This thesis systematically introduces readers to a new metal-organic framework approach to fabricating nanostructured materials for electrochemical applications. Based on the metal-organic framework (MOF) approach, it also demonstrates the latest ideas on how to create optimal MOF and MOF-derived nanomaterials for electrochemical reactions under controlled conditions. The thesis offers a valuable resource for researchers who want to understand electrochemical reactions at nanoscale and optimize materials from rational design to achieve enhanced electrochemical performance. It also serves as a useful reference guide to fundamental research on advanced electrochemical energy storage materials and the synthesis of nanostructured materials.

This book provides a review of the latest advances in anion exchange membrane fuel cells. Starting with an introduction to the field, it then examines the chemistry and catalysis involved in this energy technology. It also includes an introduction to the mathematical modelling of these fuel cells before discussing the system design and performance of real-world systems. Anion exchange membrane fuel cells are an emerging energy technology that has the potential to overcome many of the obstacles of proton exchange membrane fuel cells in terms of the cost, stability, and durability of materials. The book is an essential reference resource for professionals, researchers, and policymakers around the globe working in academia, industry, and government.

This volume describes the recent developments in the free-radical mediated synthesis and elaboration of heterocycles. The first chapter, dealing with radical cascade processes illustrates the power and the beauty of radical chemistry with some striking examples of total synthesis of complex natural heterocycles. As organic chemists strive towards sustainability, radical chemistry has recently seen major advances and efforts in this direction, including C-H activation of arenes and unactivated alkyl groups. Photochemical activation, for a long time the preferred mode of activation in radical chemistry has also seen an unexpected revival with the advent of visible light metal- and organocatalyzed photoredox processes. A survey of these emerging areas is provided along with the concepts at the origin of these developments. The venerable Minisci reaction allows for direct access to functionalized heterocycles. This process has lately seen an interesting renaissance and is discussed in this volume. Addition of heteroatom-centered radicals onto unsaturated systems constitutes another powerful method to construct heterocycles. Examples of such a strategy are proposed along with the formation of various heterocycles relying on homolytic substitution at sulfur, phosphorus and selenium. Additionally free-radical functionalization of reactive functional groups including isonitriles, isothiocyanates and related unsaturated systems which offer a straightforward route towards useful aromatic and non-aromatic heterocycles are discussed. Finally, as metals are able to trigger single electron transfer both in reductive and oxidative modes this provides another possibility for the synthesis of heterocycles. Significant research efforts have focused on the use of samarium, copper and other metals to access a broad variety of heterocycles in a single pot process, starting from readily available raw material. Examples and mechanistic insights are discussed by experts in this area.

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.

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 of 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. All chapters from Topics in Organometallic Chemistry are published OnlineFirst with an individual DOI. In references, Topics in Organometallic Chemistry is abbreviated as Top Organomet Chem and cited as a journal.

Global experts provide an authoritative source of information on the use of electrochemical fuel cells, and in particular discuss the use of nanomaterials to enhance the performance of existing energy systems. The book covers the state of the art in the design, preparation, and engineering of nanoscale functional materials as effective catalysts for fuel cell chemistry, highlights recent progress in electrocatalysis at both fuel cell anode and cathode, and details perspectives and challenges in future research.

This book provides microscopic insights into chemical properties of NO on metal surfaces. NO/metal systems have been studied intensively to understand heterogeneous catalysis to detox exhaust NOx gas. The identification and componential analysis of various and mixed chemical species of NO adsorbed onto the surfaces have been significant challenges faced by conventional experimental techniques, such as vibrational spectroscopies. The author investigated "individual" NO molecules on Cu surfaces using low-temperature scanning tunneling microscopy (STM). STM not only provides information on the geometric, electronic, and vibrational properties at the single-molecule level; it is also able to manipulate molecules on surfaces to induce chemical reaction. Exploiting those techniques, the author chemically identified individual NO-related species on the surfaces and discovered new reaction processes for NO reduction, which provides microscopic insights into the catalytic mechanisms. The author also visualized wave functions of electrons in a valence orbital of NO and demonstrated that the wave functions are modified by the formation of covalent bonding or hydrogen bonding. This is, namely, "the visualization of quantum mechanics in real space," which is certainly worth reading. Furthermore, the book demonstrates that direct observation of valence orbitals helps to elucidate the reactivity of molecules adsorbed onto surfaces. This innovative approach to studying molecular properties will contribute to further development of STM and its related methods.

This book presents a detailed history of chemical warfare development during the First World War and discusses design approaches to gas masks and the performance of new filter materials that decontaminate chemical warfare agents (CWA) when applied in the vapor phase. It describes multifunctional nanocomposites containing zinc and zirconium (hydr)oxides, graphite oxide and silver or gold nanoparticles as reactive adsorbents for the degradation of the CWAs vapors. In addition it examines in detail the surface properties that are most important in the mineralization performance.

This thesis presents detailed mechanistic studies on a series of important C-H activation reactions using combined computational methods and mass spectrometry experiments. It also provides guidance on the design and improvement of catalysts and ligands. The reactions investigated include: (i) a nitrile-containing template-assisted meta-selective C-H activation, (ii) Pd/mono-N-protected amino acid (MPAA) catalyzed meta-selective C-H activation, (iii) Pd/MPAA catalyzed asymmetric C-H activation reactions, and (iv) Cu-catalyzed sp3 C-H cross-dehydrogenative-coupling reaction. The book reports on a novel dimeric Pd-M (M = Pd or Ag) model for reaction (i), which successfully explains the meta-selectivity observed experimentally. For reaction (ii), with a combined DFT/MS method, the author successfully reveals the roles of MPAA ligands and a new C-H activation mechanism, which accounts for the improved reactivity and high meta-selectivity and opens new avenues for ligand design. She subsequently applies ion-mobility mass spectrometry to capture and separate the [Pd(MPAA)(substrate)] complex at different stages for the first time, providing support for the internal-base model for reaction (iii). Employing DFT studies, she then establishes a chirality relay model that can be widely applied to MPAA-assisted asymmetric C-H activation reactions. Lastly, for reaction (iv) the author conducts detailed computational studies on several plausible pathways for Cu/O2 and Cu/TBHP systems and finds a reliable method for calculating the single electron transfer (SET) process on the basis of benchmark studies.

The principal aim of this book is to introduce chemists through a tutorial approach to the use of microwaves by examining several experiments of microwave chemistry and materials processing. It will subsequently enable chemists to fashion their own experiments in microwave chemistry or materials processing. Microwave heating has become a popular methodology in introducing thermal energy in chemical reactions and material processing in laboratory-scale experiments. Several research cases where microwave heating has been used in a wide range of fields have been reported, including organic synthesis, polymers, nanomaterials, biomaterials, and ceramic sintering, among others. In most cases, microwave equipment is used as a simple heat source. Therefore the principal benefits of microwave radiation have seldom been taken advantage of. One reason is the necessity to understand the nature of electromagnetism, microwave engineering, and thermodynamics. However, it is difficult for a chemist to appreciate these in a short time, so they act as barriers for the chemist who might take an interest in the use of microwave radiation. This book helps to overcome these barriers by using figures and diagrams instead of equations as much as possible.

In this thesis, the author outlines the construction of active structure and modulation of catalytic reactivity of Pt-based bi-component catalysts, from the model systems to real supported catalysts. The thesis investigates the promotion effect of the second components on catalytic performance of Pt catalysts, and presents the reversible generation of the "sandwich-like" structure of Pt-Ni catalysts, containing both surface NiO1-X and subsurface Ni by alternating redox treatments at medium temperature. With the aid of single layer graphene, the dynamic process of chemical reactions occurring on the Pt(111) surface can be visualized using in-situ LEEM and DUV-PEEM techniques, the results of which are included here. The author reveals that the graphene layer exhibits a strong confinement effect on the chemistry of molecules underneath and the intercalated CO can desorb from the Pt surface around room temperature and in UHV, which may promote the CO oxidation confined under graphene.

This book introduces carbon nanotubes as a matrix for efficient nanohybrid catalysis. The preparation and use of such materials in ultra-grade water purification is described. Simple chemical methods for purification and functionalization of carbon nanotubes prior to their use is also detailed. The author also discusses the potential use of nanotube-based nanobiohybrid catalysts in the removal of organic pollutants.

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.

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 outstanding thesis describes a detailed investigation into the use of low-oxidation-state group 14 complexes in catalysis, developed at the cutting edge of inorganic and organometallic chemistry. It includes the preparation of a number of landmark compounds, some of which challenge our current understanding of metal-metal bonding and low-oxidation-state main group chemistry. Among the many highlights of this thesis, the standout result is the development of the first well-defined, low- oxidation-state main group hydride systems as highly efficient catalysts in the hydroboration of carbonyl substrates, including carbon dioxide, which are as efficient as those observed in more traditional, transition-metal catalyses. These results essentially define a new subdiscipline of chemistry.

This handbook is a valuable resource for scientists, engineers, graduate students, managers, decision makers, and those who are interested in ionic liquids. Many industrial applications rely on the use of Ionic Liquid Mixtures, as in solar energy storage, waste recycling or batteries.Physicochemical Properties of Ionic Liquid Mixtures is a useful handbook that contains the following features: - the physicochemical properties and property models of mixtures containing ionic liquids - supplemented by a comprehensive database of properties listing ionic liquid systems collected from more than 800 dependable literature sources - over 60,000 data entries on 39 types of physicochemical properties for 1388 mixtures, including binary, ternary, quaternary and other mixtures.

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 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.

This book focuses on direct nitrogenation strategies to incorporate one or more N-atoms into simple substrates especially hydrocarbons via C-H and/or C-C bond cleavage, which is a green and sustainable way to synthesize nitrogen-containing compounds. The book consists of seven chapters demonstrating interesting advances in the preparation of amines, amides, nitriles, carbamides, azides, and N-heterocyclic compounds and illustrating the mechanisms of these novel transformations. It offers an accessible introduction to nitrogenation reactions for chemists involved in N-compound synthesis and those interested in discovering new reagents and reactions. Ning Jiao is a Professor of Chemistry at Peking University, China.

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 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 book is a comprehensive, theoretical, practical, and thorough guide to XAFS spectroscopy. The book addresses XAFS fundamentals such as experiments, theory and data analysis, advanced XAFS methods such as operando XAFS, time-resolved XAFS, spatially resolved XAFS, total-reflection XAFS, high energy resolution XAFS, and practical applications to a variety of catalysts, nanomaterials and surfaces. This book is accessible to a broad audience in academia and industry, and will be a useful guide for researchers entering the subject and graduate students in a wide variety of disciplines.

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.

This book addresses electrocatalysis based on chalcogenides, particularly in the nanoscale domain. Special attention is paid to the hydrogen evolution reaction (HER) and the oxygen reduction reaction (ORR). The book provides an introduction to materials synthesis; the basic principles of electrocatalysis; related precious metal versus non-precious metal catalytic center chalcogenides as well as supports; and the role of such supports in stabilizing the catalytic centers. In short: pursuing a bottom-up approach, it covers the properties of this class of electrocatalysts and examines their applications in low-temperature fuel systems such as microfluidic fuel cells for portable devices. Accordingly, it is ideally suited for all professionals and researchers interested in electrochemistry, renewable energy and electrocatalysis, and non-precious metal centers for chemical energy conversion.