Research Catalog

Title

Design and applications of single-site heterogeneous catalysts : contributions to green chemistry, clean technology and sustainability / Sir John Meurig Thomas.

Author

Thomas, J. M. (John Meurig)

Publication

London : Imperial College Press ; Hackensack, NJ : Distributed by World Scientific Pub., ©2012.

Items in the Library & Off-site

Details

Description

xxvii, 293 pages : illustrations (chiefly color); 23 cm

Summary

For far too long chemists and industrialists have relied on the use of aggressive reagents such as nitric and sulphuric acids, permanganates and dichromates to prepare the massive quantities of both bulk and fine chemicals that are needed for the maintenance of civilised life materials such as fuels, fabrics, foodstuffs, fertilisers and pharmaceuticals. Now, owing to recent advances made in the synthesis of nanoporous solids, it is feasible to design new solid catalysts that enable benign, mild oxidants to be used, frequently without utilising solvents, to manufacture the products that the chemical, pharmaceutical, agro- and bio-chemical industries require. These new solid agents are designated single-site heterogeneous catalysts (SSHCs). Their principle characteristics are that all the active sites present in the high-area solids are identical in their atomic environment and hence in their energy of interaction with reactants, just as in enzymes. Single-site heterogeneous catalysts now occupy a position of growing importance both academically and in their potential for commercial exploitation. This text, the only one devoted to such catalysts, dwells both on principles of design and on applications, such as the benign synthesis of nylon 6 and vitamin B3. It equips the reader with unifying insights required for future catalytic adventures in the quest for sustainability in the materials used by humankind. Anyone acquainted with the language of molecules, be they an undergraduate in the physical and biological sciences, as well as graduates in engineering and materials science, should be able to assimilate the principles and examples presented in this book. Inter alia, it describes how clean technology and green processes may be carried out in an environmentally responsible manner.

Alternative Title

Contributions to green chemistry, clean technology and sustainability

Subject

• Green chemistry
• Catalysts
• Heterogeneous catalysis
• Environmental management
• catalyst
• environmental control
• Miljökemi
• Miljöledning

Genre/Form

• Handbook
• Handbooks and manuals.
• Guides et manuels.

Bibliography (note)

• Includes bibliographical references and index.

Contents

• Part I Basics and Background 1 -- Chapter 1 Introduction to the Salient Features of Single-site Heterogeneous Catalysts 3 -- Chapter 2 Lessons from the Biological World: The Kinship Between Enzymes and Single-site Heterogeneous Catalysts 11 -- 2.1 The Story of Lysozyme and Its Consequences 11 -- 2.2 Hybrid Enzymes 15 -- 2.3 Immobilized Enzymes 16 -- 2.4 The Kinship between Enzymes and SSHCs 16 -- Chapter 3 Distinctions between Single-site Heterogeneous Catalysts and Immobilized Homogeneous Catalysts 23 -- 3.1 Outline of Historical Background 23 -- 3.2 Metal Cluster Compounds as Molecular Precursors for Tailored Metal Nanocatalysts 27 -- 3.3 The Essence of Surface Organometallic Chemistry (SOMC) 30 -- 3.4 Highly Active Organometallic Catalysts Based on Self-assembled Monolayers 36 -- 3.5 Colloid-bound Organometallic Catalysts of Exceptional Activity 37 -- 3.6 Analogies with Single-site Homogeneous Polymerization Catalysts 38 -- 3.7 The Taxonomy of SSHCs: A Résumé 40 -- Part II Microporous Open Structures 51 -- Chapter 4 Microporous Open Structures for the Design of New Single-site Heterogeneous Catalysts 53 -- 4.1 Introduction 53 -- 4.2 The Salient Characteristics of Microporous SSHCs 59 -- 4.3 Some Examples of Acidic Microporous SSHCs 64 -- 4.3.1 Environmentally benign, solvent-free alkylations, acylations and nitrations using acidic SSHCs 67 -- 4.3.2 Brønsted acidic microporous SSHCs for hydroisomerization (dewaxing) of alkanes: designing new catalysts in silico 69 -- 4.4 Brønsted Acidic Microporous SSHCs for the Dehydration of Alkanols: Environmentally Benign Routes to Ethylene, Propylene and Other Light Alkenes 74 -- 4.4.1 Catalytic dehydration of ethanol using Brønsted acidic SSHCs 75 -- 4.4.2 The methanol-to-olefin conversion over Brønsted acidic SSHCs 75 -- 4.4.3 Structural and mechanistic aspects of the dehydration of isomeric butanols over porous aluminosilicate acid catalysts 80 -- 4.5 Lewis Acidic Microporous SSHCs for a Range of Selective Oxidations 87 -- 4.6 Cascade Reactions with TAPO-5 88 -- 4.6.1 One-pot reactions: a contribution to environmental protection using Lewis acid active sites 90 -- 4.7 Redox Active Sites in Microporous Solids 92 -- 4.7.1 Introduction 92 -- 4.7.2 Single-site redox active centres for the benign selective oxidation of hydrocarbons in air or 02 93 -- 4.8 Insights from Quantum Chemical Computations into the Mechanism of C-H Activation at Mn^IIICatalytic Centres in Microporous Solids 102 -- 4.9 Bifunctional Single-site Microporous Catalysts: A Solvent-free Synthesis of Caprolactam, the Precursor of Nylon 6 107 -- 4.10 Single-site Metal Cluster Catalysts Supported on a Microporous Host: Reactive Environments Influence the Structure of Catalysts 109 -- Chapter 5 Single-site Heterogeneous Catalysts for the Production of Pharmaceuticals, Agrochemicals, Fine and Bulk Chemicals 121 -- 5.1 Introduction 121 -- 5.2 Fine Chemicals and Pharmaceuticals 122 -- 5.2.1 Facile, one-step production of niacin (vitamin B₃) and other nitrogen-containing chemicals with SSHCs 122 -- 5.2.2 Facile, one-step production of isonicotinic acid from 4-picoline 125 -- 5.2.3 Production of pharmaceutically important derivatives of quinoline 127 -- 5.3 Environmentally Benign Oxidative Methods of Producing Bulk Chemicals Using SSHCs 128 -- 5.3.1 The synthesis of benzaldehyde from toluene 129 -- 5.3.2 The one-step conversion of cyclohexane to adipic acid 132 -- 5.3.3 The one-step aerobic, solvent-free conversion of p-xylene to terephthalic acid 134 -- 5.4 Environmentally Benign, Brønsted Acid-catalysed Production of Bulk Chemicals with Microporous SSHCs 136 -- 5.5 Transformations Involving Lewis Acid Microporous Catalysts 137 -- 5.5.1 Conversions of sugars to lactic acid derivatives using Sn-based zeotypic SSHCs 137 -- 5.5.2 Single-site, Lewis acid microporous catalysts for the isomerization of glucose: a new efficient route to the production of high-fructose corn syrup 140 -- 5.6 Baeyer-Villiger Oxidations of Ketones to Lactones with SSHCs 141 -- 5.6.1 Introduction 141 -- 5.6.2 A redox SSHC for Baeyer-Villiger aerobic oxidations under Mukaiyama conditions 142 -- 5.6.3 Sn-centred single-site microporous catalysts for Baeyer-Villiger oxidations with H₂O₂ 144 -- 5.7 The Crucial Role of Single-site Microporous Catalysts in New Methods of Synthesizing ε-Caprolactam and Nylon 6 145 -- 5.7.1 Introduction 145 -- 5.7.2 The primacy of nylon 6 145 -- 5.7.3 Existing routes to the synthesis of ε-caprolactam 147 -- 5.7.4 The design of a green, one-step production of ε-caprolactam using a bifunctional SSHC 149 -- 5.7.5 Optimizing SSHCs for oxime production 151 -- 5.8 Envoi 152 -- Part III Mesoporous Open Structures 157 -- Chapter 6 Epoxidations and Sustainable Utilization of Renewable Feedstocks, Production of Vitamin E Intermediates, Conversion of Ethene to Propene and Solvent-free, One-step Synthesis of Esters 159 -- 6.1 Introduction 159 -- 6.2 A Comprehensive Picture of the Nature and Mechanism of the Ti^IV-catalysed Epoxidation of Alkenes 162 -- 6.2.1 Mechanism of the Ti^IV-centred epoxidation of alkenes 165 -- 6.2.2 An alternative method of introducing isolated Ti centres to mesoporous silica 169 -- 6.2.3 The use of H₂O₂ over Ti^IV-grafted mesoporous silica catalysts: a further step towards sustainable epoxidation 171 -- 6.2.4 Ti_IV mesoporous catalysts have an important role to play in a sustainable way to utilize renewable feedstocks from fats and vegetable sources 173 -- 6.3 Other Examples of Single-site, Metal-centred Catalysts Grafted onto Mesoporous Silica 175 -- 6.4 Titanium Cluster Sites for the Production of Vitamin E (Benzoquinone) Intermediates 176 -- 6.5 Single-site Metal Complexes Grafted onto Mesoporous Silica 179 -- 6.5.1 Stability and recyclability of supported metal-ligand complex catalysts: a critical note 181 -- 6.6 A Trifunctional, Mesoporous Silica-based Catalyst: Highly Selective Conversion of Ethene to Propene 182 -- 6.7 Hybrid SSHCs are Chemically Robust 183 -- 6.8 The Confluence of Heterogeneous and Homogeneous Catalysis Involving Single Sites 184 -- 6.9 Beyond Mesoporous Silica 188 -- 6.9.1 The merits of clay-based single-site catalysts 188 -- 6.9.2 Pillared zeolites 191 -- 6.10 Envoi 192 -- Chapter 7 Exploiting Nanospace for Asymmetric Conversions 201 -- 7.1 Background 201 -- 7.2 Whither Chiral Zeolites 202 -- 7.3 Chiral Metal-organic Frameworks (MOFs) 206 -- 7.4 Harnessing the Asymmetric Catalytic Potential of Mesoporous Silicas Using SSHCs 210 -- 7.4.1 Background 210 -- 7.4.2 Exploiting nanospace for asymmetric catalysis: confinement of immobilized single-site chiral catalysts enhances enantioselectivity 212 -- 7.4.3 Asymmetric hydrogenation of E-α-phenylcinnamic acid and methyl benzoylformate: the advantages of using inexpensive diamine asymmetric ligands 219 -- 7.4.4 One step is better than two 221 -- 7.5 Epilogue 225 -- Chapter 8 Multinuclear, Bimetallic Nanocluster Catalysts 233 -- 8.1 Definitions: Nanoclusters are Distinct from Nanoparticles 233 -- 8.1.1 Bimetallic nanoclusters and bimetallic nanoparticles are not alloys 235 -- 8.2 The Merits of Studying Bimetallic Nanocluster Catalysts 236 -- 8.3 Why Focus on Bimetallic Catalysts Based on Platinum Group Metals (PGMs) 241 -- 8.4 Specific Examples of High-performance Bimetallic Nanocluster Catalysts for Selective Hydrogenations under Benign Conditions 244 -- 8.4.1 Bimetallic nanocluster catalysts for ammoxidation 246 -- 8.4.2 Bimetallic nanocluster catalysts for the (sustainable) synthesis of adipic acid 247 -- 8.5 Bimetallic and Trimetallic Nanocluster Catalysts Containing Tin: The Experimental.
• Introduction to the salient features of single-site heterogeneous catalysts -- Lessons from the biological world : the kinship between enzymes and single-site heterogeneous catalysts -- Distinctions between single-site heterogeneous catalysts and immobilized homogeneous catalysts -- Microporous open structures for the design of new single-site heterogeneous catalysts -- Single-site heterogeneous catalysts for the production of pharmaceuticals, agrochemicals, fine and bulk chemicals -- Epoxidations and sustainable utilization of renewable feedstocks, production of vitamin E intermediates, conversion of ethene to propene and solvent-free, one-step synthesis of esters -- Exploiting nanospace for asymmetric conversions -- Multinuclear, bimetallic nanocluster catalysts.

ISBN

• 9781848169104
• 1848169108
• 9781848169098
• 1848169094

OCLC

• ocn772112507
• 772112507
• SCSB-9266192

Owning Institutions

Princeton University Library