This thesis focuses on the controlled synthesis of Pt-Ni bimetallic nanoparticles and the study of their catalytic properties. It discusses in detail the nucleation mechanism and the growth process of bimetallic systems, which is vital for a deeper understanding of the design of bimetallic catalysts. The author presents four pioneering studies: (1) syntheses of water-soluble octahedral, truncated octahedral, and cubic Pt-Ni nanocrystals and the study of their structure-activity relationship in model hydrogenation reactions; (2) a strategy for designing a concave Pt-Ni alloy using controllable chemical etching; (3) defect-dominated shape recovery of nanocrystals, which is a new synthesis strategy for trimetallic catalysts; (4) a sophisticated construction of Au islands on Pt Ni, which is an ideal trimetallic nanoframe catalyst. This thesis inspires researchers working in materials, catalysis as well as other interdisciplinary areas.

Multiphase catalysis is a key technology for the competitive and sustainable production of fine chemicals in coming decades. A joint academic and industry consortium has developed tools for considering complex chemical and process-based requirements when setting up a catalytic system. This book shows how the resulting competence covers such supercritical fluid (SCF) technology in catalysis, ionic liquids (Il), ligand design for SFCs and Ils, thermomorphic solvent systems, reactor design and more.

In 2001 Wyn Roberts celebrated both his 70th birthday and 50 years of working in surface science, to use the term "surface science" in its broadest meaning. This book aims to mark the anniversary with a contribution of lasting value, something more than the usual festschrift issue of a relevant journal. The book is divided into three sections: Surface Science, Model Catalysts and Catalysis, topics in which Wyn has always had interests. The authors for each chapter were chosen from some of the many eminent scientists who have worked with Wyn in various ways and are all internationally acknowledged as leaders in their field. The authors have produced authoritative reviews of their own specialties which together result in a book with an unrivalled combination of breadth and depth exploring the most recent developments in surface chemistry and catalysis.

Over the past 20 years aqueous organometallic catalysis has found applications in small- scale organic synthesis in the laboratory, as well as in the industrial production of chemicals with a combined output close to one million tons per year. Aqueous/organic two-phase reactions allow easy product-catalyst separation and full catalyst recovery which mean clear benefits not only in economic but also in environmental and green chemistry contexts. Instead of putting together a series of expert reviews of specialized fields, this book attempts to give a comprehensive yet comprehensible description of the various catalytic transformations in aqueous systems as seen by an author who has been working on aqueous organometallic catalysis since its origin. Emphasis is put on the discussion of differences between related non-aqueous and aqueous processes due to the presence of water. The book will be of interest to experts and students working in catalysis, inorganic chemistry or organic synthesis, and may serve as a basis for advanced courses.

This book contains 99 of the papers that were presented at the 6th in the series of Symposia on Characterization of Porous Solids held in Alicante, Spain, May 2002. <br><br>Written by leading international specialists in the subject, the contributions represent an up-to-date and authoritative account of recent developments around the world in the major methods used to characterize porous solids. The book is a useful work of reference for anyone interested in characterizing porous solids, such as MCM-41 mesoporous materials, pillared clays, etc. Papers on pore structure determination using gas adsorption feature strongly, together with papers on small angle scattering methods, mercury porosimetry, microcalorimetry, scanning probe microscopies, and image analysis.

This proceedings contains the papers presented at the 9th International Symposium on Catalyst Deactivation, held in Lexington, KY, USA, on 7-10 October 2001.

The second supplement to the three volume reference work Comprehensive Asymmetric Catalysis critically reviews new developments to the hottest topics in the field written by recognised experts. Seven chapters which are already in the major reference work have been supplemented and additionally a new chapter on Aminohydroxylation of Carbon-Carbon Double Bonds has been included. Thus, the state of the art in this area is now re-established. Together with the basic three volume book set and Supplement 1 it is not only the principal reference source for synthetic organic chemists, but also for all scientific researchers who use chiral compounds in their work (for example, in biochemical investigations and molecular medicine) as well as for pharmaceutical chemists and other industrial researchers who prepare chiral compounds.

There is an increasing need to find cost-effective and environmentally sound methods of converting natural resources into fuels, chemicals and energy; catalysts are pivotal to such processes. Catalysis highlights major developments in this area. Coverage of this Specialist Periodical Report includes all major areas of heterogeneous and homogeneous catalysis. In each volume, specific areas of current interest are reviewed. Examples of topics include experimental methods, acid/base catalysis, materials synthesis, environmental catalysis, and syngas conversion. Catalysis will be of interest to anyone working in academia and industry that needs an up-to-date critical analysis and summary of catalysis research and applications. Specialist Periodical Reports provide systematic and detailed review coverage in major areas of chemical research. Compiled by teams of leading experts in their specialist fields, this series is designed to help the chemistry community keep current with the latest developments in their field. Each volume in the series is published either annually or biennially and is a superb reference point for researchers.

This thesis addresses two fundamental areas in contemporary organic chemistry: synthesis of natural products and catalytic asymmetric synthesis. Firstly, a new methodology, developed by our research group, which allows the asymmetric synthesis of lactones, a structural unit ubiquitous in natural products, was utilised in the synthesis of a number of natural product analogues that showed significant biological activity. Secondly, the development of a catalytic asymmetric synthesis of a key structural motif present in a number of natural products and pharmaceuticals was accomplished. During the course of this work we discovered dual stereo control, which is significant because it allows the configuration of a new stereo centre to be controlled by a simple change of proton source.

This book is devoted to the emerging field of techniques for visualizing atomic-scale properties of active catalysts under actual working conditions, i.e. high gas pressures and high temperatures. It explains how to understand these observations in terms of the surface structures and dynamics and their detailed interplay with the gas phase. This provides an important new link between fundamental surface physics and chemistry, and applied catalysis. The book explains the motivation and the necessity of operando studies, and positions these with respect to the more traditional low-pressure investigations on the one hand and the reality of industrial catalysis on the other. The last decade has witnessed a rapid development of new experimental and theoretical tools for operando studies of heterogeneous catalysis. The book has a strong emphasis on the new techniques and illustrates how the challenges introduced by the harsh, operando conditions are faced for each of these new tools. Therefore, one can also read this book as a collection of recipes for the development of operando instruments. At present, the number of scientific results obtained under operando conditions is still limited and mostly focused on a simple test reaction, the catalytic oxidation of CO. This reaction thus forms a natural binding element between the chapters, linking the demonstrations of new techniques, and also connecting the theoretical and experimental studies. Some first results on other reactions are also presented. If there is one thing that can be concluded already in this early stage, it is that the catalytic conditions themselves can have dramatic effects on the structure and composition of the surfaces of catalysts, which, in turn can greatly affect the mechanisms, the activity, and the selectivity of the chemical reactions that they catalyze.

Knoevenagel Reaction of Unprotected Sugars, By M.-C. Scherrmann; Carbohydrate-Based Lactones: Synthesis and Applications, By N. M. Xavier, A. P. Rauter, and Y. Queneau; Heterogeneously-Catalyzed Conversion of Carbohydrates, By K. De Oliveira Vigier and F. Jerome; Palladium-Catalyzed Telomerization of Butadiene with Polyols: From Mono to Polysaccharides, By S. Bouquillon, J. Muzart, C. Pinel, and F. Rataboul; Monosaccharides, By J.A. Galbis and M.G. Garcia-Martin; Natural Sources, By L. Weignerova and V. K en; Synthesis and Applications of Ionic Liquids Derived from Natural Sugars; By C. Chiappe, A. Marra, and A. Mele"

With the recent advent of nanotechnology, research and development in the area of nanostructured catalysts has gained unprecedented prominence. Novel materials with potentially exciting new applications in catalysis are being discovered at a much higher rate than ever before. Innovative tools to fabricate, manipulate, characterize, and evaluate such materials are being developed and expanded. To keep pace with this extremely rapid growth, it is necessary to take a breath from time to time, to critically assess the current knowledge and provide thoughts for future developments. This book represents one of these moments, as a number of prominent scientists in nanostructured catalysts join forces to provide insightful reviews of their areas of expertise; thus, offering an overall picture of the state-of-the art of the field.

Nanostructured materials designate an increasing number of materials with designed shapes, surfaces, structures, pore systems, etc. In general, nanostructured catalysts have modified surfaces, including materials whose surfaces have been altered via such techniques as grafting and tethering of organic or organometallic species, or through various deposition procedures including electro, electroless, and vapor deposition, or simple adsorption. Materials with designed regular pore systems, such as zeolites, metallophosphates, periodic mesoporous materials, nanoporous organic, and organometallic materials are also members of the large family of nanostructured materials. These materials are of paramount importance, particularly in catalysis.

One of the most distinctive characteristics of this book is the fact that it is all-inclusive, since most of the materialslisted above have been dealt with in a concise and informative manner. With fourteen up-to-date reports on the design, synthesis, and catalytic properties of nanostructured materials, this book sets the stage for things to come in this area. The development of novel catalysts, taking advantage of the many interesting attributes of periodic nanoporous materials, and the discovery of innovative materials, such as polymer- silica nanocomposites and confined nanoparticles, are some of the leading ideas for future work in the increasingly important field of nanostructured catalysts.

This multi-authored book provides a comprehensive overview of the latest developments in porous CO2 capture materials, including ionic liquid derived carbonaceous adsorbents, porous carbons, metal-organic frameworks, porous aromatic frameworks, micro porous organic polymers. It also reviews the sorption techniques such as cyclic uptake and desorption reactions and membrane separations. In each category, the design and fabrication, the comprehensive characterization, the evaluation of CO2 sorption/separation and the sorption/degradation mechanism are highlighted. In addition, the advantages and remaining challenges as well as future perspectives for each porous material are covered.

This book is aimed at scientists and graduate students in such fields as separation, carbon, polymer, chemistry, material science and technology, who will use and appreciate this information source in their research. Other specialists may consult specific chapters to find the latest, authoritative reviews.

Dr. An-Hui Lu is a Professor at the State Key Laboratory of Fine Chemicals, School of Chemical Engineering, Faculty of Chemical, Environmental and Biological Science and Technology, Dalian University of Technology, China.

Dr. Sheng Dai is a Corporate Fellow and Group Leader in the Chemical Sciences Division at Oak Ridge National Laboratory (ORNL) and a Professor of Chemistry at the University of Tennessee, USA."

Catalysis, which until recently had largely been limited to the production of large volume chemical, is now being increasingly used in the production of medium and small volume chemicals. Simultaneously, the role of process intensification in enhancing overall productivity is being increasingly recognised. This usually takes the form of reaction rate enhancement by extending known or emerging laboratory techniques to industrial scale production. Organic Synthesis Engineering describes the application of catalysis in its various forms in organic synthesis, and addresses both the chemical and engineering aspects of catalysts (particularly solid catalysts). It also outlines different techniques of reaction rate and/or selectivity enhancement - a feature not found in any existing books on reaction engineering.

This book covers whole aspects of the sulfur isologues of amides. Starting from the synthetic methods of thioamides, a range of synthetic applications to the construction of carbon-sulfur and carbon-carbon bonds, to asymmetric reactions, to formation of heterocycles are described. Among the array of thiocarbonyl compounds, thioamides are readily handled in room temperature air. Some of their characteristic features are that the polarity of C=S bonds in thioamides is much smaller than C=O bonds in ordinary amides, that thioamides possess higher HOMO and lower LUMO when compared with those of ordinary amides, and that carbon atoms alpha to the C=S and nitrogen atoms in thioamides are more acidic than those in ordinary amides. Theoretical studies further disclose their features. Thioamides are also used as ligands to a wide variety of metals. Their unique photophysical properties and catalytic activities are described here. Characteristic features of biologically relevant thioamides, e.g., thiopeptides and related compounds, are the final focus of the book.

In this thesis, the author investigates the chemistry and application of molecules containing urea and amide bonds. These bonds are some of the strongest known and are fundamental to biological processes. The author describes his discovery that sterically hindered ureas undergo solvolysis at room temperature under neutral conditions. This is a remarkable finding, since ureas are inert under these conditions and a general rule of chemistry is that hindered substrates are less reactive. Remarkably, the author translates these results to the correspondingly sterically hindered amides. This thesis has resulted in a number of outstanding publications in high profile journals. The unique method for breaking urea and amide bonds developed in this study is likely to have far reaching consequences for biological protein manipulation.

This book describes state-of-the-art borylation chemistry using copper(I) catalysis. Enantioselective reactions are included to afford a variety of functionalized, complex organoboronate esters, which will find wide application in asymmetric synthesis, drug discovery, and material science. Organoboron compounds are recognized as useful reagents in organic synthesis; therefore, great effort has been devoted to the development of a simple, mild, and efficient method for their preparation in the past several years. However, the synthesis of functionalized organoboron compounds remains a challenging issue because known reactions often require the use of highly reactive organometallic carbon nucleophiles. This book focuses on conceptually new, formal nucleophilic copper(I)-catalyzed borylation reactions with diboron compounds that show high selectivity and excellent functional group compatibility. Theoretical studies based on density functional theory calculations to understand the reaction mechanisms have also been described. Advances in this novel borylation chemistry will allow the rapid and efficient synthesis of complex molecules with potentially interesting properties in combination with the boron functionalization process.

Sean Ashton's doctoral thesis, which he finished at the Technical University in Munich, describes the challenge of constructing a Differential Electrochemical Mass Spectrometer instrument (DEMS). DEMS combines an electrochemical cell with mass spectrometry via a membrane interface, allowing gaseous and volatile electrochemical reaction species to be monitored online. The thesis carefully introduces the fuel cell electrocatalyst development concerns before reviewing the pertinent literature on DEMS. This is followed by the presentation and discussion of the new extended design, including a thorough characterization of the instrument. The capabilities of the new setup are demonstrated in two research studies: The methanol oxidation reaction on Pt and PtRu catalysts, and the electrochemical corrosion of fuel cell catalyst supports. Despite both topics having long since been studied, new insights can be obtained through careful investigations with the new DEMS instrument that are of great, general interest. The thesis and the instrument thus show the way for future investigations in the field.

This book introduces readers to industrially important enzymes and discusses in detail their structures and functions, as well as their manifold applications. Due to their selective biocatalytic capabilities, enzymes are used in a broad range of industries and processes. The book highlights selected enzymes and their applications in agriculture, food processing and discoloration, as well as their role in biomedicine. In turn, it discusses biochemical engineering strategies such as enzyme immobilization, metabolic engineering, and cross-linkage of enzyme aggregates, and critically weighs their pros and cons. Offering a wealth of information, and stimulating further research by presenting new concepts on enzymatic catalytic functions in basic and applied contexts, the book represents a valuable asset for researchers from academia and industry who are engaged in biochemical engineering, microbiology and biotechnology.

The subject of dioxygen activation and homogeneous catalytic oxidation by metal complexes has been in the focus of attention over the last 20 years. The widespread interest is illustrated by its recurring presence among the sessions and subject areas of important international conferences on various aspects of bioinorganic and coordination chemistry as well as catalysis. The most prominent examples are ICCC, ICBIC, EUROBIC, ISHC, and of course the ADHOC series of meetings focusing on the subject itself. Similarly, the number of original and review papers devoted to various aspects of dioxygen activation are on the rise. This trend is due obviously to the relevance of catalytic oxidation to biological processes such as dioxygen transport, and the action of oxygenase and oxidase enzymes related to metabolism. The structural and functional modeling of metalloenzymes, particularly of those containing iron and copper, by means of low-molecular complexes of iron, copper, ruthenium, cobalt, manganese, etc., have provided a wealth of indirect information helping to understand how the active centers of metalloenzymes may operate. The knowledge gained from the study of metalloenzyme models is also applicable in the design of transition metal complexes as catalytsts for specific reactions. This approach has come to be known as biomimetic or bioinspired catalysis and continues to be a fruitful and expanding area of research.

There is an increasing challenge for chemical industry and research institutions to find cost-efficient and environmentally sound methods of converting natural resources into fuels chemicals and energy. Catalysts are essential to these processes and the Catalysis Specialist Periodical Report series serves to highlight major developments in this area. This series provides systematic and detailed reviews of topics of interest to scientists and engineers in the catalysis field. The coverage includes all major areas of heterogeneous and homogeneous catalysis and also specific applications of catalysis such as NOx control kinetics and experimental techniques such as microcalorimetry. Each chapter is compiled by recognised experts within their specialist fields and provides a summary of the current literature. This series will be of interest to all those in academia and industry who need an up-to-date critical analysis and summary of catalysis research and applications. Catalysis will be of interest to anyone working in academia and industry that needs an up-to-date critical analysis and summary of catalysis research and applications. Specialist Periodical Reports provide systematic and detailed review coverage in major areas of chemical research. Compiled by teams of leading experts in their specialist fields, this series is designed to help the chemistry community keep current with the latest developments in their field. Each volume in the series is published either annually or biennially and is a superb reference point for researchers. www.rsc.org/spr

The activation of dioxygen by metal ions has both synthetic potential and biological relevance. Dioxygen is the cleanest oxidant for use in emission-free technologies to minimize pollution of the environment. The book gives a survey of those catalyst systems based on metal complexes which have been discovered and studied in the last decade. They activate molecular oxygen and effect the oxidation of various organic compounds under mild conditions. Much of the recent progress is due to a search for biomimetic catalysts that would duplicate the action of metalloenzymes. Mechanistic aspects are emphasized throughout the book. An introductonary chapter reviews the chemistry of transition metal dioxygen complexes, which are usually the active intermediates in the catalytic reactions discussed. Separate chapters are devoted to oxidation of saturated, unsaturated and aromatic hydrocarbons, phenols, catechols, oxo-compounds, phosphorus, sulfur and nitrogen compounds.

In order to meet the ever-increasing demands for enantiopure compounds, heteroge- ous, homogeneous and enzymatic catalysis evolved independently in the past. Although all three approaches have yielded industrially viable processes, the latter two are the most widely used and can be regarded as complementary in many respects. Despite the progress in structural, computational and mechanistic studies, however, to date there is no universal recipe for the optimization of catalytic processes. Thus, a trial-and-error approach remains predominant in catalyst discovery and optimization. With the aim of complementing the well-established fields of homogeneous and enzymatic catalysis, organocatalysis and artificial metalloenzymes have enjoyed a recent revival. Artificial metalloenzymes, which are the focus of this book, result from comb- ing an active but unselective organometallic moiety with a macromolecular host. Kaiser and Whitesides suggested the possibility of creating artificial metallo- zymes as long ago as the late 1970s. However, there was a widespread belief that proteins and organometallic catalysts were incompatible with each other. This severely hampered research in this area at the interface between homogeneous and enzymatic catalysis. Since 2000, however, there has been a growing interest in the field of artificial metalloenzymes for enantioselective catalysis. The current state of the art and the potential for future development are p- sented in five well-balanced chapters. G. Roelfes, B. Feringa et al. summarize research relying on DNA as a macromolecular host for enantioselective catalysis.

Multi-scale Quantum Models for Biocatalysis explores various molecular modelling techniques and their applications in providing an understanding of the detailed mechanisms at play during biocatalysis in enzyme and ribozyme systems. These areas are reviewed by an international team of experts in theoretical, computational chemistry, and biophysics.

This book presents detailed reviews concerning the development of various techniques, including ab initio molecular dynamics, density functional theory, combined QM/MM methods, solvation models, force field methods, and free-energy estimation techniques, as well as successful applications of multi-scale methods in the biocatalysis systems including several protein enzymes and ribozymes.

This book is an excellent source of information for research professionals involved in computational chemistry and physics, material science, nanotechnology, rational drug design and molecular biology and for students exposed to these research areas."

Atomically dispersed metal cations and small polyatomic cationic structures co-ordinated to the surface of porous matrices exhibit different properties from the same cationic species contained in a bulk oxide or supported on amorphous carriers. This subject is treated to an extensive review, showing how an understanding of it is essential to the development of a new generation of solid catalysts. There are also exciting opportunities to shape the catalytic properties of the transition metal cations in microporous and mesoporous matrices. The book covers both theoretical and experimental aspects, including the distribution of framework Al atoms in Si-rich zeolites, distribution and siting of charge-exchanged metal cations, electronic, adsorptive and catalytic properties of metal cations, and correlation of metal cation structure and siting with catalytic activity.