The contents of this title are based on topics to be discussed by invited lecturers, which deal with periodic mesoporous organosilicas, stability and catalytic activity of aluminosilicate mesostructures, electron microscopy studies of ordered materials, imprinted polymers and highly porous metal-organic frameworks. The other contributions deal with tailoring the surface and structural properties of nanoporous materials, giving a detailed characterization as well as demonstrating their usefulness for advanced adsorption and catalytic applications.
Nanoporous Materials III contains the invited lectures and peer-reviewed oral and poster contributions to be presented at the 3rd Conference on Nanoporous Materials, which will be hosted in Ottawa, Canada, June 2002. The work covers complementary approaches to and recent advances in the field of nanostructured materials with pore sizes larger than 1nm, such as periodic mesoporous molecular sieves M41S and FSM16 and related materials including clays, carbon molecular sieves, colloidal crystal templated organic and inorganic materials, porous polymers and sol gels. The broad range of topics covered in relation to the synthesis and characterization of ordered mesoporous materials are of great importance for advanced adsorption, catalytic and separation processes as well as the development of nanotechnology. The contents of this title are based on topics to be discussed by invited lecturers, which deal with periodic mesoporous organosilicas, stability and catalytic activity of aluminosilicate mesostructures, electron microscopy studies of ordered materials, imprinted polymers and highly porous metal-organic frameworks. The other contributions deal with tailoring the surface and structural properties of nanoporous materials, giving a detailed characterization as well as demonstrating their usefulness for advanced adsorption and catalytic applications.
Cover 1
CONTENTS 10
Preface 6
Organizing Committee 8
Intemational Advisory Committee 8
Section I: Plenary Lectures 20
Chapter 1. Recent Developments in the Synthesis and Chemistry of Periodic Mesoporous Organosilicas 20
Chapter 2. Porous Materials: Looking Through the Electron Microscope 46
Chapter 3. Molecular Imprinting - A Way to Prepare Effective Mimics of Natural Antibodies and Enzymes 54
Section II: Synthesis of Mesoporous Silicas 64
Chapter 4. Plugged Hexagonal Mesoporous Templated Silica: A Unique Micro- and Mesoporous Material with Internal Silica Nanocapsules 64
Chapter 5. Imprinting of the Surface of Mesoporous Silicates using Organic Structure Directing Agents 72
Chapter 6. Synthesis and Characterization of Polymer-Templated Ordered Silica with Cage-like Mesostructure 80
Chapter 7. The Modeling of Wall Structure of Siliceous MCM-41 Based on the Formation Process 88
Chapter 8. Pore Size Adjustment of Bimodal-mesoporous Silica Molecular Sieves 96
Chapter 9. Alcothermal Synthesis of Large Pore, High Quality MCM-48 Silica 104
Chapter 10. Studies of MCM-41 Obtained from Different Sources of Silica 112
Chapter 11. Synthesis and Characterization of Hexagonal Mesoporous Materials Using Hydrothermal Restructuring Method 120
Chapter 12. Synthesis of Highly Ordered Mesoporous Compounds with Control of Morphology Using a Non-ionic Surfactant as Template 120
Chapter 13. Towards a Better Understanding on the Mechanism of Mesoporous Formation via an Assembly of Cn(EO)m TMOS 136
Chapter 14. Mesoporous Silicas via Organic-Inorganic Hybrids Based on Charged Polymers 146
Chapter 15. Mesoporous Silicas of Hierarchical Structure by Hydrothermal Surfactant-Templating under Mild Alkaline Conditions 152
Section III: Synthesis of Framework-Modified Mesoporous Silicas 160
Chapter 16. Synthesis and Characterisation of Super-microporous Aluminosilicates Prepared via Primary Amine Templating 160
Chapter 17. A1-MCM-41 Synthesis Studies Using Al-Isopropoxide as A1 Source 170
Chapter 18. Mesoporous Aluminosilicates from Coal Fly Ash 178
Chapter 19. New Route for Synthesis of Highly Ordered Mesoporous Silica with Very High Titanium Content 186
Chapter 20. Synthesis and Characterization of Ti-containing Mesoporous Alumina Molecular Sieves 192
Section IV: Synthesis of Surface-Modified Mesoporous Silicas 202
Chapter 21. Organizing One-Dimensional Molecular Wires in Ordered Mesoporous Silica 202
Chapter 22. Synthesis and Catalytic Properties of Organically Modified Ti-HMS 208
Chapter 23. Synthesis and Characterization of Methyl- and Vinyl-Functionalized Ordered Mesoporous Silicas with High Organic Content 216
Chapter 24. Polyfunctionalized Silica Adsorbents Obtained by Using Dodecylamine as Template Jaroniec and Stephan Mann 224
Chapter 25. Characterization of Mesoporous Thin Films Formed with Added Organophosphonate and Organosilane 232
Chapter 26. Improving the Hydro-Stability of MCM-41 by Post-Synthesis Treatment and Hexamethyldisilazane Coating 240
Chapter 27. Adsorption of CO on Zn-Cu(I)/HMCM-41 248
Section V: Synthesis of Mesoporous Metal Oxides 254
Chapter 28. Design of Transition Metal Oxide Mesoporous Thin Films 254
Chapter 29. Mesoporous Alumina as A Support for Hydrodesulphurization Catalysts 262
Chapter 30. Preparation and XAFS Spectroscopic Characterization of Mesoporous Titania with Surface Area more than 1200 m2/g 270
Chapter 31. Mesoporous Zirconium Oxides: An Investigation of Physico-chemical Synthesis Parameters 276
Chapter 32. Single Crystal Particles of Mesoporous (Nb, Ta)2O5 284
Section VI: Synthesis of Other Nanostructured Materials and Nanoparticles 292
Chapter 33. Preparation of Exfoliated Zeolites from Layered Precursors - The Role of pH and Nature of Intercalating Media 292
Chapter 34. Control of Mesopore Structure of Smectite-type Materials Synthesized with a Hydrothermal Method 300
Chapter 35. Synthesis, Characterization and Catalytic Application of Mesoporous Sulfated Zirconia 308
Chapter 36. Synthesis of Mesoporous Silicoaluminophosphates (SAPO) 316
Chapter 37. Synthesis and Characterization of Mesostructured Vanadium-Phosphorus-Oxide Phases 320
Chapter 38. Novel Macroporous Vanadium-Phosphorus-Oxides with Three-Dimensional Arrays of Spherical Voids 328
Chapter 39. Engineering Active Sites in Bifunctional Nanopore and Bimetallic Nanoparticle Catalystsfor One-Step, Solvent-Free Processes 336
Chapter 40. Using Au Nanoparticles-Surfactant Aqueous Solution for a Convenient Preparation of Mesoporous Aluminosilicates Containing Au-Nanoparticles 348
Chapter 41. The Use of Templated Mesoporous Materials as Tempates for the Development of Odered Arragements of Nanowire and Nanorods of Electronically Important Materials 356
Chapter 42. Synthesis and Adsorption Properties of Novel Carbons of Tailored Porosity 364
Chapter 43. Flexible Metal-Organic Frameworks with Isomerizing Building Units 372
Chapter 44. Dynamic Porous Frameworks of Coordination Polymers Controlled by Anions 382
Chapter 45. Mesoporous Polymeric Materials Based On Comb-Coil Supramolecules 390
Section VII: Characterization of Nanoporous Materials 398
Chapter 46. Electron Microscopic Investigation of Mesoporous SBA-2 398
Chapter 47. A Study of Morphology of Mesoporous Silica SBA-15 406
Chapter 48. SBA- 15 versus MCM-41: Are they the same Materials? 414
Chapter 49. Comprehensive Characterization of Iron Oxide Containing Mesoporous Molecular Sieve MCM-41 422
Chapter 50. Mesoporous Molecular Sieves of MCM-41 Type Modified with Cs, K and Mg -Physico-Chemica land Catalytic Properties 430
Chapter 51. Meso-ALPO Prepared by Thermal Decomposition of the Organic-Inorganic Composite. A FTIR Study 436
Chapter 52. Organic - Inorganic Phase Interaction in A1SBA-15 Mesoporous Molecular Sieves by DoubleResonance NMR Spectroscopy 442
Chapter 53. Adsorption of Nitrogen on Organized Mesoporous Alumina 448
Chapter 54. The Use of Ordered Mesoporous Materials for Improving the Mesopore Size Analysis: Current State and Future 456
Chapter 55. Sorption Properties and Hydrothermal Stability of MCM-41 Prepared by pH Adjustment and Salt Addition 464
Chapter 56. Acidity Characterization of MCM-41 Materials Using Solid-State NMR Spectroscopy 472
Chapter 57. Acidity of Calcined AI-, Fe-, and La-containing MCM-41 Mesoporous Materials: An Investigation of Adsorption of Pyridine 478
Chapter 58. Acid Properties of Ammonium Exchanged A1MCM-41 with Different Si/A1 Ratio 486
Chapter 59. Kinetic Evaluation of the Pyrolysis of High Density Polyethylene over H- A1MCM-41 Material 492
Chapter 60. Electrorheological Response of Mesoporous Materials under Applied Electric Fields 498
Section VIII: Catalytic Applications of Nanoporous Materials 506
Chapter 61. Synthesis and Characterization of TiO2 Loaded Cr-MCM-41 catalysts 506
Chapter 62. Photocatalytic Ethylene Polymerization over Chromium Containing Mesoporous Molecular Sieves 514
Chapter 63. Catalytic Reduction of Nitric Oxides on A1- containing Mesoporous Molecular Sieves 522
Chapter 64. Catalytic Oxidation of alpha-Eicosanol to alpha-Eicosanoic Acid Over Ti, Zr and Mn Doped MCM-48 Molecular Sieves 530
Chapter 65. Preparation of Pd/A1-MCM-41 Catalyst and Its Hydroisomerization Properties for Long Chain Alkane Compounds 536
Chapter 66. Isopropanol Dehydration over Nanostructured Sulfated MCM-41 550
Chapter 67. Effect of Si/A1 Ratio and Pore Size on Cracking Reaction over Mesoporous MCM-41 556
Chapter 68. Hydrogenation and Mild Hydrocracking of Synthetic Crude Distillate by Pt-supported Mesoporous Material Catalysts 562
Chapter 69. Carbon-Carbon Bond Forming Reactions Catalyzed by Meso- and Microporous Silicate-Quaternary Ammonium Composite 572
Chapter 70. A Selectivity of Zeolite Matrices in the Cu(II) Reduction Process 580
Chapter 71. Reduction of Binary Silver-Copper Ion Mixture in Mordenite: an Example of Synergetic Behavior 588
Chapter 72. Preparation, Characterization and Catalytic Properties of CuPC/Y Nano-composite 594
Section IX: Environmental Applications of Nanoporous Materials 602
Chapter 73. Environmental Applications of Self-Assembled Monolayers on Mesoporous Supports (SAMMS) 602
Chapter 74. A Possible Use of Modified Mesoporous Molecular Sieves in Water Treatment Processes 610
Chapter 75. Organized Mesoporous Titanium Dioxide - A Powerful Photocatalyst for the Removal of Water Pollutants 618
Chapter 76. Mesoporous Materials for Heavy Metal Ion Adsorption Synthesized by Displacement of Polymeric Template 626
Chapter 77. Organically-modified Mesoporous Silica Spheres with MCM-41 Architecture as Sorbents for Heavy Metals 634
Chapter 78. NO and NO2 Gas Sensors Based on Surface Photovoltage System are Fabricated by Self-ordered Mesoporous Silicate Film 642
Section X: Other Applications of Nanoporous Materials 650
Chapter 79. Polymerisations in Mesoporous Environments 650
Chapter 80. Incorporation of Nano-sized zeolites into a Mesoporous Matrix, TUD-1 654
Chapter 81. Formation and Stabilization of Gold Nanoparticles in Organo-Functionalized MCM-41 Mesoporous Materials and their Catalytic Applications 660
Chapter 82. Entrapment and Stabilization of Cadmium Sulphide (CdS) Nanoclusters Formed Inside Propylthiol Functionalized MCM-41 Mesoporous Materials 666
Chapter 83. SnO2 Nanoparticles in the Pores of Non-structured SiO2 and of Si-MCM-41: Comparison of their Properties in Gas Sensing 672
Chapter 84. Spontaneous Nitride Formation in the Reaction of Mesoporous Titanium Oxide with Bis(Toluene) Titanium in a Nitrogen Atmosphere. 680
Chapter 85. Isolation and Characterization of Amorphous Solids from Oil Sands Fine Tailings 688
Author Index 694
Subject Index 698
Recent developments in the synthesis and chemistry of periodic mesoporous organosilicas
Tewodros Asefaa; Geoffrey A. Ozina; Hiltrud Grondeya; Michal Krukb; Mietek Jaroniecb a Materials Chemistry Research Group, Department of Chemistry, University of Toronto, Toronto, Ontario M5S 3H6, Canada
b Department of Chemistry, Kent State University, Kent, Ohio 44242, USA
Synthetic routes have recently been developed to an entirely new class of organic-inorganic hybrid nanocomposite materials called periodic mesoporous organosilicas (PMOs) containing bridging organic groups integrated within a well-ordered mesoporous silica-based framework structure. Some of the interesting properties of these types of materials have been demonstrated but real challenges still remain including the scope of the synthesis approach and breadth of the compositional domain, reactivity and stability of the materials, their chemical and physical, electrical and mechanical properties, as well as potential applications. In this review, we will describe our past and current research concerning new synthetic strategies, unique properties and advantageous features of alkane, alkylene, aromatic, heteroatom-containing, chiral, and star-like organic functional group containing PMOs as advanced materials for diverse applications. Some of the effects of size and kind of organic groups on the order and integrity of the structure of the materials are discussed. Various synthetic routes, such as lithiation, Grignard, hydroboration, Pd-catalysed Heck coupling and alcoholysis reactions that we used to make the molecular poly(trialkoxysilyl)organic precursors are also briefly described.
1 INTRODUCTION
The synthesis of periodic mesoporous organosilica (PMO) materials containing organic groups in the framework of ordered and high surface area mesostructures is drawing increasing attention recently [1–30]. One of the main driving forces behind the synthesis of various PMOs is the traditional interest in the synthesis of ordered hybrid organic-inorganic nanocomposites wherein beneficial properties of one of the components are enhanced or new properties uncharacteristic of the individual components are created. Furthermore, the presence of organic functional groups in such ordered nanoporous materials also offers additional advantages that make the materials potentially useful as catalytic and chromatographic supports, chemical and biological sensors and membranes. Consequently, research in the field of organic-inorganic hybrid nanocomposite materials has remained an active area of investigation for the last few decades and is likely to expand in the years as well. Enormous advances made since the first types of classical organically modified silicas (ORMOSILs) and organically modified ceramics (ORMOCERS) were reported [31–33]. The successes in coupling organic and inorganic groups at a molecular level for the synthesis of hybrid organic-inorganic xerogels and amorphous materials [34–40] have also led to many advances in recent years and proved to have advantages over the simple physical mixing of the constituents in their bulk states. However, until recently, there have been no well-developed approaches to create uniform pores of controlled size in these materials. In fact, their porous structure is highly dependent on the synthesis temperature and drying conditions [39,40]. With the work of Mobil scientists in 1992 and the first report on mesoporous silica (MCM-41) materials [41–44], a new research direction in organic-inorganic nanocomposite materials emerged. The synthesis of these materials is carried out using inorganic precursors and surfactant templates and the method of supramolecular self-assembly. In many cases, the supramolecular templates can be removed without the collapse of the ordered composite, thus rendering ordered mesoporous structures.
After the first papers on materials with siliceous frameworks [41–44], synthesis techniques and compositions of mesoporous materials developed further to include various other kinds of nanocomposite and nanoporous materials. The methodology, for instance, was modified to include ordered hexagonal, cubic and lamellar structures as well as disordered structures with uniform pores [41–50] while the composition field was expanded to include Pt, TiO2, M/Ge4S10, etc. [51–57]. Furthermore, by judicial choice of templates and swelling agents, control over the size, porosity and structure of the materials have been achieved [41,49,50,58,59]. The literature in the past 10 years also contains demonstrations on potential applications of these materials in catalysis, nanoelectronics, separation, host-guest chemistry and sensing [60–66]. However, many of these applications were not achieved with the periodic structure alone. The presence of electroactive, optically active or reactive functional sites within these high surface area and ordered mesoporous materials were required for these applications to be realized in practice.
The introduction of terminal organic functional groups into periodic mesoporous silicas either through direct or indirect (post-synthetic) synthetic approaches has been successfully used as a way to functionalize this class of materials in the past few years [67–71]. However, these approaches have often resulted in materials with lower degree of structural ordering and low or moderate loading of organic groups. The recent approach of introducing organic functional groups into the framework of periodic mesoporous organosilicas (PMO) provided a way to overcome these drawbacks [1–30].
PMOs are a new class of organic-inorganic hybrid nanocomposites with uniformly distributed organic functional groups in the framework of the materials. They are synthesized like MCM-41 materials through in a one-pot surfactant-templated supramolecular self-assembly procedure but from the hydrolysis and condensation of poly(trialkoxysilyl)organic precursors ([(R’O)3Si]xR, x = 2, 3) [1–30]. The enormous choice of polysilylated molecular precursors having various types of bridging organic functional groups with for example electroptic, catalytic and hydrophilic/hydrophobic properties and the self assembly of these with various kinds of supermolecular templates are providing researchers with large varieties of periodic mono- and multi-functional organic-inorganic nanocomposite materials. The ability for molecular integration of organic and inorganic groups in the framework of these materials may have advantages over direct and indirect (grafting) methods that may create non-uniformly distributed organic groups protruding into the void spaces. Benefits include tailorable physical properties [19,20], uniform distribution of functional groups, possibility of controlling the loading of the functional groups using co-condensation approach, and unique chemical properties. Some of these bridging organic groups have also proven to be accessible for chemistry and can be further transformed chemically [1,18]. Interesting chemical differences between organics in the framework and in the channels has been reported and used to have advantages in the preparation of a new sub-class of bifunctional and multifunctional PMOs [8]. The dependence of thermal, mechanical, dielectric and adsorptions properties on the nature of the organic groups in these hybrid materials will likely result in new products, processes and devices made out of PMOs in the near future [3,19–21]. The ability to synthesize film and various curved PMO morphologies [7,19–21] may lead to advances in catalysis, chromatography and membrane science and technology.
Advances made in the synthesis and characterization of the properties of PMO materials in just less than two years have inspired investigations into new kinds of functionalized PMO materials and a search for commercial applications. However, only a few types of organic functionalized PMOs have been reported so far. They include methylene, ethane, ethylene, acetylene, thiophene, benzene and bithiophene containing PMOs, [1–30]. There is also a notable scarcity of detailed investigations of the structural integrity, and thermal and chemical stability of Si-C bonds for various kinds of organic groups in PMOs [3,8]. Herein, we review some developments in our research group mainly concerning the synthesis of various PMO materials and possible applications. Particular attention will be given to PMO materials having heteroatom and side-arm star-like organic groups, which are envisioned to enhance the reactivity and accessibility of bridging organic groups in PMOs enabling judicious surface modification that leads to the tailoring of function.
2 EXPERIMENTAL
2.1 Materials
HCl and NH3 solutions were obtained from BDH. Methanol was supplied by ACP. Hexanes, pentanes, diethylether and tetrahydrofuran (THF) were purchased from ACP and were dried with CaH2 and molecular sieves before every use. The THF and the diethylether were further distilled over Na/benzophenone. All commercially available bis(triethoxysilyl)organic compounds were obtained from Gelest. All other chemicals were received from Aldrich.
2.2 PMO PRECURSORS
2.2.1 Commercially available PMO...
| Erscheint lt. Verlag | 15.5.2002 |
|---|---|
| Sprache | englisch |
| Themenwelt | Technik ► Elektrotechnik / Energietechnik |
| Technik ► Maschinenbau | |
| ISBN-10 | 0-08-053722-7 / 0080537227 |
| ISBN-13 | 978-0-08-053722-1 / 9780080537221 |
| Haben Sie eine Frage zum Produkt? |
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