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Books > Science & Mathematics > Chemistry > Physical chemistry > Catalysis
This volume gives a detailed account into how renewables can be transformed into value-added products via homogeneous catalysis, especially via transiton metal homogeneous catalysis. The most important catalytic reactions of oleochemicals, isoprenoids, carbohydrates, lignin, proteins and carbon dioxide are described. Special emphasis is placed on carbon-carbon linkage reactions (hydroformylations, dimerisations, telomerisations, metathesis, polymerisations etc.), hydrogenations, oxidations and other important homogeneous reactions (such as isomerisations, hydrosilylations etc.). Also, tandem reactions including isomerising hydroformylations are presented. Wherever possible, the authors have included mechanistic, kinetic, and technical aspects. The reader is therefore given a total overview of the status quo of homogeneous catalysis directed to the most important renewables.
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.
This book describes the importance of catalysis for the sustainable production of biofuels and biochemicals, focusing primarily on the state-of-the-art catalysts and catalytic processes expected to play a decisive role in the "green" production of fuels and chemicals from biomass. The book also includes general sections exploring the entire chain of biomass production, conversion, environment, economy, and life-cycle assessment.
In this thesis, applications of aminoacylation ribozymes named flexizymes are described. Flexizymes have the following unique characteristics: (i) substrate RNA is recognized by two consecutive base pairs between the 3'-end of substrate RNA and the 3'-end of the flexizyme; (ii) these base pairs can be substituted with other base pairs; and (iii) various activated amino acids can be used as substrates including both canonical and noncanonical amino acids. This flexible aminoacylation of RNAs by flexizymes was used to label endogenous tRNAs to be removed, and in vitro selection using the tRNA-depleted library enabled the discovery of the novel interaction between the microRNA precursor and metabolites. Flexizymes are also used to prepare various aminoacyl-tRNAs bearing mutations at the 3'-end to engineer the translation machinery and to develop the orthogonal translation machinery. The first part of the research demonstrated that SELEX is appropriate for discovering the interaction between small RNA and ligands, and suggested that more RNA motif binding to small molecules exists in small RNAs. The second part opened a door to new opportunities for in vitro synthetic biology involving the engineering of the genetic codes and translation machineries. This research also indicated the great potential of aminoacylation by flexizymes to be applied in various fields of RNA research, which is beneficial for RNA researchers.
This book is intended to give readers an appreciation of what the future holds, as cutting-edge technologies in synthetic biology and pathway engineering and advanced bioprocessing development pave the way for providing goods and services to benefit humankind that are based on the synergy of two biomasses - i.e. of what a renewable feedstock could yield and an infinite microbial biomass could provide in terms of enzymes and biocatalysts. This 13-chapter book, with an introductory treatise on the guiding principles of green chemistry and engineering metrics, brings together a broad range of research and innovation agendas and perspectives from industries, academia and government laboratories using renewable feedstocks that include macroalgae and lignins. In addition, social-economic aspects and the pillars of competitiveness in regional cluster development are explored as we transition from fossil-fuel-based economies to a circular bioeconomy, with chemurgy and green chemistry being implicit to the innovation movement. The bulk of the book covers specific applications including the bioproduction of amino sugars, dicarboxylic acids, omega-3 fatty acids, starch and fermentable sugars from lignocellulosic materials, and phenolics as building blocks for polymer synthesis. Enzymatic systems for accessing chiral and special-purpose chemicals, as well as the development of specialized enzymes from macroalgae for biofuel and biochemical production are also addressed. Research gaps, hurdles to overcome in various biological processes, and present achievements in the production of biofuels and biochemicals from lignocellulosic materials are discussed. Going beyond the conventional expectation of discussing the production of drop-in chemicals, the book instead emphasizes how the potential of new chemicals and materials can be harnessed through innovative thinking and research. As such, it provides an invaluable reference source for researchers and graduate students interested in Chemurgy and Green Chemistry, as well as for practitioners in the field of industrial biotechnology and biobased industry. Peter C.K. Lau is a Distinguished Professor at Tianjin Institute of Industrial Biotechnology of the Chinese Academy of Sciences, and an Adjunct Professor at the Departments of Chemistry and Microbiology & Immunology, McGill University, Canada.
This book highlights the recent advances and state of the art in the use of functionalized nanostructured environments on catalysis. Nanoconfinements considered include well-defined molecular cages, imprinted self-assembled supramolecules, polymers made by living or controlled polymerization, metallorganic frameworks, carbon nanotubes, mesoporous inorganic solids, and hybrids thereof. Advantages of nanoconfinement of catalysts discussed include higher activities, improved selectivities, catalyst stabilization, cooperativity effects, simplified protocols for cascade syntheses, better catalyst recovery, and recyclability. The multiple applications that these materials offer are revolutionizing industrial sectors such as energy, electronics, sensors, biomedicine, and separation technology.
This unique thesis discusses the development of conceptually novel and synthetically valuable methods that use visible light photocatalysis. Each chapter addresses a different topic in the emerging field of photocatalysis, which has become an indispensable tool for organic synthesis. Photocatalysis employs environmentally harmless and abundant visible light in the presence of a photosensitizer, and as such offers an attractive alternative to harmful UV light in photo-mediated reactions. This book introduces the novel concept of merging gold catalysis with visible light photocatalysis in a dual catalytic fashion, which demonstrates their compatibility with each other for first time and has inspired the development of various reactions. Moreover, a novel trifluoromethylation method, which combines radical addition chemistry with a polar rearrangement to synthesize valuable fluorinated compounds, is presented, since compounds featuring fluorinated functionality are the subject of increasing attention in pharmaceutical, agrochemical and material research. It also develops an external photocatalyst-free photochemical method for the synthesis of valuable indolizine heterocycles, where the product mediates its own formation. Lastly, it describes the synthesis and characterization of two novel highly porous metal-organic frameworks (MOFs). The comprehensive text is rounded out with illustrations and color figures.
This thesis describes a series of investigations designed to assess the value of metalloenzymes in systems for artificial and adapted photosynthesis. The research presented explores the interplay between inherent enzyme properties such as structure, rates and thermodynamics, and the properties of the semiconducting materials to which the enzyme is attached. Author, Andreas Bachmeier provides a comprehensive introduction to the interdisciplinary field of artificial photosynthesis, allowing the reader to grasp the latest approaches being investigated, from molecular systems to heterogeneous surface catalysis. Bachmeier's work also uses metalloenzymes to highlight the importance of reversible catalysts in removing the burden of poor electrocatalytic rates and efficiencies which are common characteristics for most artificial photosynthesis systems. Overall, this thesis provides newcomers and students in the field with evidence that metalloenzymes can be used to establish new directions in artificial photosynthesis research.
The series Topics in Current Chemistry Collections presents critical reviews from the journal Topics in Current Chemistry organized in topical volumes. The scope of coverage is all areas of chemical science including the interfaces with related disciplines such as biology, medicine and materials science. The goal of each thematic volume is to give the non-specialist reader, whether in academia or industry, a comprehensive insight into an area where new research is emerging which is of interest to a larger scientific audience. 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 are presented using selected examples to illustrate the principles discussed. The coverage is not intended to be an exhaustive summary of the field or include large quantities of data, but should rather be conceptual, concentrating on the methodological thinking that will allow the non-specialist reader to understand the information presented. Contributions also offer an outlook on potential future developments in the field.
This thesis presents the latest developments in new catalytic C-C bond formation methods using easily accessible carboxylate salts through catalytic decarboxylation with good atom economy, and employing the sustainable element iron as the catalyst to directly activate C-H bonds with high step efficiency. In this regard, it explores a mechanistic understanding of the newly discovered decarboxylative couplings and the catalytic reactivity of the iron catalyst with the help of density functional theory calculation. The thesis is divided into two parts, the first of which focuses on the development of a series of previously unexplored, inexpensive carboxylate salts as useful building blocks for the formation of various C-C bonds to access valuable chemicals. In turn, the second part is devoted to several new C-C bond formation methodologies using the most ubiquitous transition metal, iron, as a catalyst, and using the ubiquitous C-H bond as the coupling partner.
This book presents the latest results related to photocatalytic inactivation/killing of microorganisms, which is a promising alternative disinfection method that produces less or even no disinfection byproduct. The book is divided into 13 chapters, which introduce readers to the latest developments in the photocatalytic disinfection of microorganisms, examine essential photocatalytic (PC) and photoelectrocatalytic (PEC) disinfection studies, and forecast and make recommendations for the further development of PC and PEC disinfection. Bringing together contributions by various leading research groups worldwide, it offers a valuable resource for researchers and the industry alike, as well as the general public. Taicheng An, PhD, is Chair Professor and Director at the Institute of Environmental Health and Pollution Control, School of Environmental Science and Engineering, Guangdong University of Technology, Guangzhou, China. Huijun Zhao, PhD, is Chair Professor and Director at the Centre for Clean Environment and Energy & Griffith School of Environment, Griffith University, Australia. Po Keung Wong, PhD, is a Professor at the School of Life Sciences, the Chinese University of Hong Kong, Hong Kong SAR, China.
This thesis describes the synthesis and characterization of numerous metal-metal bonded complexes that are stabilized by extremely bulky amide ligands. It provides a comprehensive overview of the field, including discussions on groundbreaking complexes and reactions, before presenting in detail, exciting new findings from the PhD studies. The thesis appeals to researchers, professors and chemistry undergraduates with an interest in inorganic and/or organometallic chemistry.
The series Topics in Current Chemistry Collections presents critical reviews from the journal Topics in Current Chemistry organized in topical volumes. The scope of coverage is all areas of chemical science including the interfaces with related disciplines such as biology, medicine and materials science. The goal of each thematic volume is to give the non-specialist reader, whether in academia or industry, a comprehensive insight into an area where new research is emerging which is of interest to a larger scientific audience. 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 are presented using selected examples to illustrate the principles discussed. The coverage is not intended to be an exhaustive summary of the field or include large quantities of data, but should rather be conceptual, concentrating on the methodological thinking that will allow the non-specialist reader to understand the information presented. Contributions also offer an outlook on potential future developments in the field.
This updated edition of a widely admired text provides a user-friendly introduction to the field that requires only routine mathematics. The book starts with the elements of fluid mechanics and heat transfer, and covers a wide range of applications from fibrous insulation and catalytic reactors to geological strata, nuclear waste disposal, geothermal reservoirs, and the storage of heat-generating materials. As the standard reference in the field, this book will be essential to researchers and practicing engineers, while remaining an accessible introduction for graduate students and others entering the field. The new edition features 2700 new references covering a number of rapidly expanding fields, including the heat transfer properties of nanofluids and applications involving local thermal non-equilibrium and microfluidic effects.
In this book, the author determines that a surface is itself a new material for chemical reaction, and the reaction of the surface provides additional new materials on that surface. The revelation of that peculiarity is what makes this book different from an ordinary textbook, and this new point of view will help to provide a new impetus when graduate students and researchers consider their results. The reaction of surface atoms provides additional new compounds, but these compounds cannot be detached from the surface. Some compounds are passive, but others work as catalysts. One superior feature of the surface is the dynamic cooperation of two or more different functional materials or sites on the same surface. This fact has been well established in the preferential oxidation of CO on platinum supported on a carbon nanotube with Ni-MgO at its terminal end. The Pt and Ni-MgO are perfectly separated, but these two are indispensable for the selective oxidation of CO in H2, where the H2O molecule plays a key role. The reader will understand that the complexity of catalysis is due to the complexity of the dynamic processes on the surface.
This book aims to introduce the basic concepts involved in industrial catalytic processes. It is profusely illustrated with experimental results with the main objective of guiding how to select a suitable catalyst for specific processes. The book is divided in two parts. In the first part the basic concepts are addressed, regarding the existing theories, activity patterns and adsorption-desorption phenomena. In the second part the key experimental methods for the physicochemical characterization of catalysts are presented, as well as the currently used catalyst pre and post treatments. The last chapter describes some important in situ characterization techniques (e.g. XPS and TEM) and surface model patterns related to surface modifications occurring during the reaction. Thoroughly illustrated with microscopy images, spectroscopy data and schematics of reaction mechanisms, the book provides a powerful learning tool for students in undergraduate and graduate level courses on the field of catalysis. Exercises and resolved problems are provided, as well as experimental procedures to support laboratory classes. Furthermore, the content is presented in a carefully chosen sequence, reflecting the 30 year teaching experience of the author. The author, Professor Martin Schmal, sees the present book as a way of conveying basic knowledge needed for the development of more efficient catalysts (i.e. nanostructured materials) and novel industrial chemical processes in the fields of environmental chemistry, fine chemistry, hydrotreating of heavy oils, hydrogen production and biomass processing.
This brief explains the principles and fundamentals of carbon dioxide utilization and highlights the transformation to fuels and value-added chemicals such as formic acid and methanol. It is divided into six chapters, including an introduction to the basics of CO2 utilization and transformation of CO2 to formic acid and methanol with homogeneous and heterogeneous catalysts, respectively. The brief will appeal to a wide readership of academic and industrial researchers focusing on homogeneous and heterogeneous catalysis, organometallic chemistry, green chemistry, energy conversion and storage.
Electrocatalysis in Balancing the Natural Carbon Cycle Explore the potential of electrocatalysis to balance an off-kilter natural carbon cycle In Electrocatalysis in Balancing the Natural Carbon Cycle, accomplished researcher and author, Yaobing Wang, delivers a focused examination of why and how to solve the unbalance of the natural carbon cycle with electrocatalysis. The book introduces the natural carbon cycle and analyzes current bottlenecks being caused by human activities. It then examines fundamental topics, including CO2 reduction, water splitting, and small molecule (alcohols and acid) oxidation to prove the feasibility and advantages of using electrocatalysis to tune the unbalanced carbon cycle. You'll realize modern aspects of electrocatalysis through the operando diagnostic and predictable mechanistic investigations. Further, you will be able to evaluate and manage the efficiency of the electrocatalytic reactions. The distinguished author presents a holistic view of solving an unbalanced natural carbon cycle with electrocatalysis. Readers will also benefit from the inclusion of: A thorough introduction to the natural carbon cycle and the anthropogenic carbon cycle, including inorganic carbon to organic carbon and vice versa An exploration of electrochemical catalysis processes, including water splitting and the electrochemistry CO2 reduction reaction (ECO2RR) A practical discussion of water and fuel basic redox parameters, including electrocatalytic materials and their performance evaluation in different electrocatalytic cells A perspective of the operando approaches and computational fundamentals and advances of different electrocatalytic redox reactions Perfect for electrochemists, catalytic chemists, environmental and physical chemists, and inorganic chemists, Electrocatalysis in Balancing the Natural Carbon Cycle will also earn a place in the libraries of solid state and theoretical chemists seeking a one-stop reference for all aspects of electrocatalysis in carbon cycle-related reactions.
This book reviews the latest advances and biomedical applications of nanozymes, which are artificial nanomaterials exhibiting enzymatic properties similar to natural enzymes, but with less limitations than natural enzymes. Nanozymes display advantages such as facile synthesis, easy surface modification, improved stability, higher catalytic power, and target-specific binding. Nanozymes containing metals, metal oxides, carbon, and metal sulfide are actually used for cancer therapy, biomolecules sensing, bioimaging, disease diagnostics and diabetes management. The book discloses underlying mechanisms, concepts, recent trends, constraints, and prospects for nanomedicine using nanozymes.
This brief presents the state of the art on enzymatic synthesis of structured triglycerides and diglycerides, focusing on glycerol as the substrate and covering interesterification of vegetable oils in one and two steps. It critically reviews the available literature on enzymatic and chemo-enzymatic synthesis of di- and triglycerides in one or more steps. The effects of the structure, length and unsaturation of the fatty acids are carefully considered, as well as the inhibitory potential of highly unsaturated complex fatty acid structures. The brief also addresses acyl migration and the use of adsorbents, taking into account the most recent literature and presenting the problem in an industrial context. It discusses experimental and analytical problems concerning, e.g. the lab scale and the scaling up to bench and pilot plants. Several examples are presented, and their successes and failures are assessed. Biocatalysts based on lipases are analyzed with regard to problems of immobilization, stability on storage time and activity after multiple uses. The need for specific Sn-2 lipases is presented and strategies for optimizing Sn-2 esterification are discussed. Lastly, practical aspects are examined, e.g. lipase "leaching" with loss of activity, taking into account the latest findings on continuous and batch reactor configurations and presenting the advantages and disadvantages of each.
The chemistry that occurs within confined spaces is the product of a collection of forces, often beyond the molecule, and is not easily ascribed to singular factors. There is a breadth of material types that can define a confined space (e.g. macrocycles, interlocked molecules, porous and non-porous crystals, organic and inorganic/coordination cages) which are rarely discussed together. Studies of supramolecular entities in the solution and solid states are also not often compared in the same discussion, even though the concepts are often similar or can be easily transferred between the two. Chapters in this book combine classical host-guest chemistry with catalysis, reactivity, and modern supramolecular chemistry. They cover the many different technologies used to describe and understand reactivity in confined spaces in one accessible title. With contributions from leading experts, Reactivity in Confined Spaces will be relevant for graduate students and researchers working in supramolecular chemistry, both organic- and inorganic-based, homogeneous and heterogeneous catalysis, polymer chemistry, and materials science in general.
This volume covers both basic and advanced aspects of organometallic chemistry of all metals and catalysis. In order to present a comprehensive view of the subject, it provides broad coverage of organometallic chemistry itself. The catalysis section includes the challenging activation and fictionalization of the main classes of hydrocarbons and the industrially crucial heterogeneous catalysis. Summaries and exercises are provides at the end of each chapter, and the answers to these exercises can be found at the back of the book. Beginners in inorganic, organic and organometallic chemistry, as well as advanced scholars and chemists from academia and industry will find much value in this title.
Carola Vogel's PhD thesis focuses on the synthesis, and structural and spectroscopic characterization of the first high valent iron nitride complexes. In her interdisciplinary and collaborative research Carola also describes the reactivity studies of a unique iron (V) nitride complex with water. These studies show that quantitative yields of ammonia are given at ambient conditions. High valent iron nitride and oxo species have been proposed as key intermediates in many bio-catalytic transformations, but until now these species have proven exceedingly challenging to isolate and study. Iron complexes in high oxidation states can thus serve as models for iron-containing enzymes to help us understand biological systems or aid our development of more efficient industrial catalysts.
The work presented in Thomas M. Gogsig's thesis deals with the discovery of new metal-catalyzed transformations ranging from Kumada-, Heck- and Suzuki-type reactions. The thesis starts with a formidable introduction to Pd-catalyzed cross-coupling reactions. New results have been obtained on: (i) Pd-catalyzed 1,2-migration reactions, (ii) Pd-catalyzed Heck reactions employing heteroaromatic tosylates, (iii) Ni-catalyzed Heck reactions, and (iv) Pd-catalyzed carbonylative Heck reaction. Metal-catalyzed cross-coupling reactions are today a highly competititve field (the 2010 Nobel Prize in Chemistry was awarded "for palladium-catalyzed cross couplings in organic synthesis", the 2001 and 2005 Nobel Prizes in closely related fields). Thomas M. Gogsig obtained new results in his thesis that will help to improve the outcome of catalytic processes and improve their scope. The results will thus become key references for tomorrow's new applications. All chapters include insightful discussions and in-depth descriptions of the key principles of these new discoveries.
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. |
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