Development and Mechanistic Study of Copper-based Water Oxidation Catalysts

Development and Mechanistic Study of Copper-based Water Oxidation Catalysts
Author: Shoshanna Barnett
Publisher:
Total Pages: 115
Release: 2013
Genre: Copper catalysts
ISBN:

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Water oxidation is a challenging reaction that has great importance for alternative energy and fuel generation. Although several water oxidation catalysts have been discovered, much improvement is needed for the technology to be viable on a global scale. In recent years, there has been focus in the development of catalysts with earth-abundant elements and, subsequently, cobalt, nickel, manganese, and iron catalysts have been reported. This dissertation discusses the discovery and study of the first reported copper-based water oxidation electrocatalyst. This catalyst is a molecular species with bipyridine and hydroxide ligands. Study of this catalyst has shown that it is among the fastest homogeneous water oxidation catalysts yet reported, with a turnover frequency of ~100 s-1. The catalyst is also relatively robust and can undergo at least 30 turnovers. Solutions of the catalyst are generated easily by reaction of bipyridine and a copper salt in a 1:1 ratio in water, followed by addition of hydroxide to obtain a solution between pH 11 and 13. The catalytic mechanism has been investigated through spectroscopic analysis to understand the speciation, electrochemical kinetics, a ligand study, and reactivity studies. While further work is still needed, these investigations have laid the groundwork for a basic understanding of the mechanism. A phenanthroline-based catalyst has also been successfully immobilized on a pyrolytic graphite electrode through physisorption. The heterogeneous catalyst shows remarkable similarities to its homogeneous counterpart. It operates at the same overpotential and activity level and displays similar pH dependent behavior. This system has important implications for catalyst immobilization in general, which is an important area of study for the development of more industrially relevant catalysts.

Water Oxidation Catalysts

Water Oxidation Catalysts
Author:
Publisher: Academic Press
Total Pages: 380
Release: 2019-06-22
Genre: Science
ISBN: 0128160837

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Water Oxidation Catalysts, Volume 74, the latest release in the Advances in Inorganic Chemistry series, presents timely and informative summaries on current progress in a variety of subject areas. This acclaimed serial features reviews written by experts in the field, serving as an indispensable reference to advanced researchers. Users will find this to be a comprehensive overview of recent findings and trends from the last decade that covers various kinds of inorganic topics, ranging from theoretical oriented supramolecular chemistry, to the quest for accurate calculations of spin states in transition metals. Provides the authority and expertise of leading contributors from an international board of authors Presents the latest release in the Advances in Inorganic Chemistry series Includes the latest information on water oxidation catalysts

Mechanistic Studies of Water Oxidation and Carbon Dioxide Reduction Using Transition Metal Catalysts with Protic Ligands

Mechanistic Studies of Water Oxidation and Carbon Dioxide Reduction Using Transition Metal Catalysts with Protic Ligands
Author: Dalton Bodine Burks
Publisher:
Total Pages: 292
Release: 2019
Genre: Electronic dissertations
ISBN:

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The majority of energy produced in the world is derived from fossil fuels which are finite and have deleterious environmental effects. For a sustainable and environmentally-friendly energy future, alternative, renewable energy sources are desired. Two reactions that could have applications towards developing renewable energy sources are water oxidation to produce hydrogen and carbon dioxide reduction to form various products (e.g. formic acid or carbon monoxide); however, these reactions require catalysts to efficiently produce the desired products. Efforts to synthesize, characterize, and study catalysts for these reactions are discussed in this dissertation. The first chapter serves as an introduction to energy-related catalytic reactions. In Chapter 2, 6,6ʹ-dihydroxybipyridine (6,6ʹ-dhbp)-a protic ligand used with several metals to produce catalysts for energy-related reactions-is studied to determine its thermodynamic acidity. In the following chapter, 6,6ʹ-dhbp is used as a ligand with copper to form complexes that are water oxidation catalysts. Chapters 4 and 5 focus on iridium and ruthenium complexes containing new bidentate ligands composed of pyridinol and N-heterocyclic carbenes (NHCs). These complexes, along with an iridium complex of 6,6ʹ-dhbp, were used as catalysts for the hydrogenation of carbon dioxide to formate and the reverse dehydrogenation of formic acid to carbon dioxide and hydrogen. However, the complexes containing the new bidentate pyridinol-NHC ligands were found to be precatalysts as they undergo transformations and decomposition during the course of the reaction. A nickel-pincer complex with a protic CNC-pincer derived of pyridinol and NHCs was used as a photocatalyst for carbon dioxide reduction in Chapter 6. The protic state of the hydroxy group in the 4-position of the pyridine ring was determined to be important for catalysis, as the deprotonated hydroxy group results in 10 times the catalytic ability as the protonated form. In the penultimate chapter, ruthenium-pincer complexes that are active carbon dioxide photoreduction catalysts are studied mechanistically by UV/vis and IR spectroscopies. The most active catalyst was studied in greater detail with real-time IR spectroscopy to help elucidate potential reaction pathways. The final chapter serves as a conclusion to summarize the results discussed in the dissertation.

Reaction Kinetics and the Development and Operation of Catalytic Processes

Reaction Kinetics and the Development and Operation of Catalytic Processes
Author: G.F. Froment
Publisher: Elsevier
Total Pages: 663
Release: 2001-04-03
Genre: Science
ISBN: 0080540295

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Reaction Kinetics and the Development and Operation of Catalytic Processes is a trendsetter. The Keynote Lectures have been authored by top scientists and cover a broad range of topics like fundamental aspects of surface chemistry, in particular dynamics and spillover, the modeling of reaction mechanisms, with special focus on the importance of transient experimentation and the application of kinetics in reactor design. Fundamental and applied kinetic studies are well represented. More than half of these deal with transient kinetics, a new trend made possible by recent sophisticated experimental equipment and the awareness that transient experimentation provides more information and insight into the microphenomena occurring on the catalyst surface than steady state techniques. The trend is not limited to purely kinetic studies since the great majority of the papers dealing with reactors also focus on transients and even deliberate transient operation. It is to be expected that this trend will continue and amplify as the community becomes more aware of the predictive potential of fundamental kinetics when combined with detailed realistic modeling of the reactor operation.

Non-Noble Metal Catalysis

Non-Noble Metal Catalysis
Author: Robertus J. M. Klein Gebbink
Publisher: John Wiley & Sons
Total Pages: 610
Release: 2019-04-29
Genre: Technology & Engineering
ISBN: 3527340610

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An expert overview of current research, applications, and economic and environmental advantages The study and development of new homogeneous catalysts based on first-row metals (Mn, Fe, Co, Ni, and Cu) has grown significantly due to the economic and environmental advantages that non-noble metals present. Base metals offer reduced cost, greater supply, and lower toxicity levels than noble metals?enabling greater opportunity for scientific investigation and increased development of practical applications. Non-Noble Metal Catalysis provides an authoritative survey of the field, from fundamental concepts and computational methods to industrial applications and reaction classes. Recognized experts in organometallic chemistry and homogeneous catalysis, the authors present a comprehensive overview of the conceptual and practical aspects of non-noble metal catalysts. Examination of topics including non-innocent ligands, proton-coupled electron transfer, and multi-nuclear complexes provide essential background information, while areas such as kinetic lability and lifetimes of intermediates reflect current research and shifting trends in the field. This timely book demonstrates the efficacy of base metal catalysts in the pharmaceutical, fine-chemical, and agrochemical industries, addressing both environmental and economic concerns. Providing essential conceptual and practical exploration, this valuable resource: -Illustrates how unravelling new reactivity patterns can lead to new catalysts and new applications -Highlights the multiple advantages of using non-noble metals in homogenous catalysis -Demonstrates how the availability of non-noble metal catalysis reduces costs and leads to immense savings for the chemical industry -Reveals how non-noble metal catalysis are more sustainable than noble metals such as palladium or platinum Non-Noble Metal Catalysis: Molecular Approaches and Reactions is an indispensable source of up-to-date information for catalytic chemists, organic chemists, industrial chemists, organometallic chemists, and those seeking to broaden their knowledge of catalytic chemistry.

Biological Inorganic Chemistry

Biological Inorganic Chemistry
Author: Ivano Bertini
Publisher: University Science Books
Total Pages: 794
Release: 2007
Genre: Science
ISBN: 9781891389436

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Part A.: Overviews of biological inorganic chemistry : 1. Bioinorganic chemistry and the biogeochemical cycles -- 2. Metal ions and proteins: binding, stability, and folding -- 3. Special cofactors and metal clusters -- 4. Transport and storage of metal ions in biology -- 5. Biominerals and biomineralization -- 6. Metals in medicine. -- Part B.: Metal ion containing biological systems : 1. Metal ion transport and storage -- 2. Hydrolytic chemistry -- 3. Electron transfer, respiration, and photosynthesis -- 4. Oxygen metabolism -- 5. Hydrogen, carbon, and sulfur metabolism -- 6. Metalloenzymes with radical intermediates -- 7. Metal ion receptors and signaling. -- Cell biology, biochemistry, and evolution: Tutorial I. -- Fundamentals of coordination chemistry: Tutorial II.

Molecular Water Oxidation Catalysis

Molecular Water Oxidation Catalysis
Author: Antoni Llobet
Publisher: John Wiley & Sons
Total Pages: 343
Release: 2014-04-14
Genre: Technology & Engineering
ISBN: 1118698622

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Photocatalytic water splitting is a promising strategy for capturing energy from the sun by coupling light harvesting and the oxidation of water, in order to create clean hydrogen fuel. Thus a deep knowledge of the water oxidation catalysis field is essential to be able to come up with useful energy conversion devices based on sunlight and water splitting. Molecular Water Oxidation Catalysis: A Key Topic for New Sustainable Energy Conversion Schemes presents a comprehensive and state-of-the-art overview of water oxidation catalysis in homogeneous phase, describing in detail the most important catalysts discovered today based on first and second row transition metals. A strong emphasis is placed on the description of their performance, as well as how they work from a mechanistic perspective. In addition, a theoretical description of some of the most relevant catalysts based on DFT are presented, as well as a description of related natural systems, such as the oxygen evolving system of photosystem II and the heme chlorite-dismutase. This book is a valuable resource for researchers working on water oxidation catalysis, solar energy conversion and artificial photosynthesis, as well as for chemists and materials scientists with a broad interest in new sustainable energy conversion schemes.

Copper Catalysis in Organic Synthesis

Copper Catalysis in Organic Synthesis
Author: Gopinathan Anilkumar
Publisher: John Wiley & Sons
Total Pages: 504
Release: 2020-12-07
Genre: Technology & Engineering
ISBN: 3527347372

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The most current information on growing field of copper catalysis Copper Catalysis in Organic Synthesis contains an up-to-date overview of the most important reactions in the presence of copper catalysts. The contributors—noted experts on the topic—provide an introduction to the field of copper catalysis, reviewing its development, scope, and limitations, as well as providing descriptions of various homo- and cross-coupling reactions. In addition, information is presented on copper-catalyzed C–H activation, amination, carbonylation, trifluoromethylation, cyanation, and click reactions. Comprehensive in scope, the book also describes microwave-assisted and multi-component transformations as well as copper-catalyzed reactions in green solvents and continuous flow reactors. The authors highlight the application of copper catalysis in asymmetric synthesis and total synthesis of natural products and heterocycles as well as nanocatalysis. This important book: Examines copper and its use in organic synthesis as a more cost-effective and sustainable for researchers in academia and industry Offers the first up-to-date book to explore copper as a first line catalyst for many organic reactions Presents the most significant developments in the area, including cross-coupling reactions, C–H activation, asymmetric synthesis, and total synthesis of natural products and heterocycles Contains over 20 contributions from leaders in the field Written for catalytic chemists, organic chemists, natural products chemists, pharmaceutical chemists, and chemists in industry, Copper Catalysis in Organic Synthesis offers a book on the growing field of copper catalysis, covering cross-coupling reactions, C–H activation, and applications in the total synthesis of natural products.

Lectures on Electrochemical Corrosion

Lectures on Electrochemical Corrosion
Author: Marcel Pourbaix
Publisher: Springer Science & Business Media
Total Pages: 352
Release: 2012-12-06
Genre: Science
ISBN: 1468418068

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Workers in the field of corrosion and their students are most fortunate that a happy set of circumstances brought Dr. Marcel Pourbaix into their field in 1949. First, he was invited, while in the USA, to demonstrate at a two week visit to the National Bureau of Standards the usefulness of his electro chemical concepts to the study of corrosion. Secondly, also around the same time, Prof. H. H. Uhlig made a speech before the United Nations which pointed out the tremendous economic consequences of corrosion. Because of these circumstances, Dr. Pourbaix has reminisced, he chose to devote most of his efforts to corrosion rather than to electrolysis, batteries, geology, or any of the other fields where, one might add, they were equally valuable. This decision resulted in his establishing CEBELCOR (Centre BeIge d'Etude de la Corrosion) and in his development of a course at the Free University of Brussels entitled "Lectures on Electrochemical Corrosion." This book is the collection of these lectures translated into English.