Chemical redox reactions serve as an important class of transformations for the modernchemist, and advancements in homogeneous and heterogeneous catalysis are ever expanding the synthetic toolbox. Nonprecious metal catalysts and "green" reagents are sought after for their economic and environmental advantages to synthetic chemistries, and bridging seemingly disparate fields can lead to intriguing insights and developments. For decades, first-row transition metals incorporated into nitrogen-doped carbon (MNCs) have been studied for electrochemical oxygen reduction as leading alternatives to platinum in fuel cells, and more recently, MNCs have been used as catalysts for aerobic oxidation reactions in the context of organic synthesis. In this approach, protons and electrons from chemical bonds in organic molecules are used to promote oxygen reduction as balanced redox half reactions. This body of work describes our recent developments with MNC materials and their applications in organic synthesis. Chapter 1 offers an overview of MNC synthesis and characterization followed by a synopsisof the application of MNC catalysts to thermal organic transformations. This provides important context for Chapter 2 wherein we disclose our recently developed protocol for the incorporation of atomically-dispersed iron sites into nitrogen-doped carbon frameworks. The resulting MNC materials are then characterized in a cross-laboratory study targeting the quantification of active sites on MNCs prepared via diverse synthetic protocols. Chapter 3 presents the development of catalytic conditions for the formation of diazo compounds using oxygen as the terminal oxidant, initially by means of homogeneous copper catalysts. We then leveraged MNC catalysts for the same transformation and paired the formation of diazo compounds with enantioselective carbene transfer to achieve C-H insertion and cyclopropanation. This new MNC reactivity is further showcased in a flow reactor with gram-scale synthesis of diazo compounds. Chapter 4 describes ongoing work seeking to understand MNC-catalyzed hydrazone oxidation, including mechanistic insights, structure-activity relationships, and broadening this reactivity to other transformations involving proton-coupled electron transfers.

Metal air battery has captured the spotlight recently as a promising class of sustainable energy storage for the future energy systems. Metal air batteries offer many attractive features such as high energy density, environmental benignity, as well as ease of fuel storage and handling. In addition, wide range of selection towards different metals exists where different energy capacity can be achieved via careful selection of different metals. The most energy dense systems of metal-air battery include lithium-air, aluminum-air and zinc-air. Despite the choice of metal electrode, oxygen reduction (ORR) occurs on the air electrode and oxidation occurs on the metal electrode. The oxidation of metal electrode is a relatively facile reaction compared to the ORR on the air electrode, making latter the limiting factor of the battery system. The sluggish ORR kinetics greatly affects the power output, efficiency, and lifetime of the metal air battery. One solution to this problem is the use of active, affordable and stable catalyst to promote the rate of ORR. Currently, platinum nanoparticles supported on conductive carbon (Pt/C) are the best catalyst for ORR. However, the prohibitively high cost and scarcity of platinum raise critical issues regarding the economic feasibility and sustainability of platinum-based catalysts. Cost reduction via the use of novel technologies can be achieved by two approaches. The first approach is to reduce platinum loading in the catalyst formulation. Alternatively platinum can be completely eliminated from the catalyst composition. The aim of this work is to identify and synthesize alternative catalysts for ORR toward metal air battery applications without the use of platinum or other precious metals (i.e., palladium, silver and gold). Non-precious metal catalysts (NPMC) have received immense international attentions owing to the enormous efforts in pursuit of novel battery and fuel cell technologies. Different types of NPMC such as transition metal alloys, transition metal or mixed metal oxides, chalcogenides have been investigated as potential contenders to precious metal catalysts. However, the performance and stability of these catalysts are still inferior in comparison. Nitrogen-doped carbon materials (NCM) are an emerging class of catalyst exhibiting great potential towards ORR catalysis. In comparison to the metal oxides, MCM show improved electrical conductivity. Furthermore, NCM exhibit higher activity compared to chalcogenides and transition metal alloys. Additional benefits of NCM include the abundance of carbon source and environmental benignity. Typical NCM catalyst is composed of pyrolyzed transition metal macrocycles supported by high surface area carbon. These materials have demonstrated excellent activity and stability. However, the degradation of these catalysts often involves the destruction of active sites containing the transition metal centre. To further improve the durability and mass transport of NCM catalyst, a novel class of ORR catalyst based on nitrogen-doped carbon nanotubes (NCNT) is investigated in a series of studies. The initial investigation focuses on the synthesis of highly active NCNT using different carbon-nitrogen precursors. This study investigated the effect of using cyclic hydrocarbon (pyridine) and aliphatic hydrocarbon (ethylenediamine) towards the formation and activity of NCNT. The innate structure of the cyclic hydrocarbon promotes the formation of NCNT to provide higher product yield; however, the aliphatic hydrocarbon promotes the formation of surface defects where the nitrogen atoms can be incorporated to form active sites for ORR. As a result, a significant increase in the ORR activity of 180 mV in half-wave potential is achieved when EDA was used as carbon-nitrogen precursor. In addition, three times higher limiting current density was observed for the NCNT synthesized from ethylenediamine. Based on the conclusion where highly active NCNT was produced from aliphatic hydrocarbon, similar carbon-nitrogen precursors with varying carbon to nitrogen ratio in the molecular structure (ethylenediamine, 1, 3-diaminopropane, 1, 4-diaminobutane) were adapted for the synthesis of NCNT. The investigation led to the conclusion that higher nitrogen to carbon ratio in the molecular structure of the precursors benefits the formation of active NCNT for ORR catalysis. The origin of such phenomena can be correlated with the higher relative nitrogen content of the resultant NCNT synthesized from aliphatic carbon precursor that provided greater nitrogen to carbon ratio. As the final nitrogen content increased in the molecular structure, the half-wave potential of the resultant NCNT towards ORR catalysis was increased by 120 mV. The significant improvement hints the critical role of nitrogen content towards ORR catalysis.

This book discusses systematically the theoretical research and the applications of electrochemical oxygen reduction. Oxygen reduction reaction is a common issue in electrochemistry, but is also an important process involved in the field of energy, cryogenic fuel cells, metal–air cells, oxygen sensors and hydrogen peroxide preparation. This book is divided into 6 chapters; it starts with a description of dynamic mechanisms, followed by a detailed introduction on the related experimental methods and related catalyst preparation technology. By providing the basic methods and testing techniques, and by demonstrating their applications, it helps readers gain a better understanding of oxygen reduction reactions, making it a valuable resource for the industrialization of scientific research achievements. Accordingly, the book appeals to a broad readership, particularly graduate students, those working at universities and research organizations, and industrial researchers.

This introductory textbook covers all aspects of catalysis. It also bridges computational methods, industrial applications and green chemistry, with over 600 references. The book is aimed at chemistry and chemical engineering students, and is suitable for both senior undergraduate- and graduate-level courses, with many examples and hands-on exercises. The author, a renowned researcher in catalysis, is well known for his clear teaching and writing style (he was voted "lecturer of the year" by the chemistry students). Following an introduction to green chemistry and the basics of catalysis, the book covers the principles and applications of homogeneous catalysis, heterogeneous catalysis and biocatalysis. Each chapter includes up-to-date industrial examples, that demonstrate how catalysis helps our society reach the goals of sustainable development. Since its publication in 2008, Catalysis: Concepts and Green Applications has become the most popular textbook in catalysis. This second edition is updated with the latest developments in catalysis research in academia and industry. It also contains 50 additional exercises, based on the suggestions of students and teachers of chemistry and chemical engineering from all over the world. The book is also available in the Chinese language (https://detail.tmall.com/item.htm?spm=a212k0.12153887.0.0.4e60687dUTEDKm&id=619581126247). Additional teaching material (original figures as PowerPoint lecture slides) is freely available in the Supplementary Material.

Luminescent Metal Nanoclusters: Synthesis, Characterization, and Applications provides a comprehensive accounting of various protocols used for the synthesis of metal nanoclusters, their characterization techniques, toxicity evaluation and various applications and future prospects. The book provides detailed experimental routes, along with mechanisms on the formation of benign metallic clusters using biomaterials and a comprehensive review regarding the preparation, properties and prospective applications of these nano clusters in various fields, including therapeutic applications. Various methods to protect nanocluster materials to increase their stability are emphasized, including the incorporation of ligands (protein, small molecule, DNA, thiols). This book addresses a gap in the current literature by bringing together the preparation, characterization and applications of all the possible types of reported metal nanoclusters and their hybrids. It is suitable for materials scientists and engineers in academia and those working in research and development in industry. It may also be of interest to those working in the interdisciplinary nanotechnology community, such as physical chemists. - Covers the most relevant material categories of luminescent nanoclusters such as metal nanoclusters, nano composites and alloy nanoclusters - Provides a comprehensive overview of the various available methods used for the protection of nanoclusters - Discusses the latest advances and future opportunities in addressing challenges in producing benign nanomaterials such as toxicity and stability

Photoelectrocatalysis: Fundamentals and Applications presents an in-depth review of the topic for students and researchersworking on photoelectrocatalysis-related subjects from pure chemistry to materials and environmental chemistry inorder to propose applications and new perspectives. The main advantage of a photoelectrocatalytic process is the mildexperimental conditions under which the reactions are carried out, which are often possible at atmospheric pressure androom temperature using cheap and nontoxic solvents (e.g., water), oxidants (e.g., O2 from the air), catalytic materials (e.g.,TiO2 on Ti layer), and the potential exploitation of solar light. This book presents the fundamentals and the applications of photoelectrocatalysis, such as hydrogen production fromwater splitting, the remediation of harmful compounds, and CO2 reduction. Photoelectrocatalytic reactors and lightsources, in addition to kinetic aspects, are presented along with an exploration of the relationship between photocatalysisand electrocatalysis. In addition, photocorrosion issues and the application of selective photoelectrocatalytic organictransformations, which is now a growing field of research, are also reported. Finally, the advantages/disadvantages andfuture perspectives of photoelectrocatalysis are highlighted through the possibility of working at a pilot/industrial scale inenvironmentally friendly conditions. Presents the fundamentals of photoelectrocatalysis Outlines photoelectrocatalytic green chemistry Reviews photoelectrocatalytic remediation of harmful compounds, hydrogen production, and CO2 reduction Includes photocorrosion, photoelectrocatalytic reactors, and modeling along with kinetic aspects

In 1972, a very powerful catalytic cycle for carbon-carbon bond formation was 2 first discovered by the coupling reaction of Grignard reagents at the sp -carbon. Over the past 30 years, the protocol has been substantially improved and expanded to other coupling reactions of Li,B,N,O,Al,Si,P,S,Cu,Mn,Zn,In,Sn, and Hg compounds. These reactions provided an indispensable and simple methodology for preparative organic chemists. Due to the simplicity and rel- bility in the carbon-carbon, carbon-heteroatom, and carbon-metalloid bo- formations,as well as high efficiency of the catalytic process,the reactions have been widely employed by organic chemists in various fields. Application of the protocol ranges from various syntheses of complex natural products to the preparation of biologically relevant molecules including drugs, and of sup- molecules, and to functional materials. The reactions on solid surfaces allow robot synthesis and combinatorial synthesis. Now, many organic chemists do not hesitate to use transition metal complexes for the transformation of org- ic molecules. Indeed, innumerable organic syntheses have been realized by the catalyzed reactions of transition metal complexes that are not achievable by t- ditional synthetic methods. Among these, the metal-catalyzed cross-coupling reactions have undoubtedly contributed greatly to the development of such a new area of “metal-catalyzed organic syntheses”. An excellent monograph for the cross-coupling reactions and other met- catalyzed C-C bond-forming reactions recently appeared in Metal-catalyzed Cross-coupling Reactions (Wiley-VCH,1998).

Exciting results are still emerging from the many research groups working in this fertile area and the book is an excellent stimulus to researchers at the start of the 21st century."--BOOK JACKET.