Over the past twenty years, Catalysis by Heteropolyacids (HPAs) has received wide attention and led to new and promising developments both at academic and industrial level. In particular, heterogeneous catalysis is particularly attractive because it generally satisfies most of green chemistry's requirements. By emphasizing the development of third generation catalysts, this volume presents trends and opportunities in academic and industrial research. The book appeals to postgraduates, researchers, and chemists working in the field of environmentally benign catalysts as well as catalytic processes.

Most chemical reactions in industry and biology are catalytic and play a role at some stage of the processing of about 80% of the goods manufactured in the U.S., yet catalysis is a neglected subject in chemical education. The fragmentary treatment accorded the topic until now is integrated. It covers, in a unified way, catalysis in solutions, by enzymes, in synthetic polymers within the molecular scale cages of zeolites and other molecular sieves, and on surfaces of inorganic solids. The central ideas are chemical; principles are illustrated by emphasizing industrial reactions and catalysts.

This book highlights major achievements made in the last five years concerning sustainable C(sp3)-H bond functionalization and offers a promising and emerging tool-kit for organic synthesis. The book is divided into three chapters demonstrating key advances in C(sp3)-H bond functionalization. Chapter 1 reviews transition-metal-catalyzed C(sp3)-H bond functionalization using different directing groups, while Chapter 2 addresses the new methods of transition-metal-catalyzed and metal-free C(sp3)-H bond functionalization without directing groups, in addition to briefly highlighting redox-neutral C(sp3)-H bond functionalization. In closing, Chapter 3 examines visible-light photoredox catalysis, an emerging and highly sustainable C(sp3)-H bond functionalization strategy. The book offers an intriguing and useful reference guide for a broad readership working and/or interested in the fields of organic, organometallic, and green chemistry.

Advances in Polymer Science enjoys a longstanding tradition and good reputation in its community. Each volume is dedicated to a current topic, and each review critically surveys one aspect of that topic, to place it within the context of the volume. The volumes typically summarize the significant developments of the last 5 to 10 years and discuss them critically, presenting selected examples, explaining and illustrating the important principles, and bringing together many important references of primary literature. On that basis, future research directions in the area can be discussed. Advances in Polymer Science volumes thus are important references for every polymer scientist, as well as for other scientists interested in polymer science - as an introduction to a neighboring field, or as a compilation of detailed information for the specialist.

This book underscores the essential principles of photocatalysis and provides an update on its scientific foundations, research advances, and current opinions, and interpretations. It consists of an introduction to the concepts that form the backbone of photocatalysis, from the principles of solid-state chemistry and physics to the role of reactive oxidizing species. Having recognised the organic link with chemical kinetics, part of the book describes kinetic concepts as they apply to photocatalysis. The dependence of rate on the reaction conditions and parameters is detailed, the retrospective and prospective aspects of the mechanism of photocatalysis are highlighted, and the adsorption models, photocatalytic rate expressions, and kinetic disguises are examined. This book also discusses the structure, property, and activity relationship of prototypical semiconductor photocatalysts and reviews how to extend their spectral absorption to the visible region to enable the effective use of visible solar spectrum. Lastly, it presents strategies for deriving substantially improved photoactivity from semiconductor materials to support the latest applications and potential trends.

Direct Alcohol Fuel Cells: Materials, Performance, Durability and Applications begins with an introductory overview of direct alcohol fuel cells (DAFC); it focuses on the main goals and challenges in the areas of materials development, performance, and commercialization. The preparation and the properties of the anodic catalysts used for the oxidation of methanol, higher alcohols, and alcohol tolerant cathodes are then described. The membranes used as proton conductors in DAFC are examined, as well as alkaline membranes, focusing on the electrical conductivity and alcohol permeability. The use of different kinds of carbon materials as catalyst supports, gas diffusion layers, and current collectors in DAFC is also discussed. State of the art of the modeling is used to estimate performance and durability. The closing chapter reviews the use of DAFC in portable equipment and mobile devices and features a detailed discussion on the mechanisms of component degradation which limits their durability. This book is written to facilitate the understanding of DAFC technology, applications, and future challenges. It is an excellent introduction for electrochemical and material engineers interested in small fuel cells as portable energy sources, scientists focused on materials science for energy production and storage, as well as policy-makers in the area of renewable energies.

This book presents wet chemical sol-gel and hydrothermal methods for 1D oxide nanostructure preparation. These methods represent an attractive route to multifunctional nanomaterials synthesis, as they are versatile, inexpensive and, thus, appropriate for obtaining a wide range of oxide materials with tailored morphology and properties. Three specific oxides (SiO2, TiO2, ZnO) are discussed in detail in order to illustrate the principle of the sol-gel and hydrothermal preparation of 1D oxide nanostructures. Other oxides synthesized via this method are also briefly presented. Throughout the book, the correlation between the tubular structure and the physico-chemical properties of these materials is highlighted. 1D oxide nanostructures exhibit interesting optical and electrical properties, due to their confined morphology. In addition, a well-defined geometry can be associated with chemically active species. For example, the pure SiO2 nanotubes presented a slight photocatalytic activity, while the Pt-doped SiO2 tubular materials act as microreactors in catalytic reactions. In the case of titania and titanate nanotubes, large specific surface area and pore volume, ion-exchange ability, enhanced light absorption, and fast electron-transport capability have attracted significant research interest. The chemical and physical modifications (microwave assisted hydrothermal methods) discussed here improve the formation kinetics of the nanotubes. The ZnO nanorods/tubes were prepared as random particles or as large areas of small, oriented 1D ZnO nanostructures on a variety of substrates. In the latter case a sol-gel layer is deposited on the substrate prior to the hydrothermal preparation. Using appropriate dopants, coatings of ZnO nanorods with controlled electrical behavior can be obtained.

This book describes the fundamental concepts, the latest developments and the outlook of the field of nanozymes (i.e., the catalytic nanomaterials with enzymatic characteristics). As one of today's most exciting fields, nanozyme research lies at the interface of chemistry, biology, materials science and nanotechnology. Each of the book's six chapters explores advances in nanozymes. Following an introduction to the rise of nanozymes research in the course of research on natural enzymes and artificial enzymes in Chapter 1, Chapters 2 through 5 discuss different nanomaterials used to mimic various natural enzymes, from carbon-based and metal-based nanomaterials to metal oxide-based nanomaterials and other nanomaterials. In each of these chapters, the nanomaterials' enzyme mimetic activities, catalytic mechanisms and key applications are covered. In closing, Chapter 6 addresses the current challenges and outlines further directions for nanozymes. Presenting extensive information on nanozymes and supplemented with a wealth of color illustrations and tables, the book offers an ideal guide for readers from disparate areas, including analytical chemistry, materials science, nanoscience and nanotechnology, biomedical and clinical engineering, environmental science and engineering, green chemistry, and novel catalysis.

Find out how theoretical calculations are used to determine, elucidate and propose mechanisms for Pd-catalyzed C-C cross-coupling reactions in Max Garcia Melchor's outstanding thesis. Garcia Melchor investigates one of the most significant and useful types of reactions in modern organic synthesis; the Pd-cross coupling reaction. Due to its versatility, broad scope and selectivity under mild conditions, this type of reaction can now be applied in fields as diverse as the agrochemical and pharmaceutical industry. Garcia Melchor studies the reaction intermediates and transition states involved in the Negishi, the copper-free Sonogashira and the asymmetric version of Suzuki-Miyaura coupling. He also characterizes and provides a detailed picture of the associated reaction mechanisms. The author has won numerous prizes for this work which has led to over eight publications in internationally renowned journals.

In his thesis, Florian Schweinberger investigates the influence of the precise size of catalytically active species on reactivity. In order to do this he carries out studies both in UHV and under ambient conditions for supported, size-selected Platium clusters (8-68 atoms). Schweinberger probed the electronic structure, adsorption properties and reactivity of two olefins on surfaces and Pt clusters in the submonolayer range. With adsorbed trichloroethene (TCE) a possible cluster-adsorbate induced change in the electronic structure, and for ethene a low-temperature, size-dependent self-/hydrogenation was observed.In a collaborative approach, Schweinberger and colleagues investigated Pt clusters under ambient pressure conditions. They characterised the clusters at at the local and integral level and tested for temperature stability. Experiments in gas phase ?-reactors and in liquid, as part of a hybrid photocatalytic system, revealed size-dependent reactivity.Overall this thesis is not only of interest for those who want to perform similar experiments but also provides superb scientific insights for researchers in the field.

The series Structure and Bonding publishes critical reviews on topics of research concerned with chemical structure and bonding. The scope of the series spans the entire Periodic Table and addresses structure and bonding issues associated with all of the elements. It also focuses attention on new and developing areas of modern structural and theoretical chemistry such as nanostructures, molecular electronics, designed molecular solids, surfaces, metal clusters and supramolecular structures. Physical and spectroscopic techniques used to determine, examine and model structures fall within the purview of Structure and Bonding to the extent that the focus is on the scientific results obtained and not on specialist information concerning the techniques themselves. Issues associated with the development of bonding models and generalizations that illuminate the reactivity pathways and rates of chemical processes are also relevant. The individual volumes in the series are thematic. The goal of each volume is to give the reader, whether at a university or in industry, a comprehensive overview of an area where new insights are emerging that are of interest to a larger scientific audience. Thus each review within the volume critically surveys one aspect of that topic and places it within the context of the volume as a whole. The most significant developments of the last 5 to 10 years should be presented using selected examples to illustrate the principles discussed. A description of the physical basis of the experimental techniques that have been used to provide the primary data may also be appropriate, if it has not been covered in detail elsewhere. The coverage need not be exhaustive in data, but should rather be conceptual, concentrating on the new principles being developed that will allow the reader, who is not a specialist in the area covered, to understand the data presented. Discussion of possible future research directions in the area is welcomed. Review articles for the individual volumes are invited by the volume editors. Readership: research scientists at universities or in industry, graduate students Special offer For all customers who have a standing order to the print version of Structure and Bonding, we offer free access to the electronic volumes of the Series published in the current year via SpringerLink.

Contains a balanced discussion of homogeneous catalytic reactions that are used in industry, featuring every documented example employed in a current commercial process, or that have a broad application in the organic synthesis laboratory. Incorporates synthesis with chiral catalysts in chapters on hydrogenation, CO chemistry and olefin oxidation. New additions include Tennessee Eastman's coal-based acetic anhydride plant and IFP's Dimersol process for dimerizing propylene as well as major changes in the areas on pharmaceuticals, flavors, fragrances, agricultural and electronic chemicals.

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 presents an in-depth study into the utility of σ-bond metathesis in Group 2 mediated reactivity. A comprehensive introduction defines the state of the art in both Group 2 mediated catalysis and dehydrocoupling. Structural investigations giving rise to a range of mixed s-block metal hydrides including a remarkable dodecabimetallic decahydride are then described. Subsequent extensive mechanistic work focussing on both silicon-nitrogen and boron-nitrogen dehydrocoupling gives insights into both congeneric effects down Group 2 and ligand effects centring upon magnesium. These studies show the striking effects of these factors, as well as the electronic nature of the hydridic coupling partner.  Finally, the unprecedented introduction of single-electron transfer steps into Group 2 catalytic manifolds is described. The use of the stable radical TEMPO to induce single-electron transfer to substituents bound to Group 2 centres coupled with σ-bond metathesis allows a novel hydrogen release from silanes.

Daniel Halwidl presents the development of an effusive molecular beam apparatus, which allows the dosing of gases, liquids, and solids in ultra-high vacuum. The apparatus is designed to adsorb precise and reproducible doses to a defined area on metal oxide samples, which is required in Temperature Programmed Desorption and other surface chemistry experiments. The design and the construction of the apparatus is described. The properties of the molecular beam are experimentally confirmed. The beam profile has a core diameter of 3.5 mm and a standard core pressure of 4 x 10-8 mbar, while the background pressure is 4 orders of magnitude lower.

The book reports on the results of the BrenaRo Winterschool 2011, held on November 21-22 in Aachen, Germany. The different chapters cover a number of aspects of the topic of energy generation, with a particular focus on energy generation from biomass. They presents new findings concerning engine development, process engineering, and biological and chemical conversion of biomass to fuels, and highlight the importance of an interdisciplinary approach, combining chemistry, biology and engineering research, to the use of renewable energy sources. All in all, this book provides readers with a snapshot of the state-of-the-art in renewable energy conversion, and gives an overview of the ongoing work in this field in Germany.

The series Topics in Organometallic Chemistry presents critical overviews of research results in organometallic chemistry. As our understanding of organometallic structure, properties and mechanisms increases, new ways are opened for the design of organometallic compounds and reactions tailored to the needs of such diverse areas as organic synthesis, medical research, biology and materials science. Thus the scope of coverage includes a broad range of topics in pure and applied organometallic chemistry, where new breakthroughs are being achieved that are of significance to a larger scientific audience. The individual volumes of Topics in Organometallic Chemistry are thematic. Review articles are generally invited by the volume editors.

This thesis describes novel strategies for the rational design of several cutting-edge high-efficiency photocatalysts, for applications such as water photooxidation, reduction, and overall splitting using a Z-Scheme system. As such, it focuses on efficient strategies for reducing energy loss by controlling charge transfer and separation, including novel faceted forms of silver phosphate for water photooxidation at record high rates, surface-basic highly polymerised graphitic carbon nitride for extremely efficient hydrogen production, and the first example of overall water splitting using a graphitic carbon nitride-based Z-Scheme system. Photocatalytic water splitting using solar irradiation can potentially offer a zero-carbon renewable energy source, yielding hydrogen and oxygen as clean products. These two ‘solar’ products can be used directly in fuel cells or combustion to provide clean electricity or other energy. Alternatively they can be utilised as separate entities for feedstock-based reactions, and are considered to be the two cornerstones of hydrogenation and oxidation reactions, including the production of methanol as a safe/portable fuel, or conventional catalytic reactions such as Fischer-Tropsch synthesis and ethylene oxide production. The main driving force behind the investigation is the fact that no photocatalyst system has yet reported combined high efficiency, high stability, and cost effectiveness; though cheap and stable, most suffer from low efficiency.

The series Topics in Organometallic Chemistry presents critical overviews of research results in organometallic chemistry. As our understanding of organometallic structure, properties and mechanisms increases, new ways are opened for the design of organometallic compounds and reactions tailored to the needs of such diverse areas as organic synthesis, medical research, biology and materials science. Thus the scope of coverage includes a broad range of topics in pure and applied organometallic chemistry, where new breakthroughs are being achieved that are of significance to a larger scientific audience. The individual volumes of Topics in Organometallic Chemistry are thematic. Review articles are generally invited by the volume editors.

This thesis reports the discovery of metal nanoparticles having new structures that do not exist in bulk state and that exhibit hydrogen storage ability or CO oxidation activity. Research into the reaction of hydrogen with metals has attracted much attention because of potential applications as effective hydrogen storage materials, as permeable films, or as catalysts for hydrogenation. Also, CO oxidation catalysts have been extensively developed because of their importance to CO removal from car exhaust or fuel-cell systems. At the same time, atomic-level (solid solution) alloying has the advantage of being able to continuously control chemical and physical properties of elements by changing compositions and/or combinations of constituent elements. This thesis provides a novel strategy for the basis of inter-elemental fusion to create highly efficient functional materials for energy and material conversions.

In this thesis, the author describes the total synthesis of natural product Maoecrystal V in detail. In the first part of the thesis, the author introduces the research background and reviews the research progress in total synthesis of Maoecrystal V. In the second part, the author develops a novel and concise approach for the stereo selective construction of the tetracyclic model system of Maoecrystal V. The model system is accomplished in 8 steps with 20% yield. In the third part, the author describes the first successful total synthesis of Maoecrystal V and investigates four strategies for constructing the key tetrahydrofuran oxa-bridge skeleton. The total synthesis starts from a known compound and is accomplished in 17 steps with 1.2% yield. The successful total synthesis of Maoecrystal V will contribute to the development of efficient synthetic strategies for natural products and other compounds with complex structures.

Urea-SCR Technology for deNOx After Treatment of Diesel Exhausts presents a complete overview of the selective catalytic reduction of NOx by ammonia/urea. The book starts with an illustration of the technology in the framework of the current context (legislation, market, system configurations), covers the fundamental aspects of the SCR process (catalysts, chemistry, mechanism, kinetics) and analyzes its application to useful topics such as modeling of full scale monolith catalysts, control aspects, ammonia injections systems and integration with other devices for combined removal of pollutants.

The union of covalent and noncovalent chemistries manifested in the mechanical bond represents one of the great chemical triumphs of the last half century. However, until recently, the preparation of mechanically interlocked compounds has often been an inefficient and limiting process. This thesis provides a detailed account of the great strides taken to increase the synthetic accessibility of donor-acceptor mechanically interlocked molecules by the application of highly efficient and ultra mild chemical transformations during their template-directed synthesis. These new departures in synthesis have indeed played a transformative role in that more complex, higher-order, and functional architectures - once only a dream - are now comfortably within reach. Specifically, the formation of mechanical bonds in higher order rotaxanes and catenanes has become ever easier through the use of highly efficient click chemistries. The resulting mechanically interlocked compounds are functional molecular media for a host of applications including information storage, mechanical actuation, and drug release.

Advances in Polymer Science enjoys a longstanding tradition and good reputation in its community. Each volume is dedicated to a current topic, and each review critically surveys one aspect of that topic, to place it within the context of the volume. The volumes typically summarize the significant developments of the last 5 to 10 years and discuss them critically, presenting selected examples, explaining and illustrating the important principles, and bringing together many important references of primary literature. On that basis, future research directions in the area can be discussed. Advances in Polymer Science volumes thus are important references for every polymer scientist, as well as for other scientists interested in polymer science - as an introduction to a neighboring field, or as a compilation of detailed information for the specialist.

The series Structure and Bonding publishes critical reviews on topics of research concerned with chemical structure and bonding. The scope of the series spans the entire Periodic Table and addresses structure and bonding issues associated with all of the elements. It also focuses attention on new and developing areas of modern structural and theoretical chemistry such as nanostructures, molecular electronics, designed molecular solids, surfaces, metal clusters and supramolecular structures. Physical and spectroscopic techniques used to determine, examine and model structures fall within the purview of Structure and Bonding to the extent that the focus is on the scientific results obtained and not on specialist information concerning the techniques themselves. Issues associated with the development of bonding models and generalizations that illuminate the reactivity pathways and rates of chemical processes are also relevant. The individual volumes in the series are thematic. The goal of each volume is to give the reader, whether at a university or in industry, a comprehensive overview of an area where new insights are emerging that are of interest to a larger scientific audience. Thus each review within the volume critically surveys one aspect of that topic and places it within the context of the volume as a whole. The most significant developments of the last 5 to 10 years should be presented using selected examples to illustrate the principles discussed. A description of the physical basis of the experimental techniques that have been used to provide the primary data may also be appropriate, if it has not been covered in detail elsewhere. The coverage need not be exhaustive in data, but should rather be conceptual, concentrating on the new principles being developed that will allow the reader, who is not a specialist in the area covered, to understand the data presented. Discussion of possible future research directions in the area is welcomed. Review articles for the individual volumes are invited by the volume editors. Readership: research scientists at universities or in industry, graduate students Special offer For all customers who have a standing order to the print version of Structure and Bonding, we offer free access to the electronic volumes of the Series published in the current year via SpringerLink.