
Design And Applications Of Single-site Heterogeneous Catalysts
Contributions To Green Chemistry, Clean Technology And Sustainability
Hardcover | 18 April 2012
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322 Pages
22.86 x 15.24 x 1.91
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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. Such aggressive reagents generate vast quantities of environmentally harmful and often toxic by-products, including the oxides of nitrogen, of metal oxides and carbon dioxide.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 principal 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, including undergraduates 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.
Industry Reviews
A true marriage of the practical and the fundamental, John Thomas's masterly account of single-site heterogeneous catalysts, a remarkably effective form of matter guiding desired chemical transformation, is a sheer joy to read. -- Roald Hoffmann "Nobel Laureate, Chemistry, 1981"
Catalysis is that crucial process that strongly increases the efficiency of chemical reactions in living organisms as well as in industry. It thus also greatly contributes to sustainability through conservation of resources and energy. Sir John Thomas, leader in the field, provides a perceptive view unifying the different areas from biology to sustainability. -- Jean-Marie Lehn "Nobel Laureate, Chemistry, 1987, Honorary Professor, College du France"
Chemical reactions are hugely important to society - chemists make things that people need through greener, cleaner and less energy-consuming processes. Catalysis is therefore now even more important. John Meurig Thomas is internationally recognised as the fount of all knowledge here, which is why his excellent treatise is so valuable. -- Sir John Cadogan FRS "former Director of Research, British Petroleum Co, first Director General, UK Research Councils"
This beautifully written text by a world-leading expert in catalysis constitutes a succinct account of the new approaches that are required to meet the challenges posed by the need for clean technology and the sustainable use of natural resources. It is warmly recommended as a guide to both beginners and experts who wish to address the increasing necessity to pursue 'green' chemistry. -- Michel Che "President-Founder of European Federation of Catalysis Societies (EFCATS), Past President of International Association of Catalysis Societies (IACS)"
This book provides a highly readable and wide-ranging overview of the fascinating landscape of contemporary catalysis. -- Martyn Poliakoff CBE FRS "Professor of Chemistry, University of Nottingham, Foreign Secretary of the Royal Society"
This book will certainly become a milestone in the attempts to develop unifying concepts in catalysis. -- Gerhard Ertl "Nobel Laureate, Chemistry, 2007"
Understanding and controlling catalysis at the molecular level is one of the grand challenges of contemporary physical and biomolecular sciences. This excellent volume provides a uniquely comprehensive survey of the state-of-the-art in this exciting and rapidly developing field, and profits from the unrivalled insight of the author into catalytic science. -- Richard Catlow FRS "Dean of Mathematical and Physical Sciences, University College London"
| Foreword | p. vii |
| Preface | p. ix |
| Acknowledgements | p. xiii |
| Permissions | p. xxiii |
| Basics and Background | p. 1 |
| Introduction to the Salient Features of Single-site Heterogeneous Catalysts | p. 3 |
| Lessons from the Biological World: The Kinship Between Enzymes and Single-site Heterogeneous Catalysts | p. 11 |
| The Story of Lysozyme and Its Consequences | p. 11 |
| Hybrid Enzymes | p. 15 |
| Immobilized Enzymes | p. 16 |
| The Kinship between Enzymes and SSHCs | p. 16 |
| Distinctions between Single-site Heterogeneous Catalysts and Immobilized Homogeneous Catalysts | p. 23 |
| Outline of Historical Background | p. 23 |
| Metal Cluster Compounds as Molecular Precursors for Tailored Metal Nanocatalysts | p. 27 |
| The Essence of Surface Organometallic Chemistry (SOMC) | p. 30 |
| Highly Active Organometallic Catalysts Based on Self-assembled Monolayers | p. 36 |
| Colloid-bound Organometallic Catalysts of Exceptional Activity | p. 37 |
| Analogies with Single-site Homogeneous Polymerization Catalysts | p. 38 |
| The Taxonomy of SSHCs: A Résumé | p. 40 |
| Microporous Open Structures | p. 51 |
| Microporous Open Structures for the Design of New Single-site Heterogeneous Catalysts | p. 53 |
| Introduction | p. 53 |
| The Salient Characteristics of Microporous SSHCs | p. 59 |
| Some Examples of Acidic Microporous SSHCs | p. 64 |
| Environmentally benign, solvent-free alkylations, acylations and nitrations using acidic SSHCs | p. 67 |
| Brønsted acidic microporous SSHCs for hydroisomerization (dewaxing) of alkanes: designing new catalysts in silico | p. 69 |
| Brønsted Acidic Microporous SSHCs for the Dehydration of Alkanols: Environmentally Benign Routes to Ethylene, Propylene and Other Light Alkenes | p. 74 |
| Catalytic dehydration of ethanol using Brønsted acidic SSHCs | p. 75 |
| The methanol-to-olefin conversion over Brønsted acidic SSHCs | p. 75 |
| Structural and mechanistic aspects of the dehydration of isomeric butanols over porous aluminosilicate acid catalysts | p. 80 |
| Lewis Acidic Microporous SSHCs for a Range of Selective Oxidations | p. 87 |
| Cascade Reactions with TAPO-5 | p. 88 |
| One-pot reactions: a contribution to environmental protection using Lewis acid active sites | p. 90 |
| Redox Active Sites in Microporous Solids | p. 92 |
| Introduction | p. 92 |
| Single-site redox active centres for the benign selective oxidation of hydrocarbons in air or 02 | p. 93 |
| Insights from Quantum Chemical Computations into the Mechanism of C-H Activation at MnIII Catalytic Centres in Microporous Solids | p. 102 |
| Bifunctional Single-site Microporous Catalysts: A Solvent-free Synthesis of Caprolactam, the Precursor of Nylon 6 | p. 107 |
| Single-site Metal Cluster Catalysts Supported on a Microporous Host: Reactive Environments Influence the Structure of Catalysts | p. 109 |
| Single-site Heterogeneous Catalysts for the Production of Pharmaceuticals, Agrochemicals, Fine and Bulk Chemicals | p. 121 |
| Introduction | p. 121 |
| Fine Chemicals and Pharmaceuticals | p. 122 |
| Facile, one-step production of niacin (vitamin B3) and other nitrogen-containing chemicals with SSHCs | p. 122 |
| Facile, one-step production of isonicotinic acid from 4-picoline | p. 125 |
| Production of pharmaceutically important derivatives of quinoline | p. 127 |
| Environmentally Benign Oxidative Methods of Producing Bulk Chemicals Using SSHCs | p. 128 |
| The synthesis of benzaldehyde from toluene | p. 129 |
| The one-step conversion of cyclohexane to adipic acid | p. 132 |
| The one-step aerobic, solvent-free conversion of p-xylene to terephthalic acid | p. 134 |
| Environmentally Benign, Brønsted Acid-catalysed Production of Bulk Chemicals with Microporous SSHCs | p. 136 |
| Transformations Involving Lewis Acid Microporous Catalysts | p. 137 |
| Conversions of sugars to lactic acid derivatives using Sn-based zeotypic SSHCs | p. 137 |
| Single-site, Lewis acid microporous catalysts for the isomerization of glucose: a new efficient route to the production of high-fructose corn syrup | p. 140 |
| Baeyer-Villiger Oxidations of Ketones to Lactones with SSHCs | p. 141 |
| Introduction | p. 141 |
| A redox SSHC for Baeyer-Villiger aerobic oxidations under Mukaiyama conditions | p. 142 |
| Sn-centred single-site microporous catalysts for Baeyer-Villiger oxidations with H2O2 | p. 144 |
| The Crucial Role of Single-site Microporous Catalysts in New Methods of Synthesizing ¿-Caprolactam and Nylon 6 | p. 145 |
| Introduction | p. 145 |
| The primacy of nylon 6 | p. 145 |
| Existing routes to the synthesis of ¿-caprolactam | p. 147 |
| The design of a green, one-step production of ¿-caprolactam using a bifunctional SSHC | p. 149 |
| Optimizing SSHCs for oxime production | p. 151 |
| Envoi | p. 152 |
| Mesoporous Open Structures | p. 157 |
| 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 | p. 159 |
| Introduction | p. 159 |
| A Comprehensive Picture of the Nature and Mechanism of the TiIV-catalysed Epoxidation of Alkenes | p. 162 |
| Mechanism of the TiIV-centred epoxidation of alkenes | p. 165 |
| An alternative method of introducing isolated Ti centres to mesoporous silica | p. 169 |
| The use of H2O2 over TiIV-grafted mesoporous silica catalysts: a further step towards sustainable epoxidation | p. 171 |
| TiIV mesoporous catalysts have an important role to play in a sustainable way to utilize renewable feedstocks from fats and vegetable sources | p. 173 |
| Other Examples of Single-site, Metal-centred Catalysts Grafted onto Mesoporous Silica | p. 175 |
| Titanium Cluster Sites for the Production of Vitamin E (Benzoquinone) Intermediates | p. 176 |
| Single-site Metal Complexes Grafted onto Mesoporous Silica | p. 179 |
| Stability and recyclability of supported metal-ligand complex catalysts: a critical note | p. 181 |
| A Trifunctional, Mesoporous Silica-based Catalyst: Highly Selective Conversion of Ethene to Propene | p. 182 |
| Hybrid SSHCs are Chemically Robust | p. 183 |
| The Confluence of Heterogeneous and Homogeneous Catalysis Involving Single Sites | p. 184 |
| Beyond Mesoporous Silica | p. 188 |
| The merits of clay-based single-site catalysts | p. 188 |
| Pillared zeolites? | p. 191 |
| Envoi | p. 192 |
| Exploiting Nanospace for Asymmetric Conversions | p. 201 |
| Background | p. 201 |
| Whither Chiral Zeolites? | p. 202 |
| Chiral Metal-organic Frameworks (MOFs) | p. 206 |
| Harnessing the Asymmetric Catalytic Potential of Mesoporous Silicas Using SSHCs | p. 210 |
| Background | p. 210 |
| Exploiting nanospace for asymmetric catalysis: confinement of immobilized single-site chiral catalysts enhances enantioselectivity | p. 212 |
| Asymmetric hydrogenation of E-¿-phenylcinnamic acid and methyl benzoylformate: the advantages of using inexpensive diamine asymmetric ligands | p. 219 |
| One step is better than two | p. 221 |
| Epilogue | p. 225 |
| Multinuclear, Bimetallic Nanocluster Catalysts | p. 233 |
| Definitions: Nanoclusters are Distinct from Nanoparticles | p. 233 |
| Bimetallic nanoclusters and bimetallic nanoparticles are not alloys | p. 235 |
| The Merits of Studying Bimetallic Nanocluster Catalysts | p. 236 |
| Why Focus on Bimetallic Catalysts Based on Platinum Group Metals (PGMs)? | p. 241 |
| Specific Examples of High-performance Bimetallic Nanocluster Catalysts for Selective Hydrogenations under Benign Conditions | p. 244 |
| Bimetallic nanocluster catalysts for ammoxidation | p. 246 |
| Bimetallic nanocluster catalysts for the (sustainable) synthesis of adipic acid | p. 247 |
| Bimetallic and Trimetallic Nanocluster Catalysts Containing Tin: The Experimental Facts | p. 249 |
| Quantum Computational Insights | p. 249 |
| The computational method | p. 253 |
| Assessing the structure and electronic properties of Ru5PtSn in the gas phase and when supported on silica (cristobalite) | p. 253 |
| Quantum insights into the structure and densities of states of RunSnn (n = 3 to 6) clusters in the gas phase | p. 258 |
| Comparisons with Nanocluster Catalysts Involving Gold, Platinum, Palladium and Iridium | p. 260 |
| Nanocluster catalysts of palladium and iridium | p. 265 |
| The role of the catalyst support | p. 267 |
| Envoi | p. 268 |
| Reference Works Dealing With Green Chemistry, Clean Technology and Sustainability | p. 277 |
| Index | p. 281 |
| Table of Contents provided by Ingram. All Rights Reserved. |
ISBN: 9781848169098
ISBN-10: 1848169094
Series: Catalytic Science Series
Published: 18th April 2012
Format: Hardcover
Language: English
Number of Pages: 322
Audience: College, Tertiary and University
Publisher: World Scientific Publishing Co Pte Ltd
Country of Publication: GB
Dimensions (cm): 22.86 x 15.24 x 1.91
Weight (kg): 0.64
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