<p>Foreword XIII</p> <p>Preface XVII</p> <p>List of Contributors XXV</p> <p><b>1 Strategies to Improve the Accessibility to the Intracrystalline Void of ZeoliteMaterials: Some Chemical Reflections 1</b><br /><i>Joaquén Pérez-Pariente and Teresa Álvaro-Münoz</i></p> <p>1.1 Introduction 1</p> <p>1.2 Strategies to Obtain New Large-Pore Materials 5</p> <p>1.3 Methodologies to Control the Crystallization Process of Zeolite Materials in the Absence of Pore-Forming Agents 9</p> <p>1.3.1 Confined Nucleation and Growth 11</p> <p>1.3.2 Use of Blocking Agents for Crystal Growth 13</p> <p>1.3.2.1 Silanization Methods 13</p> <p>1.3.2.2 Use of Surfactants in the Synthesis of Silicoaluminophosphates 16</p> <p>1.3.3 Synthesis in the Presence of Pore-Forming Agents 18</p> <p>1.4 Postsynthesis Methodologies 21</p> <p>1.4.1 Materials with High Structural Anisotropy: Layered Zeolites 21</p> <p>1.4.2 Removal/Reorganization of T Atoms in the Crystal Bulk 23</p> <p>1.5 Conclusions 24</p> <p>Acknowledgments 25</p> <p>References 25</p> <p><b>2 Zeolite Structures of Nanometer Morphology: Small Dimensions, New Possibilities 31</b><br /><i>Heloise de Oliveira Pastore and Dilson Cardoso</i></p> <p>2.1 The Structures of Zeolites 34</p> <p>2.1.1 FAU and EMT Structures: Zeolites X and Y 34</p> <p>2.1.2 LTA Structure 50</p> <p>2.1.3 BEA Structure 52</p> <p>2.1.4 Pentasil Zeolites, MFI, and MEL Structures: ZSM-5, ZSM-11, and S-1 56</p> <p>2.2 The Structures of Zeotypes: Aluminophosphates and Silicoaluminophosphates 63</p> <p>2.3 Lamellar Zeolites 66</p> <p>2.4 Conclusions and Perspectives 71</p> <p>References 75</p> <p><b>3 Nanozeolites and Nanoporous Zeolitic Composites: Synthesis and Applications 79</b><br /><i>Gia-Thanh Vuong and Trong-On Do</i></p> <p>3.1 Introduction 79</p> <p>3.2 Synthesis of Nanozeolites 81</p> <p>3.2.1 Principles 81</p> <p>3.2.2 Synthesis from Clear Solutions 87</p> <p>3.2.2.1 Parameters Affecting the Crystal Size 87</p> <p>3.2.3 Synthesis Using Growth Inhibitor 90</p> <p>3.2.4 Confined Space Synthesis 91</p> <p>3.2.5 Synthesis of Nanozeolites Using Organic Media 95</p> <p>3.3 Nanozeolite Composites 98</p> <p>3.4 Recent Advances in Application of Nanozeolites 106</p> <p>3.5 Conclusions and Perspectives 109</p> <p>References 110</p> <p><b>4 Mesostructured and Mesoporous Aluminosilicates with Improved Stability and Catalytic Activities 115</b><br /><i>Yu Liu</i></p> <p>4.1 Introduction 115</p> <p>4.2 Zeolite/Mesoporous Composite Aluminosilicates 116</p> <p>4.2.1 Synthesis of Zeolite/Mesoporous Composite Material 116</p> <p>4.2.2 Catalytic Evaluation of Zeolite/Mesoporous Composite Material 124</p> <p>4.3 Posttreatment of Mesostructured Materials 128</p> <p>4.3.1 Posttreatment of Mesoporous Materials by Zeolite Structure-Directing Agents or Zeolite Nanocrystals 128</p> <p>4.3.2 Postsynthesis Grafting of Aluminum Salts on theWalls of Mesostructured Materials 133</p> <p>4.4 Mesostructured and Mesoporous Aluminosilicates Assembled from Digested Zeolite Crystals 135</p> <p>4.5 Mesostructured and Mesoporous Aluminosilicates Assembled from Zeolite Seeds/Nanoclusters 141</p> <p>4.5.1 Assembly of Mesostructured Aluminosilicates from Zeolite Y Seeds 141</p> <p>4.5.2 Assembly of Mesostructured Aluminosilicates from Pentasil Zeolite Seeds 145</p> <p>4.6 Conclusions 152</p> <p>References 153</p> <p><b>5 Development of Hierarchical Porosity in Zeolites by Using Organosilane-Based Strategies 157</b><br /><i>David P. Serrano, José M. Escola, and Patricia Pizarro</i></p> <p>5.1 Introduction 157</p> <p>5.2 Types of Silanization-Based Methods 159</p> <p>5.2.1 Functionalization of Protozeolitic Units with Organosilanes 159</p> <p>5.2.1.1 Fundamentals of the Method 159</p> <p>5.2.1.2 Influence of the Organosilane Type 163</p> <p>5.2.1.3 Application to Different Zeolites 166</p> <p>5.2.1.4 Influence of the Silica Source 168</p> <p>5.2.1.5 Reduction of the Gel Viscosity by Means of Alcohols 169</p> <p>5.2.1.6 State of the Aluminum and Acidity 171</p> <p>5.2.2 Use of Silylated Polymers 173</p> <p>5.2.3 Use of Amphiphile Organosilanes 175</p> <p>5.3 Catalytic Applications 180</p> <p>5.3.1 Fine Chemistry 180</p> <p>5.3.2 Oil Refining and Petrochemistry 185</p> <p>5.3.3 Production of Advanced Fuels 189</p> <p>5.4 Conclusions 193</p> <p>5.5 New Trends and Future Perspectives 195</p> <p>References 196</p> <p><b>6 Mesoporous Zeolite Templated from Polymers 199</b><br /><i>Xiangju Meng and Feng-Shou Xiao</i></p> <p>6.1 Introduction 199</p> <p>6.2 Cationic Polymer Templating 200</p> <p>6.3 Nonionic Polymer Templating 203</p> <p>6.4 Silane-Functionalized Polymer Templating 208</p> <p>6.5 Polymer–Surfactant Complex Templating 210</p> <p>6.6 Morphology Control of Mesoporous Zeolites Using Polymers 212</p> <p>6.7 Zeolites with Oriented Mesoporous Channels 218</p> <p>6.8 Microfluidic Synthesis of Mesoporous Zeolites 220</p> <p>6.9 Nonsurfactant Cationic Polymer as a Dual-Function Template 220</p> <p>6.10 Conclusions 224</p> <p>References 224</p> <p><b>7 Nanofabrication of Hierarchical Zeolites in Confined Space 227</b><br /><i>Zhuopeng Wang and Wei Fan</i></p> <p>7.1 Introduction of Confined Space Synthesis 227</p> <p>7.2 General Principles of Confined Space Synthesis 228</p> <p>7.3 Crystallization Mechanisms of Zeolite under Hydrothermal Conditions 228</p> <p>7.4 Preparation of Synthesis Gel within the Confined Space of Inert Matrices 230</p> <p>7.5 Crystallization of Zeolite within Confined Space 230</p> <p>7.6 Synthesis of Hierarchical Zeolites in Carbon Blacks, Nanotubes, and Nanofibers by SAC Method 232</p> <p>7.7 Synthesis of Hierarchical Zeolites within Ordered Mesoporous Carbons by SAC and VPTMethods 234</p> <p>7.8 Synthesis of Hierarchical Zeolites within Carbon Aerogels, Polymer Aerogels, and other Carbon Materials 241</p> <p>7.9 Synthesis of Hierarchical Zeolites within Carbon Materials Using Seeded Growth Method 243</p> <p>7.10 Confined Synthesis of Zeolites in Polymer and Microemulsions 248</p> <p>7.11 Conclusions 250</p> <p>References 253</p> <p><b>8 Development of Hierarchical Pore Systems for Zeolite Catalysts 259</b><br /><i>Masaru Ogura and Masahiko Matsukata</i></p> <p>8.1 Introduction 259</p> <p>8.2 Alkali Treatment of ZSM-5: Effects of Alkaline Concentration, Treatment Temperature, and Treatment Duration 260</p> <p>8.3 Desilication of ZSM-5: Effects of Temperature and Time 263</p> <p>8.4 Alkali Treatment of ZSM-5 with Various Si/Al Molar Ratios: Effect of Si/Al on Mesopore Formation 263</p> <p>8.5 Desilication of ZSM-5: Effects of Other Descriptors 272</p> <p>8.6 Desilication of Silicalite-1 273</p> <p>8.7 Desilication of Other Zeolites: Multidimensionalization of Low-Dimensional Microstructures 277</p> <p>8.8 Desilicated Zeolites for Applications – Test Reactions 280</p> <p>8.9 Desilicated Zeolites for Applications – Superior Diffusion 284</p> <p>8.10 Desilicated Zeolites for Novel Applications 289</p> <p>8.11 Summary 291</p> <p>References 292</p> <p><b>9 Design and Catalytic Implementation of Hierarchical Micro–Mesoporous Materials Obtained by Surfactant-Mediated Zeolite Recrystallization 295</b><br /><i>Irina I. Ivanova, Elena E. Knyazeva, and Angelina A. Maerle</i></p> <p>9.1 Introduction 295</p> <p>9.2 Mechanism of Zeolite Recrystallization 296</p> <p>9.3 Synthetic Strategies Leading to Different Types of Recrystallized Materials 301</p> <p>9.4 Coated Mesoporous Zeolites (RZEO-1) 303</p> <p>9.5 Micro–Mesoporous Nanocomposites (RZEO-2) 308</p> <p>9.6 Mesoporous Materials with Zeolitic Fragments in theWalls (RZEO-3) 312</p> <p>9.7 Conclusions 316</p> <p>Acknowledgment 318</p> <p>References 318</p> <p><b>10 Surfactant-Templated Mesostructuring of Zeolites: FromDiscovery to Commercialization 321</b><br /><i>Kunhao Li,Michael Beaver, Barry Speronello, and Javier García-Martínez</i></p> <p>10.1 Introduction 321</p> <p>10.2 Surfactant-Templated Mesostructuring of Zeolites 326</p> <p>10.3 Mesostructured Zeolite Y for Fluid Catalytic Cracking Applications 334</p> <p>10.4 Beyond Catalysis: Mesostructured Zeolite X for Adsorptive Separations 341</p> <p>10.5 Concluding Remarks 344</p> <p>References 345</p> <p><b>11 Physical Adsorption Characterization of Mesoporous Zeolites 349</b><br /><i>Matthias Thommes, Rémy Guillet-Nicolas, and Katie A. Cychosz</i></p> <p>11.1 Introduction 349</p> <p>11.2 Experimental Aspects 352</p> <p>11.2.1 General 352</p> <p>11.2.2 Choice of Adsorptive 354</p> <p>11.3 Adsorption Mechanism 357</p> <p>11.4 Surface Area, Pore Volume, and Pore Size Analysis 363</p> <p>11.4.1 Surface Area 363</p> <p>11.4.2 Pore Size Analysis 367</p> <p>11.4.2.1 General Aspects 367</p> <p>11.4.2.2 Pore Size Analysis: Hierarchically Structured Materials 370</p> <p>11.5 Probing Hierarchy and Pore Connectivity in Mesoporous Zeolites 376</p> <p>11.6 Summary and Conclusions 378</p> <p>References 379</p> <p><b>12 Measuring Mass Transport in Hierarchical Pore Systems 385</b><br /><i>Jörg Kärger, Rustem Valiullin, Dirk Enke, and Roger Gläser</i></p> <p>12.1 Types of Pore Space Hierarchies in Nanoporous Host Materials 385</p> <p>12.2 Hierarchy of Mass Transfer Parameters and Options of Their Measurement Techniques 389</p> <p>12.2.1 Diffusion Fundamentals 389</p> <p>12.2.2 Techniques of Diffusion Measurement 392</p> <p>12.2.2.1 Macroscopic Diffusion Studies: Uptake and Release 392</p> <p>12.2.2.2 Microscopic Diffusion Measurement: Molecular Displacements 396</p> <p>12.2.2.3 Microscopic Diffusion Measurement: Transient Concentration Profiles 399</p> <p>12.3 Diffusion Measurement in Various Types of Pore Space Hierarchies 400</p> <p>12.3.1 Macro/Meso 400</p> <p>12.3.2 Macro/Micro 401</p> <p>12.3.3 Meso/Meso 404</p> <p>12.3.4 Meso/Micro 407</p> <p>12.3.4.1 PFG NMR DiffusionMeasurements in Y-Type Zeolites: A Case Study with FCC Catalysts 407</p> <p>12.3.4.2 Mass Transfer in Mesoporous LTA-Type Zeolites: An In-Depth Study of Diffusion Phenomena in Mesoporous Zeolites 409</p> <p>12.3.4.3 Diffusion Studies with Mesoporous Zeolite of Structure-Type CHA: Breakdown of the Fast-Exchange Model 414</p> <p>12.3.4.4 The Impact of Hysteresis 415</p> <p>12.4 Conclusions and Outlook 416</p> <p>References 417</p> <p><b>13 Structural Characterization of Zeolites and Mesoporous Zeolite Materials by ElectronMicroscopy 425</b><br /><i>Wei Wan, Changhong Xiao, and Xiaodong Zou</i></p> <p>13.1 Introduction 425</p> <p>13.2 Characterization of Zeolites by Electron Diffraction 426</p> <p>13.2.1 Geometry of Electron Diffraction 427</p> <p>13.2.2 Conventional Electron Diffraction 428</p> <p>13.2.3 Three-Dimensional (3D) Electron Diffraction 430</p> <p>13.3 Characterization of Zeolite and Mesoporous Materials by High-Resolution Transmission Electron Microscopy 433</p> <p>13.3.1 Introduction to HRTEM 433</p> <p>13.3.2 Working with Electron-Beam-Sensitive Materials 434</p> <p>13.3.3 Structure Projection Reconstruction from Through-Focus HRTEM Images 435</p> <p>13.3.4 3D Reconstruction of HRTEM Images 437</p> <p>13.4 Characterization of Zeolite and Mesoporous Materials by Electron Tomography (ET) 440</p> <p>13.4.1 Basic Principles of Electron Tomography 440</p> <p>13.4.2 Applications of Electron Tomography on Mesoporous Zeolites 443</p> <p>13.4.2.1 Quantification of Mesopores in Zeolite Y 443</p> <p>13.4.2.2 Quantification of Pt Nanoparticles in Mesoporous Zeolite Y 444</p> <p>13.4.2.3 Orientation Relationship between the Intrinsic Micropores of Zeolite Y andMesopore Structures 445</p> <p>13.4.2.4 Single-Crystal Mesoporous Zeolite Beta Studied by Transmission Scanning Electron Microscopy (STEM) 448</p> <p>13.5 Other Types of Mesoporous Zeolites Studied by EM 450</p> <p>13.5.1 Aluminosilicate Zeolite ZSM-5 Single Crystals with b-Axis-Aligned Mesopores 450</p> <p>13.5.2 Mesoporous Zeolite LTA 451</p> <p>13.5.3 Ultrasmall EMT Crystals with Intercrystalline Mesopores from Organic Template-Free Synthesis 452</p> <p>13.5.4 Self-Pillared Zeolites with Interconnected Micropores and Mesopores 452</p> <p>13.6 Future Perspectives 454</p> <p>13.7 Conclusions 455</p> <p>Acknowledgments 456</p> <p>References 456</p> <p><b>14 Acidic Properties of Hierarchical Zeolites 461</b><br /><i>Jerzy Datka, Karolina Tarach, and Kinga Góra-Marek</i></p> <p>14.1 Short Overview of Experimental Methods Employed for Acidity Investigations 461</p> <p>14.2 Hierarchical Zeolites Obtained by Templating and Dealumination of Composite Materials 463</p> <p>14.2.1 Surfactant Templating Approach 465</p> <p>14.2.2 Dealumination 470</p> <p>14.3 Hierarchical Zeolites Obtained by Desilication 471</p> <p>14.3.1 Studies of Desilicated Zeolites Acidity 471</p> <p>14.3.1.1 Analysis of the Hydroxyl Groups Spectra 471</p> <p>14.3.1.2 Concentration of Acid Sites 474</p> <p>14.3.1.3 Studies of Acid Sites Strength 475</p> <p>14.3.1.4 Realumination: Mesopore Surface Enrichment in Al Species 476</p> <p>14.3.1.5 Nature and Origin of Lewis Acid Sites in Desilicated Zeolites 477</p> <p>14.3.2 Accessibility of Acid Sites in Desilicated Zeolites 481</p> <p>14.4 Conclusions and Future Perspectives 487</p> <p>Acknowledgments 489</p> <p>References 489</p> <p><b>15 Mesoporous Zeolite Catalysts for Biomass Conversion to Fuels and Chemicals 497</b><br /><i>Kostas S. Triantafyllidis, Eleni F. Iliopoulou, Stamatia A. Karakoulia, Christos K. Nitsos, and Angelos A. Lappas</i></p> <p>15.1 Introduction to Mesoporous/Hierarchical Zeolites 497</p> <p>15.2 Potential of Hierarchical Zeolites as Catalysts for the Production of Renewable/Biomass-Derived Fuels and Chemicals 503</p> <p>15.3 Catalytic Fast Pyrolysis (CFP) of Lignocellulosic Biomass 508</p> <p>15.4 Catalytic Cracking of Vegetable Oils 514</p> <p>15.5 Hydroprocessing of Biomass-Derived Feeds 516</p> <p>15.6 Methanol to Hydrocarbons 524</p> <p>15.6.1 Methanol to Dimethyl Ether (DME) 525</p> <p>15.6.2 Methanol to Gasoline (MTG)/Methanol to Olefins (MTO) 527</p> <p>15.7 Other Processes 533</p> <p>15.8 Summary and Outlook 535</p> <p>References 536</p> <p><b>16 Industrial Perspectives for Mesoporous Zeolites 541</b><br /><i>Roberto Millini and Giuseppe Bellussi</i></p> <p>16.1 Introduction 541</p> <p>16.2 Enhancing the Effectiveness of the Zeolite Catalysts 543</p> <p>16.2.1 Increasing the Pore Size 544</p> <p>16.2.2 Hierarchical (Mesoporous) Zeolites 546</p> <p>16.3 Industrial Assessment of Mesoporous Zeolite 555</p> <p>16.4 Conclusions 560</p> <p>References 561</p> <p>Index 565</p>