904
Conclusions 905
References 906
Adsorption and Diffusion of Nitrogen and Oxygen in Natural Mordenites 907
Abstract 907
Introduction 907
Experimental Section 908
Materials 908
Adsorption Isotherms 908
DRIFT Spectroscopy 908
Mercury Porosimetry 908
FR Spectroscopy 909
Results and Discussion 909
Conclusions 913
Acknowledgements 914
References 914
Drift Spectroscopy of Nitrogen Diffusion, Codiffusion and Counterdiffusion from N2-O2 Mixtures in Zeolites 915
Abstract 915
Introduction 915
Experimental 915
Results and Discussion 916
The NaLSX and NaZSM-5 Systems 916
The NaA System 921
Conclusions 923
References 923
Multicomponent Diffusion and Sorption Analysis of the Direct Hydroxylation of Methyl-Aromatics on Zeolites 925
Abstract 925
Introduction 925
Experimental 926
Modelling 926
Results and Discussion 928
Conclusions 931
References 932
A Molecular Dynamics (MD) Study of Methane in Silicalite-1: A Novel Moller-Plesset Potential Energy Surface 933
Abstract 933
Introduction 933
Novel Intermolecular Pair Potential 934
Molecular Dynamics Simulations 934
Results and Discussion 935
Conclusion 937
Acknowledgements 937
References 938
Random Walk Treatment of Dumb-Bell Molecules in an LTA Zeolite and in Chabazite 939
Abstract 939
Introduction 939
Simulation Details 941
Analytical Treatment and Results 941
Ethane in Cation-Free Zeolite LTA 941
Ethane and Chlorine in Silicious Chabazite 944
Conclusions 946
References 946