Catalysis Books

Book SynopsisThis book, unique in its field, is a comprehensive description of all the methodologies reported for carrying out conjugate addition reactions in a stereoselective way, using small chiral organic molecules as catalysts (organocatalysts). In the last 3-4 years, this has been a rapidly growing field in organic chemistry, and many papers have appeared reporting excellent protocols for carrying out these highly efficient transformations that compete well with other classical approaches using transition metal catalysts. A particularly attractive feature of this transformation relies upon the fact that the conjugate addition (Michael and Hetero-Michael reactions) is an extraordinarily effective means to initiate cascade processes which result in the formation of complex molecules from very small and simple starting blocks. The book, written by noted experts, covers all recent advances in this hot topic, and provides a good state-of-the-art review for organic chemists working in this field and all those who wish to start projects in this area.Trade Review"The book is focused on enantioselective organocatalysis in the context of conjugate addition reactions, a vast category of reactions that include some of the most versatile carbon-carbon and carbon-heteroatom bond-forming reactions. The authors are themselves active contributors to the area, including the development of new methodologies"."The overall organisation of this book is excellent, and is based on an appropriate selection of representative protocols that illustrate how different types of chiral organocatalysts can promote conjugate additions and control the sterochemical outcome"."The book is written with clarity and is very well structured"."Each topic is highlighted by seminal contributors from the pioneers on the subject area" * Angew Chem. Claudio Palomo Niucolau *Table of ContentsIntroduction; Enantioselective conjugate reactions via iminium activation; Enantioselective conjugate reactions via enamine activation; Enantioselective conjugate reactions via hydrogen-bonding activation; Enantioselective conjugate reactions via chiral ammonium ion formation; Organocatalytic enantioselective cascade reactions

Read more less

Book SynopsisOver the last fifteen years, N-heterocyclic carbenes (NHCs) have mostly been used as ancillary ligands for the preparation of transition metal-based catalysts. Compared to phosphorus-containing ligands, NHCs tend to bind more strongly to metal centres, avoiding the necessity for the use of excess ligand in catalytic reactions. The corresponding complexes are often less sensitive to air and moisture, and have proven remarkably resistant to oxidation. Recent developments in catalysis applications have been facilitated by the availability of carbenes stable enough to be bottled, particularly for their use as organocatalysts. This book shows how N-heterocyclic carbenes can be useful in various fields of chemistry and not merely laboratory curiosities or simple phosphine mimics. NHCs are best known for their contribution to ruthenium and palladium-catalysed reactions but the scope of this book is much broader. The synthesis of NHC ligands and their corresponding metal complexes are covered in depth. Moreover, the biological activity of NHC-containing complexes, as well as an overview of their theoretical aspects are included. Such metal species are further examined, not only in terms of their catalytic applications, but also of their stereoelectronic parameters and reactivity/stability. Finally, special attention is given to the hot topic of organocatalysis. The book will be of interest to postgraduates, academic researchers and those working in industry.Table of ContentsChapter 1: Introduction to N-Heterocyclic Carbenes: Synthesis and Stereoelectronic Parameters; Chapter 2: Computational Studies on the Reactivity of Transition Metal Complexes with N-Heterocyclic Carbene Ligands; Chapter 3: Synthesis, Activation and Decomposition of N-Heterocyclic Carbene-Containing Complexes; Chapter 4: Biologically Active N-Heterocyclic Carbene-Metal Complexes; Chapter 5: Non-Classical N-Heterocyclic Carbene Complexes; Chapter 6: Early Transition and Rare Earth Metal Complexes with N-Heterocyclic Carbenes; Chapter 7: NHC-Iron, Ruthenium, AND Osmium Complexes in Catalysis; Chapter 8: NHC-Cobalt, Rhodium, and Iridium Complexes in Catalysis; Chapter 9: NHC-Palladium Complexes in Catalysis; Chapter 10: NHC-Nickel and Platinum Complexes in Catalysis; Chapter 11: NHC-Copper, Silver AND Gold Complexes in Catalysis; Chapter 12: Oxidation Reaction with NHC Metal Complexes; Chapter 13: Reduction Reactions with NHC-Bearing Complexes; Chapter 14: N-Heterocyclic Carbenes as Organic Catalysts

Read more less

Book SynopsisThe aim of this book is to cover the very recent developments in asymmetric organocatalysis, focussing on those published since the beginning of 2008. The last decade has witnessed an explosive growth in the field of asymmetric organocatalysis with an impressive amount of new catalysts, novel methodologies, and applications in numerous reaction types, such as nucleophilic substitutions, addition reactions, as well as cycloadditions, oxidations, reductions, kinetic resolutions, and miscellaneous reactions. This very diverse and intensely developing field is too wide to cover in a single review. The timeliness of the book together with the expected impact is excellent, since nowadays asymmetric organocatalysis is arguably the most intensively developed field in organic chemistry. The book is designed to meet the demands of a postgraduate textbook,containing case studies and Q&A sections, as well as a practical book filled with facts and data useful as a working tool for the practitioner. The book is divided into ten sections, dealing successively with nucleophilic additions to electron-deficient C=C double bonds, nucleophilic additions to C=O double bonds, nucleophilic additions to C=N double bonds, nucleophilic additions to unsaturated nitrogen, nucleophilic substitutions at aliphatic carbon, cycloaddition reactions, oxidations, reductions, kinetic resolutions and desymmetrisations, and miscellaneous reactions.Trade Review"A strength of the book lies in the extensive use of graphics. Virtually every entry in the book is provided a graphic summary of the best cases for a particular report.""This compilation can be regarded as a snapshot of progress for a field that requires treatment in any modern graduate program in organic chemistry.""...the author has produced a work that is commendable by the measures of the topics selected and their organization." * Journal of the American Chemical Society (JACS),2011, 133, 2330 - 2330, Jeffrey N Johnston *"...this book was set out to update the audience on the application of asymmetric organocatalysis after several earlier review articles and this certainly meets the task with a plethora of detailed reports on important asymetric organic catalysed processes.""This book will appeal to those researchers engaged in catalysis at phD or post-doctoral level and provides a useful compendium on a wide number of organocatalytic transformations." * Chemistry World, February 2011, Benjamin Buckley *Table of ContentsIntroduction Nucleophilic additions to electron-deficient C=C double bonds Nucleophilic additions to C=O double bonds Nucleophilic additions to C=N double bonds Nucleophilic additions to unsaturated nitrogen Nucleophilic substitutions at aliphatic carbon Cycloaddition reactions Oxidations Reductions Kinetic resolutions and desymmetrisations Miscellaneous reactions General Conclusion

Read more less

Book SynopsisFischer-Tropsch Synthesis (FTS) has been used on a commercial scale for more than eighty years. It was initially developed for strategic reasons because it offered a source of transportation fuels that was independent from crude oil. Unlike crude, Fischer-Tropsch synthetic crude is rich in olefins and oxygenates, while being sulphur and nitrogen free. Consequently, the catalysis involved in refining it is significantly different and only a few catalysts have been developed for the purpose. Until now, an account of this topic has been missing from the literature, despite mounting interest in the technology. This is the first book to provide a review and analysis of the literature (journal and patent) on the catalysis needed to refine syncrude to transportation fuels. It specifically highlights the impact of oxygenates and how oxygenates affect selectivity and deactivation. This aspect is also related to the refining of biomass derived liquids. Topics covered include: dimerisation / oligomerisation, isomerisation / hydroisomerisation, catalytic cracking / hydrocracking and hydrogenation, catalytic reforming, aromatic alkylation, etherification, dehydration, and some oxygenate and wax specific conversions.Trade Review'This book provides an in-depth look at some of the technologies and processes used to upgrade synfuel stocks, including oligomerization, isomerisation, cracking/hydrocracking and hydrotreating.''This book provides an excellent and comprehensive evaluation of the catalytic processes for syncrude conversion to useful products such as fuel and oils.''The writing style is very clear and explains the processes concisely and simply'. * Stewart Brown *Table of ContentsINTRODUCTION; PRODUCTION OF SYNTHESIS GAS; FISCHER-TROPSCH SYNTHESIS; PROPERTIES OF PRIMARY PRODUCTS FROM FT; UPGRADING OF GASEOUS AND LIQUID PRODUCTS; UPGRADING OF FTS WAX; REACTIONS OF OXYGENATES; COMMERCIAL PRODUCTS FROM FT HYDROCARBONS; CATALYSIS OF FISCHER-TROPSCH REFINERIES; PATENT LITERATURE; FUTURE PERSPECTIVES; REFERENCES

Read more less

Book SynopsisP-stereogenic ligands were among the first to be used in asymmetric catalysis but synthetic difficulties and prejudices have hampered their development. However, continuous screening for new chiral ligands means that they can no longer be ignored and this rigorous reference source reflects their renaissance. The book is filled with many examples from recent primary literature. The synthetic chemist will easily be able to follow the preparation methods which are accompanied by a description of the challenges and limitations. Those working in homogenous catalysis, and wanting to increase their repertoire of ligands, will be able to establish which have already been used in each reaction and their performance. This book provides comprehensive coverage of the application of P-stereogenic ligands in homogeneous catalysis. It begins with a brief chapter on generalities of P-stereogenic compounds: history, configurational stability, and interconversions among them.The book then goes on to describe the main preparative methods, from resolution of racemates to enantioselective catalysis, before focusing on the catalytic applications of P-stereogenic ligands. Chapter 7 describes the use of the ligands in catalytic hydrogenation and related reactions whereas chapter 8 deals with other reactions, mainly C-C bond forming reactions. The aim of these two final chapters is to give an outline of the usefulness of the ligands in homogeneous catalysis.Table of ContentsIntroduction; Resolution of Racemic and Diastereomeric Mixtures; P-Stereogenic Heterocycles; P-Stereogenic Compounds Derived from Enantiopure Heterocycles P-Stereogenic Phosphines Prepared by Enantioselective Deprotonation; Preparation by Enantioselective Catalysis; Hydrogenation and Related Reactions; Miscellaneous Reactions

Read more less

Book SynopsisCarbon-carbon bond formations and functional group transformations are the most fundamental reactions for the construction of molecular frameworks and are at the forefront of organic chemistry research. The Morita-Baylis-Hillman (MBH) type reactions possess the two most important requirements - atom economy and generation of multi-functional groups. The last decade has seen exponential growth of the MBH reaction and its applications. In fact, it is already one of the most powerful carbon-carbon bond-forming methods widely used in organic synthesis. Since the 1990s, more and more research groups have initiated work on different aspects of the MBH reaction. These have focused on the scope of the substrates, novel catalysts (especially chiral catalysts), reaction mechanisms, and synthetic applications. Consequently, there is now a need for a reference detailing the chemistry of this important reaction. This unique book summarizes the MBH reaction, aza-MBH reaction and asymmetric MBH/aza-MBH reaction including the latest research and mechanistic investigations. It provides a complete overview of MBH-type reactions aimed at synthetic organic chemists of all levels within academia and industry. The chapters cover the; origin and growth of the Morita-Baylis-Hillman reaction; reactant classes and reaction conditions; catalytic mechanisms; achiral and chiral catalytic systems; transformations of functional groups; use of Morita-Baylis-Hillman adducts and derivatives as starting materials to construct compounds with carbocyclic or heterocyclic frameworks, and the applications of the MBH reaction in synthesizing natural products.Table of ContentsMorita-Baylis-Hillman Reaction; Catalytic System for the Morita-Baylis-Hillman Reaction; Transformations of Functional Groups in Morita-Baylis-Hillman Adducts; Morita-Baylis-Hillman Adducts or Derivatives for the Construction of Cyclic Frameworks; The application of Morita-Baylis-Hillman Reaction for the Synthesis of Natural Products

Read more less

Book SynopsisThere is an increasing need to find cost-effective and environmentally sound methods of converting natural resources into fuels, chemicals and energy; catalysts are pivotal to such processes. Catalysis highlights major developments in this area. Coverage of this Specialist Periodical Report includes all major areas of heterogeneous catalysis. n each volume, specific areas of current interest are reviewed. Examples of topics include experimental methods, acid/base catalysis, materials synthesis, environmental catalysis, and syngas conversion.Table of ContentsPreface; Key catalyst types for the efficient refining of Fischer–Tropsch syncrude: alumina and phosphoric acid; Recent developments and achievements in partial oxidation of methane with and without addition of steam; Precious metal catalysts for deep hydrodesulfurization; Catalytic reactions studied by angle-resolved product desorption; Quantification of cluster size effect (structure sensitivity) in heterogeneous catalysis; Photocatalysis in green chemistry and destruction of very toxic compounds; Hierarchical zeolites: materials with improved accessibility and enhanced catalytic activity; Catalysis involved in dimethylether production and as an intermediate in the generation of hydrocarbons via Fischer-Tropsch synthesis and MTG process; Selective oxidation catalysis on rhenium-oxide catalysts

Read more less

Book SynopsisImmobilization of chiral catalysts is an important tool for improving overall efficiency of catalytic processes. However, heterogeneous catalysts often suffer from decreased activities and supported but still homogeneous catalysts can help overcome this issue. This book covers the most important concepts of homogeneous supported catalysis with an emphasis on enantioselective processes. It describes the state-of-the-art and latest developments in each area whilst critically evaluating the strengths and weaknesses of this important method. The book encompasses ionically-tagged catalysts, supported organocatalysts, supported ionic liquid phases, catalysis using soluble polymers, catalytic dendrimers, fluorous catalysts, water soluble catalysts and non-covalent immobilization methods. Potential developments and ideas for the future are also highlighted. There is a growing demand for effective and recyclable catalysts so this book, covering all the important methods in the field of supported homogeneous catalysis, will appeal to many researchers in academia and industry.Trade Review"The editor of the present volume is Radovan Sebesta of Comenius University (Bratislava), an expert in organocatalysis and on the use of ionic liquids as catalyst supports." -- Miquel A. Perics, Institute of Chemical Research of Catalonia, Tarragona (Spain) * Angew. Chem. Int. Ed. 2012, 51, 8425 – 8426 *"...discusses the latest developments in the areas covered, critically evaluating the strengths and weaknesses of these methodologies" -- Miquel A. Perics, Institute of Chemical Research of Catalonia, Tarragona (Spain) * Angew. Chem. Int. Ed. 2012, 51, 8425 – 8426 *"...this volume will certainly be a useful tool for researchers working in catalysis and a useful addition to the libraries of academic chemists." -- Miquel A. Perics, Institute of Chemical Research of Catalonia, Tarragona (Spain) * Angew. Chem. Int. Ed. 2012, 51, 8425 – 8426 *Table of ContentsIonically-tagged transition-metal catalysts; Catalysis with supported organocatalysts; Supported ionic liquid phase catalysis; Metal-catalysts on soluble polymers; Catalytic dendrimers; Fluorous catalysts and chiral auxiliaries in biphasic and homogeneous systems; Aqueous-phase asymmetric catalysis; Non-covalent immobilization

Read more less

Book SynopsisThere is an increasing need to find cost-effective and environmentally sound methods of converting natural resources into fuels, chemicals and energy; catalysts are pivotal to such processes. Catalysis highlights major developments in this area. Coverage of this Specialist Periodical Report includes all major areas of heterogeneous catalysis. In each volume, specific areas of current interest are reviewed. Examples of topics include experimental methods, acid/base catalysis, materials synthesis, environmental catalysis, and syngas conversion.Table of ContentsPreface; Progress Towards Operando Raman Spectroscopy, Monitoring and Imaging; TBC; Coverage Dependent Adsorption Properties of Atomic Adsorbates on Late Transition Metal Surfaces; Green Catalysis with Metal Complexes: from Bulk to Nano Recyclable Hybrid Catalysts; TBC; TBC; Asymmetric Organocatalyzed Morita-Baylis-Hillman Reactions; Catalytic Applications of Mesoporous Materials; Polarization-Dependent Total Reflection Fluorescence

Read more less

Book SynopsisEnergy and environment issues are of paramount importance to achieve the sustainable development of our society. Alcohol-fuelled direct oxidation fuel cells (DOFCs), as a clean and highly-efficient energy harvesting engine, have attracted intensive research activity over recent decades. Electrocatalysts are the material at the very heart of the cell that determines the performance of DOFCs. The rapid advances in electrocatalysts, particularly nano-sized ones, have left current information only available in scattered journals. To be truly useful to both present and future researchers, a new book is needed to present an insightful review of the reaction nature of this research and to systematically summarize recent advances in nanocatalysts, and convey a more global perspective. Catalysts for Alcohol-fuelled Direct Oxidation Fuel Cells will present a state-of-the-art review on recent advances in nanocatalysts and electrocatalysis in DOFCs, including both proton and hydroxide ion exchange membrane fuel cells. The main topics covered include a molecular-level understanding of electrocatalysis, the design principles of electrocatalysts, recent advances in nanocatalysts and future perspectives for DOFCs. The book presents a cutting-edge collection on nanocatalysts for alcohol-fuelled direct oxidation fuel cells and brings together the most authoritative researchers in the field from both industry and academia, filling the gap between both sides. Finally, the book will provide an insightful review on electrocatalysis at the molecular- level, which will be useful for postgraduate students and junior researchers in this field. It will be an essential resource for postgraduates, researchers and policy-makers globally in academia, industry, and government institutions.Trade Review“Catalysts for Alcohol-Fuelled Direct Oxidation Fuel Cells” is aimed at a general audience with an interest in low power fuel cells, as well as experts in the area. The book is edited by Zhen-Xing Liang, Lecturer at the South China University of Technology, and Tim S. Zhao, Professor of Mechanical Engineering at the Hong Kong University of Science and Technology (HKUST) and director of the HKUST Energy Institute. The book contains seven chapters in 264 pages and reviews the catalysis of alcohol electrooxidation in low-temperature fuel cells. The reader will fi nd a general overview of the catalysis involved in the oxidation of alcohols such as methanol and ethanol. More unusually the oxidation of ethylene glycol and glycerol are also described in detail. Although the title for this book is specifi c to alcohol fuel cells it also contains individual chapters describing the oxidation of other fuels of interest such as formic acid, borohydride and sugars. The book concludes with a chapter on the challenges that alcohol fuel cells need to overcome. Role of the Platinum Group Metals Many of the book’s chapters are easy to read even for people with little experience in the area. Chapter 1, ‘Electrocatalysis of Alcohol Oxidation Reactions at Platinum Group Metals’, by Claude Lamy (University of Montpellier, France) and Christophe Coutanceau (Université de Poitiers, France), starts with a good if simplistic overview about what constitutes fuel cell effi ciency. This is an important subject and the authors’ general description can easily be followed by students in chemistry or related subjects. The authors highlight that the theoretical effi ciencies for methanol/air and ethanol/air fuel cells are actually higher than hydrogen/oxygen fuel cells. This is a great foundation for the book because it really justifi es the need for research in this area. The chapter continues with a very simplistic description of the methods used for the synthesis and characterisation of fuel cell catalysts, from well-known chemical and electrochemical approaches to more exotic methods such as plasmaenhanced techniques. The content fl ows in a logical order with this introduction followed by dedicated sections describing in detail the oxidation of different fuels. The oxidation of methanol or ethanol is described in acidic environments, mainly for the wellknown platinum-based binary catalysts PtM/C (M = ruthenium or tin), at different atomic ratios. The authors describe the differences in reactivity when using different atomic ratios such as Pt0.5Ru0.5, Pt0.8Ru0.2, Pt3Sn and Pt9Sn. These binaries are known to be active because of the effi cient removal of adsorbed carbon monoxide (via the bifunctional mechanism), a common intermediate in the oxidation of primary alcohols. In contrast, the oxidation of ethylene glycol and glycerol is described mainly in alkaline media with the authors focusing on the use of carbon supported platinum, platinum-palladium and platinum-palladium-bismuth for the oxidation of ethylene glycol and platinum, palladium and gold catalysts and their binaries and ternaries such as PtPd, PtBi, PdBi and PtPdBi for the oxidation of glycerol. The chapter offers a good introduction, although it lacks references to the use of commercial catalysts for methanol oxidation (1, 2). Catalyst Preparation Chapter 2, ‘Nanoalloy Electrocatalysts for Alcohol Oxidation Reactions’, by Jun Yin (Cornell University, New York, USA) et al. describes the use of PtAu catalysts for alcohol oxidation. The synthesis of PtAu catalysts is a very interesting topic with challenging nanoscale catalyst preparation. Nanoscale gold has been shown to produce surface oxygenated species such as gold(III) oxide, adsorbed gold hydroxide or gold(III) hydroxide which are highly active for the M1 M2 Precursors Capping agent Reduction or decomposition Wet chemical synthesis Assembly on support Thermal treatment Supported catalyst Assembly Activation (a) (b) 30 nm (c) 30 nm M1mM2100–m + Fig. 1. (a) A general scheme showing the molecularly engineered synthesis of bimetallic nanoparticles capped with a monolayer shell of oleic acid/oleylamine and the preparation of bimetallic nanoparticles supported on carbon powders or carbon nanotubes by assembly and activation. Transmission electron microscopy images showing: (b) Au22Pt78 nanoparticles supported on carbon black; and (c) Au nanoparticles supported on carbon nanotubes (Reproduced by permission of The Royal Society of Chemistry) removal of adsorbed CO, especially in alkaline media. Traditional methods for PtAu catalyst preparation are mentioned such as co-precipitation, impregnation with subsequent reduction, and calcination. More interestingly, the synthesis of Au and PtAu supported nanoparticles via the molecular encapsulation synthesis is described (Figure 1). This approach involves three steps: (a) chemical synthesis of metal nanocrystal cores with molecular encapsulation; (b) assembly of the encapsulated nanoparticles on support materials; and (c) thermal treatment of the supported nanoparticles. A brief mention of core–shell type PtAu nanoparticles is also included although no characterisation data is shown. PtAu nanoparticles with different atomic compositions are presented for the oxidation of methanol in alkaline and acidic media. An iron(II,III) oxide Fe3O4@Au@Pt ternary is presented as a more active catalyst than Pt in acidic media. The chapter fi nishes with a section dedicated to the characterisation of PtAu particles and includes experimental data from different techniques such as X-ray diffraction (XRD), Fourier transform infrared (FTIR) spectroscopy and X-ray photoelectron spectroscopy (XPS) which adds detailed information to help understand the catalysis. Quantum Mechanical Modelling Chapter 3, ‘Theoretical Studies of Formic Acid Oxidation’, by Wang Gao and Timo Jacob (Universität Ulm, Germany), is the only chapter dedicated to the use of quantum mechanical modelling for the understanding of chemical reactions at the molecular level. Although formic acid is not an alcohol, it is of interest in terms of fuel cell effi ciency for low power electronics. The authors cover the oxidation of formic acid in ultra-high vacuum conditions and also with increasing water coverage. Importantly, they pay attention to the effect of the electrochemical potential on the formic acid dehydrogenation and include a detailed discussion of the adsorbed products that are formed. A detailed and informative discussion of the different reaction pathways, direct and indirect, is presented. Readers with some experience in the fi eld will fi nd the content extremely interesting. It is slightly disappointing that the editors did not include more content towards the use of theoretical modelling for the oxidation of alcohols. Catalysis by Gold Chapter 4, ‘Gold Leaf Based Electrocatalysts’, by Rongyue Wang and Yi Ding (Shandong University, China) is dedicated to the use of nanoporous gold leaf (NPG-leaf) as an alternative catalyst for the oxidation of formic acid and alcohols in alkaline media. The chapter describes the formation of NPG by chemical dissolution also known as dealloying. This is a wellknown process and has been applied for many years in the manufacturing of high surface area catalysts. The authors present as an example the formation of NPG from a gold-silver alloy. Selective dissolution of Ag leads to the formation of a porous structure (Figure 2) (3). The authors describe the excellent research done by John Newman (University of California, Berkeley, USA) et al. (4) and Jonah Erlebacher (Johns Hopkins University, USA) et al. (5) and the reader is advised to follow up these references for further, detailed information. Overall NPG-Pt catalysts give very low benefi t compared to Pt/C. In fact, the area of dealloying is currently an ongoing research topic aimed at the design of highly active catalysts for the oxygen reduction reaction in H2/O2 fuel cells. Experts in the area such as Professor Doctor Peter Strasser, now at Technische Universität Berlin, Germany, have documented very interesting results with the study of dealloyed particles and their use as catalysts for the oxygen reduction reaction (6, 7). However, the use of dealloyed catalysts has not been well documented for alcohol oxidation. (a) 120 nm (b) 500 nm Fig. 2. Scanning electron microscopy images of a nanoporous gold leaf (Reproduced by permission of The Royal Society of Chemistry and Alkali Metal Borohydrides Chapter 5, ‘Nanocatalysts for Direct Borohydride Oxidation in Alkaline Media’ by Christophe Coutanceau et al. considers the use of alkali metal borohydrides as fuels. Sodium borohydride is preferred because it offers a compromise between specifi c energy density and relative abundance. The authors clearly explain the anodic and cathodic reactions that occur in a direct borohydride fuel cell (DBFC) and the theoretical effi ciency of a system capable of achieving the 8 electron reaction. Due to the alkaline environment used the catalysts considered are the usual binaries and ternaries, such as PdAu, PdNi and PdPtBi. The authors describe a very interesting study of the kinetics of the electrode reaction but most importantly they present a discussion of what makes a catalyst selective towards complete oxidation and also to the inhibition of hydrogen oxidation. The use of Pt0.9Bi0.1/C is presented as the most selective catalyst that leads to the 8e-- pathway without signifi cant hydrogen evolution. Although this anode catalyst led to lower performance compared to Pt/C, in terms of current density, it is of interest for a DBFC because of increased fuel effi ciency, a prime parameter for the use of the fuel. It is important to highlight that a system with high cell effi ciency is more attractive for many practical applications than a system with low effi ciency and high current density. The authors have written a very interesting chapter and this reader gained useful knowledge about the technology. The Use of Enzymes Chapter 6, ‘Bioelectrocatalysis in Direct Alcohol Fuel Cells’, by Holly Reeve and Kylie Vincent (University of Oxford, UK), is dedicated to the use of enzymes for the oxidation of sugars such as fructose, lactose and glucose. The use of sugars for fuel cells is a very interesting area for research since it is based on the generation of electricity by the oxidation of natural products. Actually, the full oxidation of a primary alcohol to carbon dioxide is also possible when using a chain of enzymes via a sequence of chemical reactions. This is a key characteristic that differentiates enzymes from metal nanoparticles. For instance, there are very few metal catalysts capable of achieving the full oxidation of dilute ethanol to CO2 without the formation of incomplete products such as acetaldehyde and acetic acid (8). The authors give a fair and realistic view of the practical problems of enzymes as catalysts due to their relatively large size, which leads to low volumetric density and their limited stability when varying conditions such as pH, temperature, pressure and solvent type. The authors highlight that biofuel cells could have their main application as bioimplantable fuel cells for pacemakers and for the purifi cation of waste water. Although research in this area is in its infancy, the authors give an excellent overview of the use of biofuel cells and the reader with an interest in biocatalysis will fi nd this chapter extremely interesting. Problems in Alcohol Oxidation The book closes with Chapter 7, ‘Challenges and Perspectives of Nanocatalysts in Alcohol-Fuelled Direct Oxidation Fuel Cells’, by Eileen Hao Yu (Newcastle University, UK) et al. This chapter covers some of the main problems in alcohol oxidation focusing on the factors affecting activity and stability, including the need for more active catalysts capable of oxidising adsorbed CO. The authors report on the use of binary and ternary catalysts in alkaline and acid media, such as PtRu, PtSn and PtRuM (M = tungsten, molybdenum, nickel) and PtSnM (M = Ni or Ru), PtAu, PdNi and PdIrNi. The use of metal oxides such as cerium(IV) oxide, nickel(II) oxide, cobalt(II,III) oxide and manganese(II,III) oxide as promoters capable of introducing oxygenated species to remove adsorbed CO is also described. A brief mention of the benefi ts and disadvantages of the use of core–shell catalysts is presented with a special emphasis on PtAu core– shell catalysts. In terms of stability, some interesting approaches are mentioned such as the use of alternative carbon supports (graphene and N-doped carbon nanotubes) and supports such as titanium dioxide and tungsten carbide. The authors, however, do not mention the main problems of anode stability, such as base metal dissolution, membrane contamination and the impact on cathode performance or relate these issues to real fuel cell data. Conclusion The authors describe in a detailed manner the electrocatalytic oxidation of primary alcohols and other relevant fuels of interest for low power fuel cells in both acid and alkaline media. The reader gains a useful introduction to the catalysis involved in the oxidation of different fuels, such as methanol, ethanol, ethylene glycol, glycerol, borohydride and sugars. While enzymes and gold catalysts have been introduced, platinum group metal catalysts, especially those based on Pt and Pd, are the state of the art for these technologies. The book only disappoints in some areas such as the lack of real fuel cell data and, for this reviewer’s taste, an overemphasis on alcohol oxidation in alkaline media. Overall, this book can be a good starting point for students and researchers with an interest in low power fuel cells. References 1 N. Cabello-Moreno, E. Crabb, J. Fisher, A. E. Russell and D. Thompsett, ECS Trans., 2008, 16, (2), 483 2 J. M. Fisher, N. Cabello-Moreno, E. Christian and D. Thompsett, Electrochem. Solid-State Lett., 2009, 12, (5), B77 3 J. Erlebacher, M. J. Aziz, A. Karma, N. Dimitrov and K. Sieradzki, Nature, 2001, 410, (6827), 450 4 R. C. Newman and K. Sieradzki, Science, 1994, 263, (5 154), 1708 5 R. Zeis, A. Mathur, G. Fritz, J. Lee and J. Erlebacher, J. Power Sources, 2007, 165, (1), 65 6 P. Mani, R. Srivastava and P. Strasser, J. Phys. Chem. C, 2008, 112, (7), 2770 7 L. Gan, M. Heggen, R. O’Malley, B. Theobald and P. Strasser, Nano Lett., 2013, 13, (3), 1131 8 A. Kowal, M. Li, M. Shao, K. Sasaki, M. B. Vukmirovic, J. Zhang, N. S. Marinkovic, P. Lui, A. I. Fre -- Alex Martinez Bonastre * Platinum Metals Rev., 2013, 57, (4), 297–301• *This is an important subject and the authors’ general description can easily be followed by students in chemistry or related subjects. Readers with some experience in the field will find the content extremely interesting. -- Alex Martinez Bonastre * Platinum Metals Rev., 2013, 57, (4), 297–301• *Table of ContentsIntroduction; Preparation of Nanocatalysts for DOFCs; Nanocatalysts for Formic Acid Oxidation Reaction; Nanocatalysts for Alcohol Oxidation Reaction (AOR); Nanocatalysts for Liquid Borohydride Oxidation; Nanocatalysts for Oxygen Reduction Reaction (ORR); Core-Shell Nanostructured Catalysts; Gold-Leaf Based Nanocatalysts; Bio-Electrocatalysts for DOFCs; Challenges and Perspectives of Nanocatalyst in DOFCs; Index

Read more less

Book SynopsisCatalysis has always been part of the development of mankind; from the fermentation of alcoholic drinks, through the development of fertilisers in the agricultural revolution and production of bulk chemicals in the 20th Century. Today, society demands improved production routes with greater product output and energy efficiency; the ultimate goal to achieving this would be having all catalytic reactions in concert, effectively functioning like a biological cell. Metal organic frameworks (MOFs) are a relatively new type of hybrid material. Their crystalline porous structure, built up from organic and inorganic building blocks, presents a vast array of composition, porosity and functionality offering enormous potential in catalytic systems. This book examines the latest research and discovery in the use of MOFs in catalysis, highlighting the extent to which these materials have been embraced by the community. Beyond presenting a digest of recent research by major players in the field, the book presents the strategies behind recent developments, providing a lasting reference for seasoned researchers and newcomers to the field.Table of Contents1. Introduction; PART A. SYNTHESIS AND CHARACTERIZATION OF MOFs; 2. Synthesis of MOFs; 3. Post-synthetic Modification of MOFs; 4. Characterization of MOFs. 1. Combined Vibrational and Electronic Spectroscopies; 5. Characterization of MOFs. 2. Long and Local Range Order Structural Determination of MOFs by Combining EXAFS and Diffraction Techniques; 6. MOFs for Energy and Environmental Applications; 7. Computational Approach to Chemical Reactivity of MOFs; PART B. CATALYSIS BY MOFs; 8. Strategies for Creating Active Sites in MOFs; 9. Catalysis at the Metallic Nodes of MOFs; 10. Catalysis at the Organic Ligands; 11. MOFs as Nanoreactors. Species Encapsulated in the IntraMOF Space; 12. Asymmetric Catalysis with Chiral MOFs; 13. Photocatalysis by MOFs; 14. Catalysis by Covalent Organic Frameworks (COFs); 15. Conclusions and Future Developments

Read more less

Book SynopsisOver 7000 papers are published in the field of catalysis each year. While the majority appear within a handful publications, keeping up with the literature can be difficult. Now in its 25th volume, the Specialist Periodical Report on Catalysis presents critical and comprehensive reviews of the hottest literature published over the last twelve months. Industrial and academic scientists face increasing challenges to find cost-effective and environmentally sound methods for converting natural resources into fuels, chemicals and energy. This series is edited by two leading researchers in the field and provides a balanced and in-depth review of the modern approaches to these challenges, covering major areas of heterogeneous and homogenous catalysis, as well as specific applications of catalysis, such as NOx control, kinetics and experimental techniques, such as microcalorimetry. With chapters detailing specific areas within the field, this series is a comprehensive reference for anyone working in Catalysis and an essential resource for any Chemistry Library.Table of ContentsPreface; Gaining insight into the kinetics of partial oxidation of light hydrocarbons on Rh, though a multiscale methodology based on advanced experimental and modelling techniques; Theoretical tools for studying gold nanoparticles as catalysts for oxidation and hydrogenation reactions; PdZn based catalysts: connecting electronic and geometric structure with catalytic performance; Structural manipulation of the catalysts for ammonia decomposition; Applications of electron beam lithography in surface science and catalysis - model-nano-array catalysts; High throughput technology; approaches of research in homogeneous and heterogeneous catalysis; Core-shell catalysts and bimodel catalysts for Fischer-Tropsch synthesis

Read more less

Book SynopsisThis book presents the latest research in the field of heterogeneous catalysis. Heterogeneous catalysis and homogeneous catalysis are important factors in increasing the development of green chemistry. Some of the challenges that we are responsible for are directing research efforts toward increasing the kinetics of heterogeneous catalysis to homogeneous catalysis levels, improving the recyclability of the catalysts, and developing new supports that can act as catalysts or cocatalysts. Following reaction kinetics and mechanisms on supported catalysts provides the degree of precision and accuracy already enjoyed by the homogeneous catalysis community. The editors present an easily-accessible digest for researchers and a reference aimed at offering guidance to new researchers in the field.Table of ContentsZeolites: Synthesis, properties, and industrial applications; Microwave assisted synthesis of solid catalytic materials; Supported metal catalysts for green reactions; Heterogeneous catalysts for asymmetric reactions; Clay-based catalyst supports; Mesoporous metals: synthesis and catalysis; Novel syntheses and catalytic reactions for periodic mesoporous organosilica; Porous carbon composites for catalytic reactions; Smart heterogeneous catalyst design on mesoporous nanomaterials

Read more less

Book SynopsisGold has traditionally been regarded as inactive as a catalytic metal. However, the advent of nanoparticulate gold on high surface area oxide supports has demonstrated its high catalytic activity in many chemical reactions. Gold is active as a heterogeneous catalyst in both gas and liquid phases, and complexes catalyse reactions homogeneously in solution. Many of the reactions being studied will lead to new application areas for catalysis by gold in pollution control, chemical processing, sensors and fuel cell technology. This book describes the properties of gold, the methods for preparing gold catalysts and ways to characterise and use them effectively in reactions. The reaction mechanisms and reasons for the high activities are discussed and the applications for gold catalysis considered.

Read more less

Book SynopsisThis brief is a concise guide that explores the theory and practical aspects of improving enantioselectivity in enzymatic kinetic resolution, with a specific focus on the role of hydrolases in this process. Enzymatic kinetic resolution is a valuable technique for obtaining enantiopure compounds, and hydrolases are highlighted as a crucial class of enzymes widely used in industries for chiral synthesis involving kinetic resolution. The book emphasizes the importance of tuning and optimizing the enzymatic kinetic resolution process to achieve the highest possible enantiomeric excess in the final product or starting material while maintaining the desired yield. Through illustrative examples, the text aims to make the concept accessible and appealing to graduate students, researchers, and young organic chemists seeking to incorporate hydrolases in their stereoselective synthesis endeavors.Table of ContentsUnderstanding Enzymatic Kinetic Resolution.- Essential Parameters: Determination and Significance - Enantioselectivity: The Decisive Factors.- Dynamic Kinetic Resolution.

Read more less

Book SynopsisThis book begins by giving a summary of sonochemistry and explains how a chemical reaction can be induced by the interaction of sound waves and gas bubbles in liquids. The work outlines how primary and secondary radicals combined with the physical effects generated during acoustic cavitation are active in the ultrasonic synthesis of a variety of functional materials. The brief covers hot topics that include ultrasonic synthesis of various functional materials covering the following broad areas: acoustic cavitation and sonochemistry, synthesis of functional polymers and their applications, synthesis of functional inorganic materials and their applications, improving functionality of food/dairy systems, synthesis of functional biomaterials and their applications, synthesis of graphene based catalytic materials. Theory is kept to a minimum. The book is aimed at individuals at universities and will also interest those in industry. It is suitable for all levels.Table of ContentsIntroduction.- Ultrasonic Synthesis of Functional Materials.- Advantages, Disadvantages and Challenges of Ultrasonic Technology.

Read more less

Book SynopsisThis volume covers recent advances in the chemistry of ylidic compounds with focus on their application in the design of ligands with unique donor properties, the development of novel organic transformations as well as the use of ylides in homogenous catalysis. Thereby, this volume particularly aims at the community of organic and organometallic chemists engaged in synthetic chemistry and catalysis as well as in the use of special ligands for the stabilization of unusual main group element species and the “transition-metal free” activation of element-element/hydrogen bonds. These fields of research are highly active and vivid research areas to which ylide chemistry has only recently started to contribute, but has already led to fascinating developments in most different directions. This volume highlights these recent developments, thus giving not only an overview over the past achievements, but also possibilities for future applications. To this end, the chapters selected in this volume combine different aspects of ylide chemistry, starting with theoretical aspects in ligand design followed by synthetic organic methods, catalytic transformations and complex chemistry. Table of ContentsStructure and Reactivity of Carbones and Ylide Stabilized Carbenes: Contributions from Theory.- Synthesis, Structure, and Reactivity of Carbodiphosphoranes,Carbodicarbenes,and Related Species.- Synthesis and Structure of Carbodicarbenes and Their Application in Catalysis.- Sulfur Ylides in Organic Synthesis and Transition Metal Catalysis.- Reactivity and Applications of α-Metalated Ylides.

Read more less

Book SynopsisThe whole range of biocatalysis, from a firm grounding in theoretical concepts to in-depth coverage of practical applications and future perspectives. The book not only covers reactions, products and processes with and from biological catalysts, but also the process of designing and improving such biocatalysts. One unique feature is that the fields of chemistry, biology and bioengineering receive equal attention, thus addressing practitioners and students from all three areas.Trade Review"...the book is excellent and could be read cover to cover or used for reference and I strongly recommend it to anyone interested in the field of biocatalysis whether they be graduate students just entering the field or more experienced practitioners." Organic Process Research & Development "This guidebook is warmly recommended to scientists in academia, industry and authorities engaged in biocatalysis because one unique feature of primary importance is that the interdisciplinary fields of chemistry, biology and bioengineering receive equal attention, thus, addressing both practioners and students from all three areas." AFS "The book nicely brings together the essentials of biocatalysis including reactions, the products and processes that utilize the methodology, and techniques for improving biocatalysts." Catalyst "I strongly recommend it to advanced students, experienced chemists, biologists, and engineers interested in or actively working in biocatalysis, as it is a rich source of information and offers an excellent opportunity to get an insight into neighbouring areas of expertise." Angewandte Chemie I.E. "The content of the book is excellent...the book is excellent and could be read cover to cover or used for reference and I strongly recommend it to anyone interested in the field of biocatalysis..." Organic Process Research & Development "With their book "Biocatalysis" Bommarius and Riebel successfully bridge the gap between textbooks and original research papers. The book is recommended for advanced students, experienced chemists and engineers interested in the area of industrial biocatalysis." CHEMBIOCHEM "...a timely and detailed summary of the important recent developments in the rapidly moving fields pertinent to harnessing the efficiency and specificity of biological catalysts. It will definitely assist research scientists' efforts to improve their own chemical transformations." Synthesis "Biocatalysis" ist ein interessantes und hervorragendes Lehrbuch zum Thema Biokatalyse...sehr interessantes Lesevergnügen...absolut lesenswert...Grundlagen zur Zellbiologie aber auch zum Thema Bioinformatik, Enzymkinetik und vielen weiteren Gebieten runden das gelungene Gesamtbild ab. Das Buch ist wahrlich eine Hilfe für Ingenieure, welche sich auf Biokatalyse spezialisieren wollen und im Umfeld zwischen Biologie, Biochemie und Chemie bestehen wollen." www.organische-chemie.ch "Ein durchaus empfehlenswertes Buch, das besonders diejenigen anspricht, die bereits vertiefte Kenntnisse in der molekularen Biologie, der (bio-)chemischen Synthese und Analytik besitzen und der englischen Fachsprache mächtig sind." Mitteil. der FG Umweltchemie und Ökotoxikologie der GDCh "Mit "Biocatalysis" liegt ein Werk vor, in dem die Autoren sorgsam die Balance halten, zwischen Lehrbuchwissen und aktuellen Forschungsergebnissen. Dadurch findet der Leser zeitökonomisch den Einstieg und vielmehr den Zugang auch in die aktuellsten Themen der Biokatalyse ohne sich durch den aktuellen Publikationsdschungel arbeiten zu müssen..." Chemie-Online "Biocatalysis" gibt einen aktuellen Überblick über das Wissen in diesem Gebiet, von den Grundlagen bis hin zu Anwendungen und einem Ausblick in die Zukunft." Bioworld "Den Autoren ist mit der Vorlage dieses Buches gelungen, ein typisches interdisziplinäres Wissenschaftsthema unter Berücksichtigung von allen Aspekten - Forschung, Entwicklung, Verfahrenstechnik, Produktion sowie prozeßbegleitende Technologien - in hervorragender Weise vorzustellen. Entscheidend für die Qualität und die Wichtung der adressierten Themen ist dabei, dass in hohem Maße die Erfahrungen aus der industriellen Verfahrensentwicklung einfließen." Arzneimittel-Forschung/Drug Research "Bommarius und Riebel präsentieren mit Biocatalysis nun ein Werk, das alle wichtigen Aspekte der Biokatalyse abdeckt. Die größte Herausforderung bestand sicher darin, aus dem umfangreichen Datenbestand die wesentlichen Fakten herauszufiltern - mit ausgezeichnetem Ergebnis. ... Positiv fällt weiterhin auf, dass jedem Kapitel eine Zusammenfassung vorangestellt ist und viele aktuelle Beispiele biokatalytischer Verfahren mit dazugehörigen Hintergrundinformationen vorgestellt werden. ... Ich kann dieses Buch fortgeschrittenen Studenten sowie erfahrenen Chemikern, Biologen und Ingenieuren, die an Biokatalyse interessiert sind oder biokatalytische Methoden verwenden, sehr empfehlen." Angewandte Chemie und Angewandte Chemie I.E. "Mit dem Buch 'Biocatalysis - Fundamentals and Applications' schließen die Autoren die Kluft zwischen Forschungsergebnissen in der Biokatalyse und deren industrieller Anwendung sowie den dahinter stehenden Grundlagen aus Biochemie, organischer Synthese, Molekularbiologie, Kinetik und Reaktionstechnik. Durch ihre Erfahrung aus der Industrie ... eignen sich die Autoren für dieses Ziel bestens. ... Das Buch bietet eine gelungene Übersicht über den aktuellen Stand der Enzymtechnologie und wendet sich dabei hauptsächlich an fortgeschrittene Studenten und den forschenden Biokatalytiker. ... ist dieses Buch sicherlich eine Bereicherung für den 'biokatalytischen' Buchmarkt." Nachrichten aus der ChemieTable of ContentsIntroduction to Biocatalysis Characterization of a (Bio-)catalyst Isolation and Preparation of Microorganisms Molecular Biology Tools for Biocatalysis Enzyme Reaction Engineering Applications of Enzymes as Bulk Actives: Detergents, Textiles, Pulp and Paper, Animal Feed Applications of Enzymes as Catalysts: Basic Chemicals, Fine Chemicals, Food, Crop Protection, Bulk Pharmaceuticals Biotechnological Processing Steps for Enzyme Manufacture Methods for the Investigation of Proteins Protein Engineering Applications of Recombinant DNA Technology: Directed Evolution Biocatalysis in Non-conventional Media Pharmaceutical Applications of Biocatalysis Bioinformatics Systems Biology for Biocatalysis Evolution of Biocatalytic Function Stability of Proteins Artificial Enzymes Design of Biocatalytic Processes Comparison of Biological and Chemical Catalysts for Novel Processes

Read more less

Book SynopsisThis long-awaited second edition of the successful introduction to the fundamentals of heterogeneous catalysis is now completely revised and updated. Written by internationally acclaimed experts, this textbook includes fundamentals of adsorption, characterizing catalysts and their surfaces, the significance of pore structure and surface area, solid-state and surface chemistry, poisoning, promotion, deactivation and selectivity of catalysts, as well as catalytic process engineering. A final section provides a number of examples and case histories. With its color and numerous graphics plus references to help readers to easily find further reading, this is a pivotal work for an understanding of the principles involved.Table of ContentsPreface XIX 1 Setting the Scene 1 1.1 Prologue: Advances since the Early 1990s 1 1.2 Introduction 13 1.2.1 Selectivity of Catalysts 14 1.3 Perspectives in Catalysis: Past, Present and Future 16 1.3.1 Applied Catalysis since the 1940s 19 1.3.2 Some Current Trends in Applied Catalysis 23 1.3.2.1 Auto-Exhaust Catalysts 23 1.3.2.2 Catalysts in Electrochemistry and Photoelectrochemistry 25 1.3.2.3 Immobilized Metals 26 1.3.2.4 Immobilized Enzymes and Cells: Present and Future 29 1.3.2.5 Ribozymes 31 1.4 Definition of Catalytic Activity 32 1.4.1 Magnitude of Turnover Frequencies and Active Site Concentrations 33 1.4.2 Volcano Plots 35 1.4.3 Evolution of Important Concepts and Techniques in Heterogeneous Catalysis 36 1.4.3.1 Mechanistic Insights from Isotopic Labelling 47 1.4.3.2 Concepts from Organometallic Chemistry 48 1.5 Key Advances in Recent Theoretical Treatments: Universability in Heterogeneous Catalysis 52 1.5.1 Some Major Current Developments in Heterogeneous Catalysis 53 1.6 Milestones Reached in Industrial Catalysis in the Twentieth Century, and Some Consequential Challenges 54 Problems 61 References 64 Further Reading 66 2 The Fundamentals of Adsorption: Structural and Dynamical Considerations, Isotherms and Energetics 67 2.1 Catalysis Must Always Be Preceded by Adsorption 67 2.1.1 Physical Adsorption, Chemisorption and Precursor States 67 2.2 The Surfaces of Clean Solids are Sometimes Reconstructed 71 2.3 There Are Many Well-Defined Kinds of Ordered Adlayers 74 2.4 Adsorption Isotherms and Isobars 79 2.4.1 The Empirical Facts 80 2.4.2 Information That Can Be Gleaned from Isotherms 80 2.4.3 Adsorption Is Almost Invariably Exothermic 85 2.5 Dynamical Considerations 86 2.5.1 Residence Times 87 2.5.2 Rates of Adsorption 88 2.5.3 Applying Statistical Mechanics to Adsorption 91 2.5.4 Adsorption Kinetics Can Often Be Represented by the Elovich Equation 93 2.5.5 Rates of Desorption 96 2.5.6 Applying Statistical Mechanics to Desorption 98 2.5.7 Influence of a Precursor State on the Kinetics of Desorption 99 2.6 Relating the Activation Energy to the Energy of Chemisorption. Universality in Heterogeneous Catalysis and the Brønsted–Evans–Polanyi (BEP) Relation 101 2.6.1 Pareto-Optimal Catalysts 104 2.7 Deriving Adsorption Isotherms from Kinetic Principles 105 2.7.1 Using the Langmuir Isotherm to Estimate the Proportions of Non-dissociative and Associative Adsorption 106 2.7.2 Other Adsorption Isotherms 109 2.7.2.1 Henry’s Adsorption Isotherm 109 2.7.2.2 Freundlich Isotherm 109 2.7.2.3 Temkin Isotherm 110 2.7.2.4 Brunauer–Emmett–Teller Isotherm 110 2.7.2.5 Developments from Polanyi’s Adsorption Theory 110 2.7.2.6 Kaganer’s Isotherm and the DKR Equation 112 2.7.2.7 Virial Equation of State 112 2.8 Energetics of Adsorption 113 2.8.1 Estimating the Binding Energies of Physically Adsorbed Species 114 2.8.2 Binding Energies of Chemisorbed Species 118 2.8.3 Estimating Heats of Adsorption from Thermodynamic Data 121 2.8.4 Decline of the Heat of Adsorption with Increasing Coverage 123 2.9 Mobility at Surfaces 126 2.10 Kinetics of Surface Reactions 127 2.10.1 The Influences of Precursor States on the Kinetics and Energy Distribution of Catalysed Reactions 130 2.10.2 Comparing the Rates of Heterogeneous and Homogeneous Reactions 131 2.11 Autocatalytic, Oscillatory and Complex Heterogeneous Reactions 132 2.11.1 An Outline of Autocatalysis 133 2.11.2 Background to Oscillating Reactions 134 2.11.3 Instabilities and Transient Phenomena in Heterogeneous Catalysis 136 2.11.4 Multiple Steady States 137 2.11.5 Transient Phenomena 139 2.11.6 Recent Thoughts on Spatio-Temporal Behaviour and Turbulence at Catalyst Surfaces 145 2.12 Microkinetics: A Summary 147 2.12.1 Building Kinetic Models 149 2.12.2 Formulation of Kinetic Models in Terms of Transition States 154 2.12.3 Degree of Rate Control 154 Problems 155 References 161 Further Reading 162 3 The Characterization of Industrial and Model Solid Catalysts 163 Part I: Characterization of Industrial Solid Catalysts 163 3.1 Non-invasive Methods Suitable for Studies Involving Catalytic Reactors 164 3.1.1 Magnetic Resonance Imaging (MRI) 165 3.1.1.1 Visualizing the Spatial Variation of Esterification, Etherification and Hydrogenation within Fixed-Bed and Trickle-Bed Reactors with MRI 166 3.1.2 Positron Emission Methods 170 3.1.3 Use of Spatially-Resolved X-ray Absorption to Probe Supported Nobel Metal Catalysts during Operating Conditions 170 Part II: Laboratory Characterization of Solid Catalysts 172 3.2 A Portfolio of Modern Methods: Introducing the Acronyms 172 3.3 Which Elements and Which Phases Are Present? 175 3.3.1 X-ray Fluorescence (XRF), X-ray Emission (XRE) and Proton-Induced X-ray Emission (PIXE) 175 3.3.2 Developing Techniques: ICPMS 177 3.3.3 X-ray Diffraction (XRD) and Small-Angle X-ray Scattering 177 3.3.3.1 Mean Size, Surface Area and Particle-Size Distribution from SAXS 180 3.3.3.2 In situ Studies by X-ray Diffraction 181 3.3.3.3 Experimental Aspects 183 3.4 Probing Surfaces with IR, HREELS, AES and XPS 184 3.4.1 Infrared Spectroscopy (IR): A Non-destructive Technique Usable on Catalysts Exposed to High Pressure 184 3.4.2 High-Resolution Electron-Energy Loss Spectroscopy (HREELS): the Most Sensitive Tool for Identifying Surface Vibrational Modes 189 3.4.3 Merits and Limitations of Electron Spectroscopy 190 3.5 Ultraviolet–Visible and Photoluminescence Spectroscopy 191 3.6 Structure and Crystallography of Surfaces: Nature of Ordered and Reconstructed Surfaces 193 3.6.1 Two- and Three-Dimensional Surface Crystallography 193 3.6.2 Notations for Describing Ordered Structures at Surfaces 198 3.6.3 How Do Bond Distances at Surfaces Compare with Those of Bulk Solids? What of Displacive Reconstructions? 199 3.6.4 EXAFS, SEXAFS, XANES and NEXAFS: Probing Bond Distances and Site Environments Even When There is No Long-Range Order 200 3.6.4.1 Origin of EXAFS and How It Is Used 200 3.6.4.2 Applications of EXAFS to the Study of Catalysts 206 3.6.4.3 SEXAFS 209 3.6.4.4 XANES and Pre-edge Structure: Deducing Site Symmetry and Oxidation States 210 3.6.4.5 NEXAFS 211 3.7 Other Structural Techniques for Characterizing Bulk and Surfaces of Catalysts 214 3.7.1 Electron Spin Resonance (ESR): Probing the Nature of Catalytically Active Sites and the Concentration of Paramagnetic Intermediates on Surfaces and in the Gas Phase 214 3.7.1.1 Examples of the Use of ESR in Heterogeneous Catalysis 215 3.7.2 Nuclear Magnetic Resonance (NMR): A Technique Applicable, at High Resolution, to Solids and Their Surfaces 216 3.7.2.1 Basic Principles 216 3.7.2.2 NMR Spectra of Solids 219 3.7.2.3 Applications of NMR to the Study of Catalysts, Adsorbents and Adsorbates 220 3.7.2.4 Future Prospects for the Study of Catalysts by Solid-State NMR 224 3.7.3 Sum Frequency Generation (SFG) and Infrared Reflection Absorption Spectroscopy (IRAS or IRRAS) 225 3.7.3.1 Essential Background and Mode of Operation 225 3.7.4 Scanning Tunnelling Microscopy (STM) and Clues for the Design of New Catalysts 229 3.7.4.1 Scanning Tunnelling Spectroscopy (STS) 238 3.7.4.2 Atomic Force Microscopy (AFM) and Fluorescence Microscopy (FM) 239 3.7.5 Electron Microscopy 240 3.7.5.1 Electron Crystallography 245 3.7.5.2 Electron Tomography (ET) 246 3.7.5.3 A Few Illustrative Examples of Static EM Images 247 3.7.5.4 In situ (Environmental) TEM 248 3.7.5.5 4D Electron Microscopy 248 3.7.6 Optical Microscopy and Ellipsometry (Non-invasive Techniques) 250 3.7.7 Neutron Scattering: A Technique of Growing Importance in the Study of Catalysts 252 3.7.7.1 Determining the Atomic Structure and Texture of Microcrystalline Catalysts, the Nature of the Active Sites and the Disposition of Bound Reactants 256 3.7.7.2 Determining the Structure of, and Identifying Functional Groups in, Chemisorbed Layers at Catalyst Surfaces 257 3.8 A Miscellany of Other Procedures 258 3.9 Determining the Strength of Surface Bonds: Thermal and Other Temperature-Programmed Methods 259 3.9.1 Temperature-Programmed Desorption (TPD) or Flash Desorption Spectroscopy (FDS) 260 3.9.2 Temperature-Programmed Reaction Spectroscopy (TPRS) 262 3.9.3 Magnitude of the Heat and Entropy of Adsorption 263 3.10 Reflections on the Current Scene Pertaining In situ Methods of Studying Catalysts 265 3.10.1 Isotopic Labelling and Transient Response 269 3.10.2 From Temporal Analysis of Products (TAP) to Steady-State Isotopic Transient Kinetic Analysis (SSITKA) 272 3.10.3 Infrared, Raman, NMR, and X-ray Absorption Spectroscopy for In situ Studies 273 3.10.4 In situ X-ray, Electron and Neutron Diffraction Studies 275 3.10.5 Combined X-ray Absorption and X-ray Diffraction and Other Techniques for In situ Studies of Catalysts 278 Problems 281 References 288 Further Reading 291 General 291 Additional 291 In situ Techniques 291 4 Porous Catalysts: Their Nature and Importance 293 4.1 Definitions and Introduction 293 4.2 Determination of Surface Area 296 4.2.1 Assessment of Porosity 298 4.2.1.1 Capillary Condensation; the Kelvin Equation and the Barrett– Joyner–Halenda Method 300 4.2.2 Evaluation of Both Micropore and Mesopore Size Using Density Functional Theory and Grand Canonical Monte Carlo Methods 300 4.2.2.1 An Explanatory Note about Density Functional Theory (DFT) in the Context of Adsorption 302 4.2.2.2 How Does One Tackle a ‘Breathing’ MOF Nanoporous Structure? 303 4.2.3 The Fractal Approach 304 4.2.4 Practical Considerations 305 4.3 Mercury Porosimetry 306 4.4 Wheeler’s Semi-empirical Pore Model 308 4.4.1 Mathematical Models of Porous Structures 310 4.4.1.1 The Dusty Gas Model 310 4.4.1.2 Random Pore Model 311 4.4.1.3 Stochastic Pore Networks and Fractals 311 4.5 Diffusion in Porous Catalysts 314 4.5.1 The Effective Diffusivity 314 4.5.1.1 Molecular (Maxwellian) Diffusion or Bulk Diffusion 316 4.5.1.2 Knudsen Diffusion 317 4.5.1.3 The Transition Region of Diffusion 318 4.5.1.4 Forced Flow in Pores 318 4.6 Chemical Reaction in Porous Catalyst Pellets 319 4.6.1 Effect of Intraparticle Diffusion on Experimental Parameters 326 4.6.2 Non-isothermal Reactions in Porous Catalyst Pellets 328 4.6.3 Criteria for Diffusion Control 331 4.6.4 Experimental Methods of Assessing the Effect of Diffusion on Reaction 334 Problems 337 References 340 Further Reading 341 Specific Books 342 General 342 5 Solid State Chemical Aspects of Heterogeneous Catalysts 343 5.1 Recent Advances in Our Knowledge of Some Metal Catalysts: In Their Extended, Cluster or Nanoparticle States 345 5.1.1 Surface and Sub-surface Chemistry of Ag Particles 345 5.1.2 Active Site of Methanol Synthesis over Cu/ZnO/Al2O3 Catalysts 347 5.1.3 Platinum as a Hydrogeneration Catalyst 349 5.1.4 An Early Report That Monoatomic Pt Functions as an Active Heterogeneous Catalyst 350 5.1.5 An Exceptionally Active, Atomically Dispersed Pt-Based Catalyst for Generating Hydrogen from Water 350 5.2 Comments on the Catalytic Behaviour of Nanogold 352 5.2.1 What a Single Atom of Palladium Can Do in the Appropriate Environment 358 5.3 Recent Advances in the Elucidation of Certain Metal-Oxide Catalysts 359 5.3.1 An Illustrative Investigation; Coupling STM, IR, Thermal Reaction Spectroscopy and DFT of Formaldehyde Formation on Vanadium Oxide Surfaces 362 5.4 Atomic-Scale Edge Structures in Industrial-Style MoS2 Nanocatalysts 363 5.5 Open-Structure Catalysts: from 2D to 3D 364 5.5.1 A Brief Guide to the Structure of Zeolitic and Closely-Related Solid Catalysts 365 5.5.1.1 Notion of Framework Density 369 5.5.2 New Families of Nanoporous Catalysts 370 5.5.2.1 The Principal Catalytic Significance of New Families of Nanoporous Solids 375 5.6 Computational Approaches 376 5.6.1 Résumé of Available Methodologies 376 5.6.1.1 Selected Applications 382 5.7 A Chemist’s Guide to the Electronic Structure of Solids and Their Surfaces 389 5.7.1 Energy Bands 390 5.7.1.1 Bands in ID and 3D Crystals 393 5.7.1.2 Energy Bands in Ionic Solids 395 5.7.1.3 Energy Bands in Transition-Metal Oxides: Understanding the Electronic Structure of the Monoxides of Ti, V, Mn and Ni 398 5.7.2 Fermi Levels in Insulators and Semiconductors 399 5.7.3 Surface Electronic States and the Occurrence of Energy Levels within the Band Gap 402 5.7.4 Band Bending and Metal–Semiconductor Junctions: Schottky Barriers 403 5.7.4.1 Depletive Chemisorption on Semiconductors 405 5.7.4.2 The Bending of Bands When Semiconductors Are Immersed in Electrolytes 406 5.7.5 Quantum Chemical Approaches to the Electronic Properties of Solids 407 5.7.6 A Brief Selection of Quantum Chemical Studies 408 5.7.6.1 Band Widths, DOS and Fermi Levels of the Transition Metals 408 5.7.6.2 Dissociative Chemisorption of CO 410 5.7.6.3 Insight from Ab initio Computations: Methanol Synthesis and Olefin Metathesis 411 5.7.7 Recent Advances in the Study of Metathesis 413 5.8 Key Advances in Recent Theoretical Treatments of Heterogeneous Catalysis 415 5.8.1 Further Comments on Density Functional Theory (DFT) 416 5.9 Selected Applications of DFT to Catalysis 419 5.9.1 CatApp: a Web Application for Surface Chemistry and Heterogeneous Catalysis 421 5.9.2 TiIV Centred Catalytic Epoxidation of c-Hexene 423 5.9.3 Mechanism of the Aerobic Terminal Oxidation of Linear Alkanes at Mn-Doped Aluminophosphate Catalysts 424 5.9.4 Rate Control and Reaction Engineering 425 5.10 Concluding Remarks Concerning DFT Calculations in Heterogeneous Catalysis 429 Problems 430 References 433 Key References Published Since the First Edition 436 Seminal Books 436 Monographs 437 Book Chapters 437 Further Reading 437 6 Poisoning, Promotion, Deactivation and Selectivity of Catalysts 439 6.1 Background 439 6.1.1 Effect of Mass Transfer on Catalytic Selectivity 440 6.1.1.1 Effect of Intraparticle Diffusion 440 6.1.1.2 Non-isothermal Conditions 445 6.1.1.3 Effect of Interparticle Mass and Heat Transfer 448 6.1.2 Bifunctional Catalysts (or Dual-Function Catalysts) 449 6.2 Catalyst Deactivation 452 6.2.1 Deactivation Processes 452 6.2.2 Deactivation Models 455 6.2.2.1 Steady-State Model 455 6.2.2.2 A Dynamic Model 459 6.2.3 Operational Consequences of Poisoning 462 6.3 Some Modern Theories of Poisoning and Promotion 463 6.3.1 General Theoretical Considerations 464 6.3.2 Theoretical Interpretation of Poisoning and Promotion 466 6.3.2.1 The Electronegativity of a Poison Seems to Be of Secondary Importance 469 6.3.2.2 Other Factors Responsible for Promotion and Poisoning 471 6.3.2.3 Influence of Surface Carbon and Sub-surface Hydrogen in Hydrogenations on Palladium 473 6.3.2.4 Concluding Remarks 473 Problems 474 References 477 Further Reading 477 General 477 Studies of Model Surfaces 477 Theory of Poisoning and Promotion 478 7 Catalytic Process Engineering 479 Part I: Recent Advances in Reactor Design 479 7.1 Novel Operating Strategies 482 7.1.1 Fixed-Bed Reactors 482 7.1.1.1 Periodic Operation 483 7.1.1.2 Concurrent Flow 485 7.1.2 Microchannel Reactors 485 7.1.3 Multifunctional Reactors 492 7.1.3.1 Integrating Exothermic and Endothermic Reactions 492 7.1.3.2 Integrating Heat Transfer and Reaction 494 7.1.3.3 Integrating Reaction and Separation 495 Part II: Traditional Methods of Catalytic Process Engineering 499 7.2 Traditional Catalytic Reactors 499 7.2.1 Experimental Laboratory Reactors 499 7.2.1.1 Batch Reactors 500 7.2.1.2 Tubular Reactors 501 7.2.1.3 Continuous Stirred-Tank Reactor 504 7.2.1.4 Recycle Reactor 506 7.2.1.5 Flowing-Solids Reactors 507 7.2.1.6 Slurry Reactors 507 7.2.2 Industrial Chemical Reactors 510 7.2.2.1 Batch Reactors 511 7.2.2.2 Continuous Tubular Reactors 513 7.2.2.3 Fluidized-Bed Reactor 522 7.2.2.4 Trickle-Bed Reactor 525 7.2.2.5 Metal Gauze Reactors 527 7.2.3 Thermal Characteristics of a Catalytic Reactor 528 Problems 534 References 538 General References for Part II 539 General 539 Kinetic Models 539 Experimental Chemical Reactor Configurations 540 Slurry Reactors 540 Further Reading 540 8 Heterogeneous Catalysis: Examples, Case Histories and Current Trends 541 8.1 Synthesis of Methanol 541 8.1.1 The Nature of the Catalyst 543 8.1.2 Insight into the Mechanism of Formation of CH3OH 544 8.1.3 Aspects of Methanol Synthesis Technology 545 8.2 Fischer–Tropsch Catalysis 546 8.2.1 Mechanistic Considerations 549 8.2.1.1 Does Synthesis Proceed via Hydroxymethylene Intermediates? 550 8.2.1.2 Schultz–Flory Statistics 554 8.2.2 Fine-Tuning the Fischer–Tropsch Process 555 8.2.3 Practical Fischer–Tropsch Catalysts and Process Conditions 556 8.2.4 Commercial Fischer–Tropsch Plants 559 8.2.5 Methanation, Steam Reforming and Water-Gas Shift Reactions 559 8.2.5.1 Methanation 559 8.2.5.2 Steam Reforming: the Most Extensively Used Means of Manufacturing Hydrogen 563 8.3 Synthesis of Ammonia 568 8.3.1 Catalyst Promoters are of Two Kinds 570 8.3.2 Kinetics of the Overall Reaction: the Temkin–Pyzhev Description 571 8.3.3 The Surface of Iron Catalysts for Ammonia Synthesis Contain Several Other Elements: but Is the Iron Crystalline? 573 8.3.3.1 Does Ammonia Synthesis Proceed via Atomically or Molecularly Adsorbed Nitrogen? 575 8.3.3.2 How and Where Are the Reactant Gases Adsorbed at the Catalyst Surface? 576 8.3.3.3 A Potential-Energy Diagram Illustrating How the Overall Reaction Leading to Ammonia Synthesis Can Be Constructed 580 8.3.3.4 How Potassium Serves as an Electronic Promoter 582 8.3.4 The Technology of Ammonia Synthesis 583 8.3.4.1 Reactor Configurations are Important Industrially 585 8.4 Oxidation of Ammonia: Stepping Toward the Fertilizer Industry 588 8.4.1 Ammonia Oxidation at Surfaces Containing Pre-adsorbed Oxygen: Hot Ad-Particles 592 8.5 In situ Catalytic Reaction and Separation 592 8.5.1 Catalytic Distillation 592 8.5.2 Catalytic Membrane Processes 596 8.6 Automobile Exhaust Catalysts and the Catalytic Monolith 601 8.6.1 The Architecture of the Three-Way Catalyst 603 8.6.2 The Catalytic Monolith 604 8.6.3 Catalytic Monoliths May Be Used in Several Applications 605 8.6.4 Rate Characteristics of Catalytic Combustion Processes 606 8.6.5 Combustion Reactions in a Catalytic Monolith Differ from Those Occurring in a Homogeneously Operated Combustor 607 8.6.6 Simulation of the Behaviour of a Catalytic Monolith is Important for Design Purposes 609 8.7 Photocatalytic Breakdown of Water and the Harnessing of Solar Energy 614 8.7.1 Prologue 614 8.7.2 Artificial Photosynthesis 615 8.7.3 The Fundamental Energies Involved 618 8.7.3.1 Oxygen Generation by Photo-Induced Oxidation of Water 619 8.7.3.2 Hydrogen Generation by Photo-Induced Reduction of Water 620 8.7.3.3 Simultaneous Generation of Hydrogen and Oxygen by Catalysed Photolysis of Water 621 8.7.4 Some Selected Practical Examples 624 8.7.4.1 The Grätzel Cell and Its Influence 626 8.7.4.2 Tandem Cells for Water Splitting by Visible Light 628 8.8 Catalytic Processes in the Petroleum Industry 629 8.8.1 Catalytic Reforming 631 8.8.2 Catalytic Cracking 633 8.8.2.1 Cracking Reactions 636 8.8.2.2 Cracking Catalysts 638 8.8.2.3 The Catalytic Cracking (FCC) Reactor 638 8.8.3 Hydrotreating 640 8.8.3.1 Total Conversion of Heavy Oils into Good Quality Distillates 644 Problems 645 References 651 Further Reading 653 9 Powering the Planet in a Sustainable Manner: Some of Tomorrow’s Catalysts (Actual and Desired) and Key Catalytic Features Pertaining to Renewable Feedstocks, Green Chemistry and Clean Technology 655 9.1 Introduction 655 Part I: Prospects, Practices and Principles of Generating Solar Fuels 658 9.2 Powering the Planet with Solar Fuel 658 9.3 Some Significant Advances in Photo-Assisted Water Splitting and Allied Phenomena 659 9.3.1 Strategies for Solar Energy Conversion 660 9.3.2 The Artificial Leaf 661 9.3.3 Earth-Abundant H2-Evolution Photocatalysts 664 9.3.4 Earth-Abundant O2-Evolution Photocatalysts 665 9.3.5 Lessons from Enzymes 666 9.3.6 A Selective Survey and Future Challenges 666 9.3.7 An Interim Status Report on Water Oxidation Photocatalysis 669 9.3.8 Core-Shell Co-Catalysts in the Photocatalytic Conversion of CO2 with Water into Methane 669 9.3.9 Modifying the Nature of TiO2 so as to Improve Its Photocatalytic Performance 670 9.3.9.1 Band Structure Engineering of Semiconductors for Enhanced Photoelectrochemical Water Splitting, with Special Reference to TiO2 and Fe2O3 674 9.3.10 Metal-Organic Frameworks (MOFs) and Their Photocatalytic Possibilities 675 9.3.11 Photocatalytic Solids for the Destruction of Toxic Pollutants and Otherwise Unwanted Molecules 676 9.4 The Hydrogen Economy 677 9.4.1 The Methanol Economy 682 Part II: Current Practices in Powering the Planet and Producing Chemicals 685 9.5 Some of Tomorrow’s Catalysts: Actual and Desired 685 9.5.1 Some Existing Industrial Catalysts Likely to be Difficult to Replace in the Near Future 687 9.5.2 Ammoxidation: Acrolein and Acrylic Acid 687 9.5.3 Poly(ethylene terephthalate) (PET) 692 9.5.4 Fischer–Tropsch Syntheses (FTS) 696 9.5.4.1 FTS Using CO2 to Generate Hydrocarbon Fuels 696 9.5.5 Adipic Acid; Nylon 6,6; Nylon 6 and Terephthalic Acid 697 9.5.5.1 The Practical Importance of Cascade Catalytic Reactions 700 9.5.6 Catalytic Cracking and Refining: the Impact of Mesostructured Y Zeolite 701 9.5.6.1 Ecofining: The Road to Green Refineries 705 9.6 A Biorefinery Capable of Producing Transportation Fuels and Commodity Chemicals that Starts with Metabolic Engineering and Ends with Inorganic Solid Catalysts 707 9.6.1 Renewables to para-Xylene and Other Aromatics 709 9.6.2 Biorefinery for Integrated Methods of Preparing Renewable Chemicals 711 9.6.3 Three Advanced Biofuels from Switchgrass Using Engineered Escherichia coli 711 9.7 Non-enzymatic Catalytic Processing of Biomass-Derived Raw Materials to Selected Chemical Products 711 9.7.1 Sustainable Chemistry by Upgrading Pyrolysis Oil 714 9.7.2 Catalytic Conversion of Microalgae into Green Hydrocarbons and Ethanol 716 9.7.2.1 Microalgae to Diesel 717 9.7.2.2 Microalgae to Bioethanol Using CO2 and Sunlight 718 9.8 Strategies for the Design of New Catalysts 719 9.8.1 The Merits and Limitations of Single-Site Heterogeneous Catalysis 720 Part III: Thermochemical Cycles and High-Flux, Solar-Driven Conversions 724 9.9 Solar-Driven, Catalysed Thermochemical Reactions as Alternatives to Fossil-Fuel-Based Energy and Chemical Economies 724 Acknowledgements 726 Problems 726 References 729 Further Reading 732 Index 733

Read more less

Book SynopsisThe Nobel Prize in Chemistry 2007 awarded to Gerhard Ertl for his groundbreaking studies in surface chemistry highlighted the importance of heterogeneous catalysis not only for modern chemical industry but also for environmental protection. Heterogeneous catalysis is seen as one of the key technologies which could solve the challenges associated with the increasing diversification of raw materials and energy sources. It is the decisive step in most chemical industry processes, a major method of reducing pollutant emissions from mobile sources and is present in fuel cells to produce electricity. The increasing power of computers over the last decades has led to modeling and numerical simulation becoming valuable tools in heterogeneous catalysis. This book covers many aspects, from the state-of-the-art in modeling and simulations of heterogeneous catalytic reactions on a molecular level to heterogeneous catalytic reactions from an engineering perspective. This first book on the topic conveys expert knowledge from surface science to both chemists and engineers interested in heterogeneous catalysis. The well-known and international authors comprehensively present many aspects of the wide bridge between surface science and catalytic technologies, including DFT calculations, reaction dynamics on surfaces, Monte Carlo simulations, heterogeneous reaction rates, reactions in porous media, electro-catalytic reactions, technical reactors, and perspectives of chemical and automobile industry on modeling heterogeneous catalysis. The result is a one-stop reference for theoretical and physical chemists, catalysis researchers, materials scientists, chemical engineers, and chemists in industry who would like to broaden their horizon and get a substantial overview on the different aspects of modeling and simulation of heterogeneous catalytic reactions.Trade Review“Overall the book is a good attempt to tackle a research topic that is very current. Indeed the book is up-to-date and there are very recent citations, many of which concern pgm applications in catalysis. In summary the book is a good introduction to the rapidly changing and wide reaching field of multiscale computational research.” (Platinum Metals Review, 2012) Table of ContentsPreface MODELING CATALYTIC REACTIONS ON SURFACES WITH DENSITY FUNCTIONAL THEORY Introduction Theoretical Background The Electrocatalytic Oxygen Reduction Reaction on Pt(111) Conclusions DYNAMICS OF REACTIONS AT SURFACES Introduction Theoretical and Computational Foundations of Dynamical Simulations Interpolation of Potential Energy Surfaces Quantum Dynamics of Reactions at Surfaces Nondissociative Molecular Adsorption Dynamics Adsorption Dynamics on Precovered Surfaces Relaxation Dynamics of Dissociated H2 Molecules Electronically Nonadiabatic Reaction Dynamics Conclusions FIRST-PRINCIPLES KINETIC MONTE CARLO SIMULATIONS FOR HETEROGENEOUS CATALYSIS: CONCEPTS, STATUS, AND FRONTIERS Introduction Concepts and Methodology A Showcase Frontiers Conclusions MODELING THE RATE OF HETEROGENEOUS REACTIONS Introduction Modeling the Rates of Chemical Reactions in the Gas Phase Computation of Surface Reaction Rates on a Molecular Basis Models Applicable for Numerical Simulation of Technical Catalytic Reactors Simplifying Complex Kinetic Schemes Summary and Outlook MODELING REACTIONS IN POROUS MEDIA Introduction Modeling Porous Structures and Surface Roughness Diffusion Diffusion and Reaction Pore Structure Optimization: Synthesis Conclusion MODELING POROUS MEDIA TRANSPORT, HETEROGENEOUS THERMAL CHEMISTRY, AND ELECTROCHEMICAL CHARGE TRANSFER Introduction Qualitative Illustration Gas-Phase Conservation Equations Ion and Electron Transport Charge Conservation Thermal Energy Chemical Kinetics Computational Algorithm Button Cell Example Summary and Conclusions EVALUATION OF MODELS FOR HETEROGENEOUS CATALYSIS Introduction Surface and Gas-Phase Diagnostic Methods Evaluation of Hetero/Homogeneous Chemical Reaction Schemes Evaluation of Transport Conclusions COMPUTATIONAL FLUID DYNAMICS OF CATALYTIC REACTORS Introduction Modeling of Reactive Flows Coupling of the Flow Field with Heterogeneous Chemical Reactions Numerical Methods and Computational Tools Reactor Simulations Summary and Outlook PERSPECTIVE OF INDUSTRY ON MODELING CATALYSIS The Industrial Challenge The Dual Approach The Role of Modeling Examples of Modeling and Scale-Up of Industrial Processes Conclusions PERSPECTIVES OF THE AUTOMOTIVE INDUSTRY ON THE MODELING OF EXHAUST GAS AFTERTREATMENT CATALYSTS Introduction Emission Legislation Exhaust Gas Aftertreatment Technologies Modeling of Catalytic Monoliths Modeling of Diesel Particulate Filters Selective Catalytic Reduction by NH3 (Urea-SCR) Modeling Diesel Oxidation Catalyst, Three-Way Catalyst, and NOx Storage and Reduction Catalyst Modeling Modeling Catalytic Effects in Diesel Particulate Filters Determination of Global Kinetic Parameters Challenges for Global Kinetic Models System Modeling of Combined Exhaust Aftertreatment Systems Conclusion

Read more less

Book SynopsisThis first book to illuminate this important aspect of chemical synthesis improves the lifetime of catalysts, thus reducing material and saving energy, costs and waste. The international panel of expert authors describes the studies that have been conducted concerning the way homogeneous catalysts decompose, and the differences between homogeneous and heterogeneous catalysts. The result is a ready reference for organic, catalytic, polymer and complex chemists, as well as those working in industry and with/on organometallics.Trade Review“The text is well-arranged thorough the monograph. The clear style makes it easy to read, further supported by the very informative formulas and figures. It is highly recommended for experts and novices and should serve as a primary source of valuable information not only for academics but also for industrial researchers. This very particular book should be an essential addition to any meaningful institutional library collection.” (Catal Lett, 1 October 2013) "This volume provides an up to date, well-informed appraisal of issues concerning activity and stability of homogeneous transition metal catalysts. It will prove to be a valuable source of information for researchers working in this field, from graduate students and academics to process chemists in industry." (Chemistry World, 2012)Table of ContentsELEMENTARY STEPS Introduction Metal Deposition Ligand Decomposition by Oxidation Phosphines Phosphites Imines and Pyridines Carbenes Reactions of Metal-Carbon and Metal-Hydride Bonds Reactions Blocking the Active Sites EARLY TRANSITION METAL CATALYSTS FOR OLEFIN POLYMERIZATION Ziegler-Natta Catalysts Metallocenes Other Single-Center Catalysts Vanadium-Based Catalysts Chromium-Based Catalysts Conclusions LATE TRANSITION METAL CATALYSTS FOR OLEFIN POLYMERIZATION Nickel- and Palladium-Based Catalysts Iron- and Cobalt-Based Catalysts Conclusions EFFECTS OF IMMOBILIZATION OF CATALYSTS FOR OLEFIN POLYMERIZATION Introduction Metallocenes and Related Complexes Other Titanium and Zirconium Complexes Vanadium Complexes Chromium Complexes Nickel Complexes Iron Complexes Conclusions DORMANT SPECIES IN TRANSITION METAL-CATALYZED OLEFIN POLYMERIZATION Introduction Ziegler-Natta Catalysts Metallocenes and Related Early Transition Metal Catalysts Late Transition Metal Catalysts Reversible Chain Transfer in Olefin Polymerization Conclusions TRANSITION METAL CATALYZED OLEFIN OLIGOMERIZATION Introduction Zirconium Catalysts Titanium Catalysts Tantalum Catalysts Chromium Catalysts Nickel Catalysts Iron Catalysts Tandem Catalysis Involving Oligomerization and Polymerization Conclusions ASYMMETRIC HYDROGENATION Introduction Incubation by Dienes in Rhodium Diene Precursors Inhibition by Substrates, Solvents, Polar Additives, and Impurities Inhibition by Formation of Bridged Species Inhibition by Ligand Decomposition Inhibition by the Product Inhibition by Metal Formation; Heterogeneous Catalysis by Metals Selective Activation and Deactivation of Enantiomeric Catalysts Conclusions CARBONYLATION REACTIONS Introduction Cobalt-Catalyzed Hydroformylation Rhodium-Catalyzed Hydroformylation Palladium-Catalyzed Alkene-CO Reactions Methanol Carbonylation Conclusions METAL-CATALYZED CROSS-COUPLING REACTIONS Introduction: A Few Historic Notes On the Mechanism of Initiation and Precursors Transmetallation Reductive Elimination Phosphine Decomposition Metal Impurities Metal Nanoparticles and Supported Metal Catalysts Conclusions ALKENE METATHESIS Introduction Molybdenum and Tungsten Catalysts Rhenium Catalysts Ruthenium Catalysts Conclusions

Read more less

Book SynopsisAdopting a didactic approach at an advanced, masters level, this concise textbook provides an array of questions & answers and features numerous industrial case studies and examples, with references for further, more detailed reading and to the latest peer-reviewed articles at the end of each chapter. A significant feature is the book's treatment of more recently developed catalytic processes and their applications in the pharmaceutical and fine chemical industries, with an indication of their present and future commercial impact. Written by a dedicated lecturer with a wealth of experience in industry, this is an invaluable tool for practicing chemical engineers and chemists who need to advance their education in this vibrant and expanding field.Trade Review“High recommended and excellent value in the paperback format.” (Organic Process Research and Development Journal, 2012) Table of ContentsFOREWORD PREFACE PART I CHEMICAL BASICS DEFINITION, OPTIONS, AND EXAMPLES: WHAT ACTUALLY IS CATALYSIS? Definition of Catalysis The Different Varieties of Catalysis The Directing Effect of the Catalyst Catalysis as a Part of "Green Chemistry" Sources of Information about Catalysis A BRIEF HISTORY: HOMOGENEOUS TRANSITION METAL CATALYSIS: A YOUNG SCIENCE A Brief History INDUSTRIAL HOMOGENEOUS CATALYSIS: WHAT IS THE ECONOMIC IMPORTANCE? Application Areas of Catalysis Important Homogeneous Catalyzed Processes Synthesis of Fine Chemicals by Homogeneous Catalysis DEFINITIONS OF IMPORTANT TERMS: SELECTIVITY, STY, TON, TOF, AND MORE. . . Conversion Yield Selectivity Other Important Target Values The Choice is Yours! BONDS, ELEMENTAL STEPS, AND CATALYST CYCLES: BASICS OF ORGANOMETALLIC CHEMISTRY Ligands Change in Oxidation State Changing of Coordination Number (CN) and Coordination Geometry The Elementary Steps Catalytic Cycles TRANSITION METAL COMPLEXES: THE "CAPTAINS" OF HOMOGENEOUS CATALYSIS Group IIIB Metals and Lanthanides Metals of Group IVB Metals of Groups VB to VIIB The "Iron Metals" of Group VIII The Noble Metals from Group VIII Gold: A Noble Metal from Group IB The Cost of Catalyst Metals The Availability of Transition Metal Catalysts A Typical Experiment: Synthesis of Pd(acac)2 THE COMPLEX LIGANDS: THE "MATES" OF HOMOGENEOUS CATALYSIS Monodentate Ligand or Chelate? Basicity of Ligands Cone Angle ("Tolman Cone Angle") The Bite Angle Costs and Accessibility of Ligands A Typical Experiment: The Synthesis of Biphephos Stability of Ligands THE SOLVENTS: THE REACTION MEDIUM Criteria for Choosing Solvents Miscibility of Solvents Solvents as Activators Solvents as Deactivators Availability and Purity of Solvents Special Solvents ASYMMETRIC CATALYSIS: THE "SPECIAL CASE" A Glossary of Asymmetric Catalysis A Quick Look Back Mechanistic Considerations Chiral Ligands Overview on Homogeneous Catalyzed Asymmetric Syntheses Industrial Applications THERMODYNAMICS OF HOMOGENEOUS CATALYSIS: WHEN DOES A CHEMICAL REACTION RUN? Gibbs Energy and Energy Plot Calculation or Assessment of the Free Reaction Enthalpy Thermodynamic Analysis of Complex Reaction Systems KINETICS OF HOMOGENEOUS CATALYSIS: HOW DOES THE REACTION PROCEED? Frequently Occurring Kinetics The Energy Diagram for Explaining Regioselectivity The Energy Diagram for Explaining Enantioselectivity Execution of Kinetic Measurements A Concrete Example: The (Isomerizing) Hydroformylation of Octenes Possible Failures in Kinetic Measurements OVERVIEW ON SPECTROSCOPIC METHODS: CAN WE SEE INTO HOMOGENEOUS CATALYSIS? UV/Visible Spectroscopy IR Spectroscopy NMR Spectroscopy Mass Spectroscopy Extended X-Ray Absorption Fine Structure Analysis Inductively Coupled Plasma Optical Emission Spectroscopy (ICP-OES) PART II PROCESS ENGINEERING FUNDAMENTALS REACTOR TYPES: WHERE DOES CATALYSIS OCCUR? Reactions in Homogeneous Liquid Phase Fluid-Fluid Systems The "Embarras de Richesses" Pressure Reactors New Trends OVERVIEW ON CATALYST RECYCLING METHODS: IS MY CATALYST ECONOMICAL? The Principles of Separation Precipitation Crystallization Adsorption THERMAL SEPARATION: THE SIMPLEST REMOVAL OF VOLATILE PRODUCTS The Basics Example: Hydroformylation Example: Oxidation of Ethene to Acetaldehyde Example: Carbonylation of Methanol to Acetic Acid IMMOBILIZATION ON SOLID SUPPORTS: FROM HOMOGENEOUS TO HETEROGENEOUS The Basic Principle Organic Supports Inorganic Supports LIQUID-LIQUID MULTIPHASE SYSTEMS: THE SMART APPROACH TO CATALYST SEPARATION Variants of Liquid?Liquid Biphasic (LLB) Systems Reaction and Separation Reactions with In-Situ Extraction Reactions with Post Extraction THERMOMORPHIC SOLVENT SYSTEMS: CLEVER ENHANCEMENTS Thermoregulated Phase-Transfer Catalysis Thermoregulated Microemulsions Thermoregulated Fluorous Solvent Systems Thermoregulated Polymer-Bound Catalysts Thermomorphic Multicomponent Solvent Systems A Retrospective Look at Catalyst Recycling Methods PART III HOMOGENEOUS CATALYZED REACTION TYPES AN OVERVIEW OF C?C-BONDING REACTIONS: A GUIDE THROUGH THE JUNGLE HYDROFORMYLATIONS: THE INDUSTRIAL ROUTE TO ALDEHYDES AND ALCOHOLS Substrates Catalysts Mechanisms Industrial Processes Asymmetric Hydroformylation A Typical Experiment: Hydroformylation of 1-Octene CARBONYLATIONS: THE VERSATILE INSERTIONS OF CARBON MONOXIDE Reactions between CO and Hydrogen Reactions of CO with Alkenes and Vinyl Arenes Reactions of CO with Dienes Reactions of CO with Alkynes Reactions of CO with Alcohols A Typical Experiment OLIGOMERIZATION AND CYCLOOLIGOMERIZATION: THE CONVERSION OF UNSATURATED ALIPHATICS INTO SHORT CHAINS OR MEDIUM-SIZED RINGS Oligomerization of Alkenes Dienes Alkynes Cooligomerizations A Typical Experiment METATHESIS: A "CHANGE-YOUR-PARTNERS" DANCE Mechanism and Catalysts Industrial Applications A Typical Experiment: Self Metathesis of 1-Octene POLYMERIZATIONS: THE PURPOSEFUL ASSEMBLY OF MACROMOLECULES Polyethylene and Ziegler Catalysts Polypropylene and Metallocene Catalysis Further Polyolefins Polydienes Polyketones Polyalkynes Post-Metallocenes Current Topics in Polymer Research A Typical Experiment TELOMERIZATIONS: THE CONSTRUCTION OF C8 AND C10 CHAINS Reactions, Mechanisms, and Catalysts Butadiene Telomerizations Telomerizations with Isoprene Telomerizations in Liquid?Liquid Biphasic Systems A Typical Experiment REACTIONS WITH CARBON DIOXIDE: THE ACTIVATION OF AN "INACTIVE" MOLECULE Carbon Dioxide and Alkanes Carbon Dioxide and Alkenes Carbon Dioxide and Dienes Carbon Dioxide and Alkynes Carbon Dioxide and Aromatics Carbon Dioxide and Hydrogen Carbon Dioxide and Epoxides Carbon Dioxide and Amines Carbon Dioxide-Containing Polymers A Typical Experiment CARBON-CARBON COUPLING WITH AROMATICS: NEW NAME REACTIONS Mizoroki-Heck Reactions Sonogashira-Hagihara Reactions Suzuki-Miyaura Reaction Cross-Couplings with Metal Organyles A Typical Experiment HYDROGENATIONS: C-H BOND FORMATION Catalysts and Mechanisms Asymmetric Hydrogenation Hydrogenation of Various Functional Groups Technical Applications A Typical Experiment OXIDATIONS: FORMATION OF C-O BONDS Wacker Oxidations Epoxidations Asymmetric Dihydroxylations Oxidative Cleavage of C=C Double Bonds Oxidations of Alkyl Aromatics A Typical Experiment AMINATIONS: FORMATION OF C-N BONDS Amination of Aryl Halides Hydroamination of Alkenes Hydroaminations of Dienes Hydroamination of Alkynes Amination of Functional Groups . . .Some More Aminations A Typical Experiment ISOMERIZATIONS: MIGRATION OF DOUBLE BONDS AND REARRANGEMENT OF THE CARBON BACKBONE Isomerization of Alkenes Isomerization of Substituted Alkenes Rearrangement of the Backbone A Typical Experiment PART IV NEW TRENDS TANDEM REACTIONS: MULTIPLE SYNTHESIS STEPS IN ONE POT Multicomponent Reactions Multifunctional Catalysis Tandem and Related Reactions A Typical Experiment COMBINATORIAL CHEMISTRY AND HIGH-THROUGHPUT CATALYST SCREENING: THE FAST WAY TO OPTIMUM RESULTS Basics and Definitions Parallel Reactor Systems Sequential Reactor Systems GREEN SOLVENTS: WORKING WITH ECO-FRIENDLY SOLVENTS Ionic Liquids Supercritical Fluids Fluorous Solvents Polyethers Conclusions ALKANE ACTIVATIONS: ACQUISITIONS OF NEW FEEDSTOCKS Mechanistic Considerations Alkane Oxidations Alkane Carbonylations Alkane Metathesis Alkane Hydrogenolysis Alkane Borylation Alkane Sulfonation A Look Back MORE EFFICIENT LIGANDS: THE BEST IS THE ENEMY OF THE GOOD Nitrogen-Containing Ligands Unusual Phosphorus Ligands Ligands Containing Elements from Group VIA Ligands Containing Elements from Group IVA NANOCATALYSIS: BETWEEN HOMOGENEOUS AND HETEROGENEOUS CATALYSIS Synthesis and Properties of Nanocatalysts Stabilization of Nanoparticles Heterogenization of Nanoparticles on Solid Supports Catalysis Involving Metal Nanoparticles HOMOGENEOUS CATALYSIS WITH RENEWABLES: USING NATURE.S TREASURES Catalytic Conversion of Fatty Compounds Catalytic Reactions of Carbohydrates Catalytic Reactions of Terpenes ELECTROCATALYSIS/SONOCATALYSIS/PHOTOCATALYSIS/MICROWAVE/EXTREME PRESSURE: ALTERNATIVE METHODS OF ACTIVATION Electrocatalysis Photocatalysis Sonocatalysis Microwave Catalysis Extreme High-Pressure Catalysis PROCESS DEVELOPMENT IN MINIPLANTS: FROM LABORATORY TO PRODUCTION Miniplant with Continuously Stirred-Tank Reactor (Miniplant I) Miniplant with Loop Reactor and Phase Separator (Miniplant II) Miniplant with Jetloop Reactor and Phase Separator (Miniplant III) Miniplant with a Mixer?Settler Battery (Miniplant IV) THE FUTURE OF HOMOGENEOUS CATALYSIS: A LOOK AHEAD New Resources New Reactions New Catalysts New Methods ANSWERS TO THE QUICKIES

Read more less

Book SynopsisGreen, clean and renewable are the hottest keywords for catalysis and industry. This handbook and ready reference is the first to combine the fields of advanced experimentation and catalytic process development for biobased materials in industry. It describes the entire workflow from idea, approach, research, and process development, right up to commercialization. A large part of the book is devoted to the use of advanced technologies and methodologies like high throughput experimentation, as well as reactor and process design models, with a wide selection of real-life examples included at each stage. The contributions are from authors at leading companies and institutes, providing firsthand information and knowledge that is hard to find elsewhere. This work is aimed at decision makers, engineers and chemists in industry, chemists and engineers working with/on renewables, chemists in the field of catalysis, and chemical engineers.Trade Review“Overall, especially for an edited book, this is a well organized book showing the overall story, rather than giving only pieces of a puzzle . . . It makes for an entertaining read. The book is certainly more suited to researchers in the field or at least with some background information.” (Green Processing and Synthesis, 1 August 2013) Table of ContentsTHE NEXT FEEDSTOCK TRANSITION PREFACE THE INDUSTRIAL PLAYING FIELD FOR THE CONVERSION OF BIOMASS TO RENEWABLE FUELS AND CHEMICALS Introduction The Renewables Arena Renewable Fuels Renewable Chemicals Conclusions SELECTING TARGETS Introduction Target Selection Can Focus on Specific Structures or General Technologies Previous Selection Efforts Corroboration of the Value of Screening Studies The Importance of Outcomes and Comparisons of Outcomes Evaluation Processes Can be Comprised of a Variety of Criteria Catalysis Aspects Conclusions THE DEVELOPMENT OF CATALYTIC PROCESSES FROM TERPENES TO CHEMICALS Introduction Strain Engineering for the Production of Terpenes Terpene Building Blocks of Commercial Interest Sesquiterpenes as Chemical Building Blocks: ß-Farnesene Polymers Lubricants Conclusions FURAN-BASED BUILDING BLOCKS FROM CARBOHYDRATES Importance of Furans as Building Blocks Sources of Carbohydrates Carbohydrate Dehydration Conclusions and Further Perspectives A WORKFLOW FOR PROCESS DESIGN - USING PARALLEL REACTOR EQUIPMENT BEYOND SCREENING Introduction The Evolution of Parallel Reactor Equipment The Evolution of Research Methodology - Conceptual Process Design Essential Workflow Elements Other Examples of Parallel Reactor Equipment Applied Beyond Screening - Long-Term Catalyst Performance Concluding Remarks BRASKEM'S ETHANOL TO POLYETHYLENE PROCESS DEVELOPMENT Introduction Ethanol and Brazil Commercial Plants for Ethanol Dehydration Legislation and Certification Process Description Polymerization Conclusion FATS AND OILS AS RAW MATERIAL FOR THE CHEMICAL INDUSTRY Introduction - Setting the Scene, Definitions Why Fats and Oils Need Catalytic Transformation Catalytic Process Development - Conceptual Fatty Alcohols: Then and Now, a Case Study Conclusion and Outlook: Development Challenges for the Future PRODUCTION OF AROMATIC CHEMICALS FROM BIOBASED FEEDSTOCK Introduction Chemical Routes to Aromatic Chemicals from Biomass Biological Routes to Specific Aromatic Chemicals Lignin - The Last Frontier Considerations for Scale-Up and Commercialization Conclusion ORGANOSOLV BIOREFI NING: CREATING HIGHER VALUE FROM BIOMASS Introduction Concepts and Principles of Biorefinery Technologies Catalytic Processes Employed in Biorefining An Organosolv Biorefinery Process for High-Value Products Conclusions BIOMASS-TO-LIQUIDS BY THE FISCHER - TROPSCH PROCESS Basics of Fischer - Tropsch Chemistry and BTL Cobalt Fischer - Tropsch Catalysis Fischer - Tropsch Reactors Biomass Pretreatment and Gasification Biomass-to-Liquids Process Concepts BTL Pilot and Demonstration Plants XTL Energy and Carbon Efficiencies BTL Summary and Outlook CATALYTIC TRANSFORMATION OF EXTRACTIVES Introduction Fine and Special Chemicals from Crude Tall Oil Compounds Fine and Special Chemicals from Turpentine Compounds Conclusions Acknowledgment ENVIRONMENTAL ASSESSMENT OF NOVEL CATALYTIC PROCESSES BASED ON RENEWABLE RAW MATERIALS - CASE STUDY FOR FURANICS Introduction Energy Savings by Catalytic Processes LCA Methodology Case Study: Energy Analysis and GHG Balance of Polyethylene Furandicarboxylate (PEF) as a Potential Replacement for Polyethylene Terephthalate (PET) Discussion and Conclusions CARBON DIOXIDE: A VALUABLE SOURCE OF CARBON FOR CHEMICALS, FUELS AND MATERIALS Introduction The Conditions for Industrial Use of CO2 Carbon Dioxide Conversion Energy Products from CO2 Production of Inorganic Carbonates Enhanced Fixation of CO2 into Aquatic Biomass Conclusion and Future Outlook INDEX

Read more less

Book SynopsisHighlighting the key aspects and latest advances in the rapidly developing field of molecular catalysis, this book covers new strategies to investigate reaction mechanisms, the enhancement of the catalysts' selectivity and efficiency, as well as the rational design of well-defined molecular catalysts. The interdisciplinary author team with an excellent reputation within the community discusses experimental and theoretical studies, along with examples of improved catalysts, and their application in organic synthesis, biocatalysis, and supported organometallic catalysis. As a result, readers will gain a deeper understanding of the catalytic transformations, allowing them to adapt the knowledge to their own investigations. With its ideal combination of fundamental and applied research, this is an essential reference for researchers and graduate students both in academic institutions and in the chemical industry. With a foreword by Nobel laureate Roald Hoffmann. Trade Review"Overall this book gives a very enjoyable overview of many aspects of the highly diverse field of catalysis, as viewed through the lens of the Heidelberg Collaborative Research Centre on molecular catalysis. I am very happy to recommend it to aspiring or established researchers in this area." (AOC, 2016)Table of ContentsForeword Introduction MECHANISMS OF ELEMENTARY REACTIONS IN CATALYTIC PROCESSES Quantum Dynamics of Molecular Elementary Processes in Catalytic Transformations Activation of Small Molecules with Metal and Metal Oxide Clusters in Inert Gas Matrices Towards Single-Molecule Catalysis Intermediates and Elementary Reactions in Gold Catalysis Diastereoselectivity in Alkene Metathesis NEW CATALYSTS - NEW AND OLD REACTIONS Oxidation Catalysis with High-Valent Nonheme Iron Complexes Single-Site Organochromium Catalysts for High Molecular Weight Polyolefins Ligand Design and Mechanistic Studies for Ni-Catalyzed Hydrocyanation and 2-Methyl-3-Butenenitrile Isomerization Based upon Rh-Hydroformylation Research Strongly Electron Donating Tridentate N-Heterocyclic Biscarbene Ligands for Rhodium and Iridium Catalysis NHCP Ligands for Catalysis CATALYSTS IN SYNTHESIS Ir-Catalyzed Asymmetric Allylic Substitution Reactions - Fundamentals and Applications in Natural Products Synthesis Sequential Catalysis Involving Metal Catalyzed Cycloisomerizations and Cyclizations C-N-Coupling Reactions in Catalytic One-Pot Syntheses using Molecular Group 4 Catalysts Sequential Catalysis for the Stereoselective Synthesis of Complex Polyketides Modular Assembly of Chiral Catalysts with Polydentate Stereodirecting Ligands STRUCTURES AND MECHANISMS IN BIOLOGICAL SYSTEMS Beating and Employing X-Ray-Induced Radiation Damage in Structural Studies of Hemoproteins The Catalytic Strategy of P-O Bond Cleaving Enzymes: Comparing EcoRV and Myosin Selective Hybrid Catalysts Based on Nucleic Acids STUDIES OF IMMOBILIZED CATALYSTS Dendrimers as Platforms for Stereoselective Catalysis Solid Phases as Protective Environments for Biomimetic Catalysts High-Throughput Screening of Catalysts and Reactions Index

Read more less

Book SynopsisFocusing on the basic principles of semiconductor photocatalysis, this book also gives a brief introduction to photochemistry, photoelectrochemistry, and homogeneous photocatalysis. In addition, the author - one of the leading authorities in the field - presents important environmental and practical aspects. A valuable, one-stop source for all chemists, material scientists, and physicists working in this area, as well as novice researchers entering semiconductor photocatalysis.Table of ContentsPreface XI Acknowledgments XIII 1 Introduction 1 1.1 A Brief History of Photochemistry 1 1.2 Catalysis, Photochemistry, and Photocatalysis 5 2 Molecular Photochemistry 9 2.1 Absorption and Emission 9 2.2 Intensity of Electronic Transitions 14 2.2.1 Contribution of Nuclei 14 2.2.2 Contribution of Spin 17 2.2.3 Contribution of Orbitals 17 2.3 Excited States Radiative Lifetimes 17 2.4 Energy and Electron Transfer 19 2.4.1 Energy Transfer 19 2.4.2 Electron Transfer 21 2.5 Proton Transfer and Hydrogen Abstraction 23 2.6 Photosensitization 23 2.7 Rates and Quantum Yields 25 2.8 Quenching of Excited States 26 2.8.1 Identification of the Reactive Excited State 28 2.9 Absorption, Emission, and Excitation Spectra 28 2.10 Classification and Reactivity of Excited States 30 2.10.1 Organic Molecules 30 2.10.1.1 π,π* States 30 2.10.1.2 n,π* States 30 2.10.1.3 Charge-Transfer (CT) States 32 2.10.1.4 Triplet and Singlet Oxygen Reactions 36 2.10.2 Inorganic and Organometallic Complexes 38 2.10.2.1 Metal-Centered (MC) States 39 2.10.2.2 Ligand-Centered (LC) States 42 2.10.2.3 Charge Transfer Metal to Ligand (CTML) States 42 2.10.2.4 Charge Transfer Ligand to Metal (CTLM) States 42 2.10.2.5 Charge Transfer to Solvent (CTTS) States 43 2.10.2.6 Intervalence Transfer (IT) States 43 3 Molecular Photocatalysis 47 3.1 Hydrogenation of 1,3-Dienes 47 3.2 Co-Cyclization of Alkynes with Nitriles 47 3.3 Enantioselective Trifluoromethylation of Aldehydes 48 3.4 Photoinduced Electron Transfer Catalysis 50 3.5 Reduction and Oxidation of Water 51 4 Photoelectrochemistry 55 4.1 Electronic Structure and Nature of Excited States 55 4.1.1 The (Optical) Bandgap 55 4.1.1.1 Measurement of the Bandgap Energy 58 4.1.1.2 Influence of Crystal Size 63 4.1.2 The Photonic Bandgap 64 4.1.3 Emission Spectra 65 4.2 Photocorrosion 68 4.3 Interfacial Electron Transfer 70 4.3.1 Introduction 70 4.3.2 Thermal Interfacial Electron Transfer (IFET) 73 4.3.2.1 IFET at the Metal/Liquid Interface 73 4.3.2.2 IFET at the Semiconductor/Liquid Interface 76 4.3.3 Photochemical Interfacial Electron Transfer 78 4.3.3.1 IFET in Large Semiconductor Crystals 78 4.3.3.2 IFET in Small Semiconductor Crystals 82 5 Semiconductor Photocatalysis 85 5.1 Mechanisms, Kinetics, and Adsorption 85 5.1.1 General Classification of Reactions 85 5.1.2 Rates, Quantum Yields, and Their Comparability 91 5.1.2.1 Direct Semiconductor Photocatalysis 91 5.1.3 Influence of Semiconductor Nature and Particle Size on Chemical Selectivity 108 5.1.3.1 Control of Chemoselectivity by Surface States and Redox Amplification 110 5.2 Characterization of Photocatalysts 111 5.2.1 General Methods 111 5.2.2 Flatband and Quasi-Fermi Potentials 112 5.2.2.1 Measurements in Absence of Light 112 5.3 Preparation and Properties of Photocatalysts 124 5.3.1 Pristine Compounds and Solid Solutions 128 5.3.1.1 TiO2 128 5.3.1.2 WO3 129 5.3.1.3 α-Fe2O3 130 5.3.1.4 BiVO4 130 5.3.1.5 Ta2O3, TaON, Ta3N5, and MTaO2N 130 5.3.1.6 CuO, Cu2O 131 5.3.1.7 GaN–ZnO 131 5.3.1.8 CdS and ZnS 133 5.3.2 Grafting of CdS and TiO2 onto Inorganic Supports 133 5.3.2.1 Grafting onto a Nonconducting Support 133 5.3.2.2 Grafting onto a Semiconducting Support 135 5.3.3 Grafting of Metal Halides and Metal Oxides onto Titania 136 5.3.3.1 Metal Chloride-Grafted Titania 136 5.3.4 Metal-Loaded Powders 141 5.3.5 Nonmetal-Modified Titania 141 5.3.5.1 Nitrogen-Modified Titania 142 5.3.5.2 “Carbon”-Modified Titania 146 5.3.5.3 Miscellaneous 147 5.4 Type A Reactions 148 5.4.1 WaterSplitting 149 5.4.1.1 One-Particle Photocatalysis 153 5.4.1.2 Two-Particle Photocatalysis 155 5.4.1.3 Reduction and Oxidation of Water 157 5.4.2 Aerobic Oxidations 159 5.4.2.1 Direct Photocatalysis 159 5.4.2.2 Indirect Photocatalysis 165 5.4.3 Nitrogen Fixation 165 5.4.3.1 Fixation by UV Irradiation 165 5.4.3.2 Fixation by Visible Irradiation 167 5.4.3.3 Formation of Ammonia, Hydrazine, and Nitrate 169 5.4.3.4 Role of ChlorideIons 171 5.4.3.5 Mechanism 172 5.4.4 Carbon Dioxide Fixation 173 5.4.5 Organic Reactions 176 5.4.5.1 Oxidative C–N Cleavage 177 5.4.5.2 Intramolecular C–N and C–C Coupling 178 5.4.5.3 Intermolecular C–C and C–N Coupling 178 5.4.5.4 Intermolecular C–O Coupling 181 5.4.5.5 Anaerobic Dehydrodimerization and Intermediary Water Reduction 182 5.5 Type B Reactions 188 5.5.1 C–N Coupling 188 5.5.2 C–C Coupling 192 5.5.2.1 Addition of Olefins to Imines 192 5.5.2.2 Addition of Olefins to Amines 198 5.5.3 C–H Activation of Alkanes 198 5.6 Environmental Aspects 202 5.6.1 Abiotic Nitrogen Fixation 202 5.6.2 Photocatalysis and Chemical Evolution 203 5.6.3 Detoxification of Air and Water 204 5.6.4 Antibacterial and Antiviral Effects 204 5.6.5 Amphiphilic Properties of Titania 205 5.7 Titaniain Food and Personal Care Products 206 5.8 Photoreactors 206 5.8.1 Laboratory Photoreactors 206 5.8.2 Solar Photoreactors and Kinetic Modeling 208 References 211 Index 245

Read more less

Book SynopsisA comprehensive overview covering the principles and preparation of catalysts, as well as reactor technology and applications in the field of organic synthesis, energy production, and environmental catalysis. Edited and authored by renowned and experienced scientists, this reference focuses on successful reaction procedures for applications in industry. Topics include catalyst preparation, the treatment of waste water and air, biomass and waste valorisation, hydrogen production, oil refining as well as organic synthesis in the presence of heterogeneous and homogeneous catalysts and continuous-flow reactions. With its practical relevance and successful methodologies, this is a valuable guide for chemists at universities working in the field of catalysis, organic synthesis, pharmaceutical or green chemistry, as well as researchers and engineers in the chemical industry.Table of ContentsList of Contributors XVII Preface XXI 1 General Introduction to Microwave Chemistry 1Satoshi Horikoshi and Nick Serpone 1.1 ElectromagneticWaves and Dielectric Materials 1 1.2 Microwave Heating 2 1.3 The Various Types of Microwave Heating Phenomena 4 1.3.1 Conduction Loss Heating (Eddy Current Loss and Joule Loss) 5 1.3.2 Dielectric Heating 5 1.3.3 Magnetic Loss Heating (Eddy Current Loss and Hysteresis Loss Heating) 6 1.3.4 Penetration Depth of Microwaves 6 1.4 Fields of Applications with Microwave Heating 9 1.5 Microwaves in Solid Material Processing 11 1.6 Microwaves in Organic Syntheses 12 1.7 Microwave Chemical Equipment 12 1.8 Chemical Reactions Using the Characteristics of Microwave Heating 17 1.9 Microwave Frequency Effect in Chemical Syntheses 21 1.10 Summary 25 References 25 Part I Fundamentals 29 2 Loss Mechanisms and Microwave-Specific Effects in Heterogeneous Catalysis 31A.E. Stiegman 2.1 Introduction 31 2.2 Heterogeneous Catalyst Systems 33 2.3 Physics of Microwave Absorption 33 2.4 Microwave Loss Processes in Solids 35 2.4.1 Dielectric Loss 35 2.4.2 Charge Carrier Processes 36 2.4.2.1 Conduction Loss 36 2.4.2.2 Space–Charge Recombination 37 2.4.2.3 Dipolar Loss 38 2.4.3 Magnetic Loss Processes 40 2.5 Loss Processes and Microwave-Specific Catalysis: Lessons from Gas–Carbon Reactions 41 2.5.1 Thermochemical Considerations 42 2.6 Final Comments on Microwave-Specific Effects in Heterogeneous Catalysis 45 Acknowledgments 45 References 46 3 Transport Phenomena and Thermal Property under Microwave Irradiation 49Yusuke Asakuma 3.1 Introduction 49 3.2 Bubble Formation 50 3.3 Convection 53 3.4 Surface Tension 56 3.5 Discussion of Nonthermal Effect for Nanobubble Formation 58 References 59 4 Managing Microwave-Induced Hot Spots in Heterogeneous Catalytic Systems 61Satoshi Horikoshi and Nick Serpone 4.1 What Are Hot Spots? 61 4.2 Microwaves in Heterogeneous Catalysis 61 4.3 Microwave-Induced Formation of Hot Spots in Heterogeneous Catalysis 63 4.3.1 Hot Spot Phenomenon 63 4.3.2 Mechanism(s) of Formation of Hot Spots 68 4.3.3 Particle Aggregation by Polarization of Activated Carbon Particulates 69 4.3.4 Control of the Occurrence of Hot Spots 73 References 75 Part II Applications – Preparation of Heterogeneous Catalysts 77 5 Preparation of Heterogeneous Catalysts by a Microwave Selective Heating Method 79Satoshi Horikoshi and Nick Serpone 5.1 Introduction 79 5.2 Synthesis of Metal Catalysts on Carbonaceous Material Supports 79 5.3 Photocatalysts 81 5.3.1 Preparation of TiO2/AC Particles 83 5.3.2 Proposed Mechanism of Formation of TiO2/AC Particles 86 5.3.3 Photoactivity ofMW-Prepared TiO2/AC Composite Particles in the Degradation of Isopropanol 87 5.4 Microwave-Assisted Syntheses of Catalytic Materials for Fuel Cell Applications 88 5.4.1 Microwave-Assisted Synthesis of Pt/C Catalyst Particulates for a H2 Fuel Cell 89 5.4.2 Preparation of Nanocatalysts for a Methanol Fuel Cell 91 5.4.3 Effects of pH on Pt Particle Size and Electrocatalytic Activity of Pt/CNTs for Methanol Electro-oxidation 93 5.5 Other Catalysts Prepared by Microwave-Related Procedures 94 5.6 Concluding Remarks 103 References 103 Part III Applications – Microwave Flow Systems and Microwave Methods Coupled to Other Techniques 109 6 Microwaves in Cu-Catalyzed Organic Synthesis in Batch and Flow Mode 111Faysal Benaskar, Narendra Patil, Volker Rebrov, Jaap Schouten, and Volker Hessel 6.1 Introduction 111 6.2 Microwave-Assisted Copper Catalysis for Organic Syntheses in Batch Processes 112 6.2.1 Bulk and Nano-structured Metals in a Microwave Field 112 6.2.1.1 Interaction of Bulk Metal with Microwaves 112 6.2.1.2 Metallic Catalyst Particle Size and Shape Effect on Microwave Heating 113 6.2.1.3 Polymetallic Systems in Microwave Chemistry 115 6.2.2 Microwave-Assisted Copper Catalysis for Chemical Synthesis 116 6.2.2.1 Bulk Copper Particles for Catalysis and Microwave Interaction 116 6.2.2.2 Microwave-Assisted Copper-Catalyzed Bond Formation Reactions 117 6.2.3 Supported Cu-Based Catalyst for Sustainable Catalysis in Microwave Field 120 6.2.3.1 Microwave Activation and Synthesis of Cu-Based Heterogeneous Catalysts 120 6.2.3.2 Cu-Supported Catalyst Systems for C–O, C–C, C–S, and C–N Coupling Reactions 121 6.3 Microwave-Assisted Copper Catalysis for Organic Syntheses in Flow Processes 122 6.3.1 Microwave-Assisted Catalyzed Organic Synthesis in Flow Processes 122 6.3.1.1 Microwave Heating in Homogeneously Catalyzed Processes 122 6.3.1.2 Microwave Energy Efficiency and Uniformity in Catalyzed Flow Processes 124 6.3.2 Structured Catalyst in Microwave-Assisted Flow Processing for Organic Reactions 130 6.3.2.1 Thin-Film Flow Reactors for Organic Syntheses 130 6.3.2.2 Structured Fixed-Bed Reactors for Flow Synthesis 131 6.3.2.3 Scale-Up of Microwave-Assisted Flow Processes 133 6.4 Concluding Remarks 136 References 136 7 Pilot Plant for Continuous Flow Microwave-Assisted Chemical Reactions 141Mitsuhiro Matsuzawa and Shigenori Togashi 7.1 Introduction 141 7.2 Continuous Flow Microwave-Assisted Chemical Reactor 142 7.2.1 Basic Structure 142 7.3 Pilot Plant 145 7.3.1 Design ofWaveguide 145 7.3.2 Configuration of Pilot Plant 147 7.3.3 Water Heating Test 148 7.3.4 Sonogashira Coupling Reaction 151 7.4 Conclusions 153 Acknowledgment 154 References 154 8 Efficient Catalysis by Combining Microwaves with Other Enabling Technologies 155Giancarlo Cravotto, Laura Rinaldi, and Diego Carnaroglio 8.1 Introduction 155 8.2 Catalysis with Hyphenated and Tandem Techniques 157 8.3 Microwave and Mechanochemical Activation 159 8.4 Microwave and UV Irradiation 162 8.5 Microwave and Ultrasound 164 8.6 Conclusions 166 References 166 Part IV Applications – Organic Reactions 171 9 Applications of Microwave Chemistry in Various Catalyzed Organic Reactions 173Rick Arneil Desabille Arancon, Antonio Angel Romero, and Rafael Luque 9.1 Introduction 173 9.1.1 Homogeneous Catalysis 175 9.2 Microwave-Assisted Reactions in Organic Solvents 175 9.3 Microwave-Assisted Reactions inWater-Coupling Reactions 179 9.3.1 The Heck Reactions 180 9.3.2 The Suzuki Reaction 186 9.4 Conclusions and Prospects 190 Acknowledgments 190 References 191 10 Microwave-Assisted Solid Acid Catalysis 193Hyejin Cho, Christian Schäfer, and Béla Török 10.1 Introduction 193 10.2 Microwave-Assisted Clay Catalysis 193 10.3 Zeolites in Microwave Catalysis 199 10.4 Microwave Application of Other Solid Acid Catalysts 205 10.4.1 Heteropoly Acids 205 10.4.2 Acidic Ion-Exchange Resins (Nafion-H, Amberlyst, Dowex) 206 10.4.2.1 Nafion-H 206 10.4.2.2 Amberlyst 207 10.4.2.3 Dowex 208 10.5 Conclusions and Outlook 209 References 209 11 Microwave-Assisted Enzymatic Reactions 213Takeo Yoshimura, ShigeruMineki, and Shokichi Ohuchi 11.1 Introduction 213 11.2 Synthewave (ProLabo) 217 11.2.1 Lipase 217 11.2.2 Glucosidase 220 11.3 Discover Series (CEM) 220 11.3.1 Lipase (Synthesis, Esterification) 220 11.3.2 Enzymatic Resolution 228 11.3.3 β-Glucosidase, β-Galactosidase 232 11.3.4 Aldolase 233 11.4 Mechanism of the Microwave-Assisted Enzymatic Reaction 233 References 236 Part V Applications – Hydrogenation and Fuel Formation 239 12 Effects of Microwave Activation in Hydrogenation–Dehydrogenation Reactions 241Leonid M. Kustov 12.1 Introduction 241 12.2 Specific Features of Catalytic Reactions Involving Hydrogen 242 12.3 Hydrogenation Processes under MWConditions 246 12.4 Dehydrogenation 250 12.5 Hydrogen Storage 252 12.6 Hydrogenation of Coal 254 Acknowledgment 254 References 254 13 Hydrogen Evolution from Organic Hydrides throughMicrowave Selective Heating in Heterogeneous Catalytic Systems 259Satoshi Horikoshi and Nick Serpone 13.1 Situation of Hydrogen Energy and Feature of Stage Methods 259 13.2 Selection of Organic Hydrides as the Hydrogen Carriers 261 13.3 Dehydrogenation of Hydrocarbons with Microwaves in Heterogeneous Catalytic Media 262 13.3.1 Selective Heating by the Microwave Method 262 13.3.2 Dehydrogenation of Tetralin in a Pt/AC Heterogeneous Catalytic Dispersion Subjected to a Microwave Radiation Field 263 13.3.3 Effects of the Tetralin: Pt/AC Ratio on Tetralin Dehydrogenation 264 13.3.4 Dehydrogenation of an Organic Carrier in a Continuous Flow System 266 13.3.5 Dehydrogenation of Methylcyclohexane in a Microwave Fixed-Bed Reactor 269 13.3.6 Simulation Modeling for Microwave Heating of Pt/AC in the Methylcyclohexane Solution 271 13.4 Dehydrogenation of Methane with Microwaves in a Heterogeneous Catalytic System 272 13.5 Problems and Improvements of Microwave-Assisted Heterogeneous Catalysis 273 Acknowledgments 277 References 277 Part VI Applications – Oil Refining 281 14 Microwave-Stimulated Oil and Gas Processing 283Leonid M. Kustov 14.1 Introduction 283 14.2 Early Publications 283 14.3 Use of Microwave Activation in Catalytic Processes of Gas and Oil Conversions 285 14.3.1 Hydrogen Production 285 14.3.2 CO2 Conversion 286 14.3.3 Synthesis Gas (Syngas) Production 286 14.3.4 Methane Decomposition 287 14.3.5 Methane Steam Reforming 288 14.3.6 Oxidative Coupling of Methane 288 14.3.7 Partial Oxidation and Other Hydrocarbon Conversion Processes 291 14.3.8 Oxidative Dehydrogenation 294 14.3.9 Oil Processing 295 14.4 Prospects for the Use of Microwave Radiation in Oil and Gas Processing 295 Acknowledgment 297 References 297 Part VII Applications – Biomass andWastes 301 15 Algal Biomass Conversion under Microwave Irradiation 303Shuntaro Tsubaki, Tadaharu Ueda, and Ayumu Onda 15.1 Introduction 303 15.2 Microwave Effect on Hydrothermal Conversion – Analysis Using Biomass Model Compounds 304 15.2.1 Degradation Kinetics of Neutral Sugars under Microwave Heating 304 15.2.2 Effects of Ionic Conduction on Hydrolysis of Disaccharides under Hydrothermal Condition 308 15.3 Hydrolysis of Biomass Using Ionic Conduction of Catalysts 309 15.3.1 Hydrolysis of Starch and Crystalline Cellulose Using Microwave Irradiation and Polyoxometalate Cluster 309 15.3.2 Hydrolysis Fast-Growing Green Macroalgae Using Microwave Irradiation and Polyoxometalate Cluster 311 15.4 Dielectric Property of Algal Hydrocolloids inWater 313 15.4.1 Comparison of Dielectric Property of Aqueous Solution of Hydrocolloids Obtained from Algae and Land Plants 313 15.4.2 The Effects of the Degree of Substitution of Acidic Functional Groups on Dielectric Property of Aqueous Solution of Algal Hydrocolloids 315 15.4.3 The Correlation of Loss Tangent at 2.45 GHz and Other Physical Properties of Sodium Alginates and Carrageenans inWater 316 15.5 Summary and Conclusions 319 Acknowledgments 319 References 319 16 Microwave-Assisted Lignocellulosic Biomass Conversion 323TomohikoMitani and TakashiWatanabe 16.1 Introduction 323 16.2 Lignocellulosic Biomass Conversion 324 16.3 Multi-mode Continuous Flow Microwave Reactor 325 16.4 Direct-Irradiation Continuous Flow Microwave Reactor 327 16.4.1 Concept of Reactor 327 16.4.2 Designing of Microwave Irradiation Section 327 16.4.3 Prototypes of Reactors 329 16.5 Pilot-Plant-Scale Continuous Flow Microwave Reactor 331 16.5.1 Concept of Reactor 331 16.5.2 Designing of Microwave Irradiation Section 331 16.5.3 Demonstration Experiments of Microwave Pretreatment 333 16.6 Summary and Conclusions 335 References 335 17 Biomass andWaste Valorization under Microwave Activation 337Leonid M. Kustov 17.1 Introduction 337 17.2 Vegetable Oil and Glycerol Conversion 338 17.3 Conversion of Carbohydrates 339 17.4 Cellulose Conversion 340 17.5 Lignin Processing 342 17.6 Waste and Renewable Raw Material Processing 343 17.7 Carbon Gasification 347 17.8 Prospects for the Use of Microwave Irradiation in the Conversion of Biomass and Renewables 348 Acknowledgment 350 References 350 Part VIII Applications – Environmental Catalysis 355 18 Oxidative and Reductive Catalysts for Environmental Purification Using Microwaves 357Takenori Hirano 18.1 Introduction 357 18.2 Microwave Heating of Catalyst Oxides Used for Environmental Purification 358 18.3 Microwave-Assisted Catalytic Oxidation of VOCs, Odorants, and Soot 361 18.4 Microwave-Assisted Reduction of NOx and SO2 364 18.5 Conclusions 367 References 367 19 Microwave-/Photo-Driven Photocatalytic Treatment of Wastewaters 369Satoshi Horikoshi and Nick Serpone 19.1 Situation ofWastewater Treatment by Photocatalytic Classical Methods 369 19.2 Experimental Setup of an Integrated Microwave/Photoreactor System 370 19.3 Microwave-/Photo-Driven PhotocatalyticWastewater Treatment 371 19.3.1 Degradation of Rhodamine B Dye 371 19.3.2 Change of TiO2 Surface Condition under a Microwave Field 376 19.3.3 Specific Nonthermal Microwave Effect(s) in TiO2 Photoassisted Reactions 377 19.3.4 Microwave Frequency Effects on the Photoactivity of TiO2 379 19.3.5 Increase in Radical Species on TiO2 under Microwave Irradiation 380 19.3.6 Microwave Nonthermal Effect(s) as a Key Factor in TiO2 Photoassisted Reactions 382 19.4 Microwave Discharge Electrodeless Lamps (MDELs) 386 19.4.1 The Need for More Efficient UV Light Sources 386 19.4.2 Purification ofWater Using TiO2-Coated MDEL Systems in Natural Disasters 387 19.5 Summary Remarks 389 References 389 Index 393

Read more less

Book SynopsisHighlighting sustainable catalytic processes in synthetic organic chemistry and industry, this useful guide places special emphasis on catalytic reactions carried out at room temperature. It describes the fundamentals, summarizes key advances, and covers applications in industrial processes in the field of energy generation from renewables, food science, and pollution control. Throughout, the latest research from various disciplines is combined, such as homogeneous and heterogeneous catalysis, biocatalysis, and photocatalysis. The book concludes with a chapter on future trends and energy challenges for the latter half of the 21st century. With its multidisciplinary approach this is an essential reference for academic and industrial researchers in catalysis science aiming to design more sustainable and energy-efficient processes.Table of Contents1 Introduction to Room-Temperature Catalysis 1Eduardo J. Garcia-Suarez and Anders Riisager 1.1 Introduction 1 1.2 Room-Temperature Homogeneous Catalysts 2 1.2.1 Ionic-Liquid-Based Catalytic Systems at Room Temperature 2 1.2.2 Transition Metal Homogeneous Catalysts 6 1.2.2.1 Group 9-Based Homogeneous Catalysts (Co, Rh, Ir) 6 1.2.2.2 Group 10-Based Homogeneous Catalysts (Ni, Pd, Pt) 7 1.2.2.3 Group 11-Based Homogeneous Catalysts (Ag, Au) 10 1.3 Room-Temperature Heterogeneous Catalysts 10 1.3.1 Group 9-Based Heterogeneous Catalysts (Co, Rh, Ir) 11 1.3.2 Group 10-Based Heterogeneous Catalysts (Ni, Pd, Pt) 13 1.3.3 Group 11-Based Heterogeneous Catalysts (Cu, Pt, Au) 23 1.4 Conclusions and Perspectives 29 References 31 2 Functionalized Ionic Liquid-based Catalytic Systems with Diversified Performance Enhancements 35Shiguo Zhang and Yanlong Gu 2.1 Introduction 35 2.2 Functionalized ILs for Enhancing Catalytic Activity 36 2.3 Functionalized ILs for Improving Reaction Selectivity 38 2.4 Functionalized ILs for Facilitating Catalyst Recycling and Product Isolation 40 2.5 Functionalized ILs for Making Relay Catalysis 43 2.6 Cation and Anion Synergistic Catalysis in Ionic Liquids 45 2.7 Functionalized ILs for Aqueous Catalysis 46 2.8 Catalysis by Porous Poly-ILs 47 2.9 Functionalized IL-Based Carbon Material for Catalysis 49 2.10 Summary and Conclusions 54 References 54 3 Heterogeneous Room Temperature Catalysis – Nanomaterials 59Liyu Chen and Yingwei Li 3.1 Introduction 59 3.2 Solid-Acid-Based Nanomaterials 60 3.3 Grafted-Metal-Ions-Based Nanomaterial 65 3.4 Metal NPs-Based Nanomaterial 67 3.4.1 Metal NPs Stabilized by Ligands 67 3.4.2 Metal NPs@Polymers 68 3.4.3 Metal NPs@Metal Oxides 70 3.4.4 Metal NPs@Carbonaceous Support 72 3.4.5 Metal NPs@Siliceous Base Support 74 3.4.6 Metal NPs@MOF Nanocomposites 77 3.5 Metal Oxide NPs-Based Nanomaterial 82 3.6 Summary and Conclusions 83 References 84 4 Biocatalysis at Room Temperature 89Ivaldo Itabaiana Jr and Rodrigo O. M. A. De Souza 4.1 Introduction 89 4.2 Transaminases 90 4.2.1 General Features 90 4.2.2 Transaminase Applications at Room Temperature 90 4.3 Hydrolases 98 4.3.1 General Features 98 4.3.2 Application of Hydrolases at Room Temperature 100 4.3.2.1 Lipases 100 4.3.2.2 Aldol Additions 101 4.3.2.3 Michael Addition 102 4.3.2.4 Mannich Reaction 102 4.3.2.5 C-Heteroatom and Heteroatom–Heteroatom Bond Formations 103 4.3.2.6 Epoxidation 103 4.3.2.7 Synthesis of Heterocycles 104 4.3.2.8 Kinetic Resolutions 105 4.3.3 Cutinases 107 4.4 Laccases 108 4.4.1 General Features 108 4.4.2 Applications of Laccases 110 4.5 Enzymes in Ionic Liquids 115 4.5.1 General Features 115 References 125 5 Room Temperature Catalysis Enabled by Light 135Timothy Noël 5.1 Introduction 135 5.2 UV Photochemistry 136 5.3 Visible Light Photoredox Catalysis 139 5.4 Room Temperature Cross-Coupling Enabled by Light 141 5.5 Photochemistry and Microreactor Technology –A Perfect Match? 144 5.6 The Use of Photochemistry in Material Science 146 5.7 Solar Fuels 149 5.8 Conclusion 151 References 151 6 Mechanochemically Enhanced Organic Transformations 155Davin Tan and Tomislav Frišcic 6.1 Introduction 155 6.2 Mechanochemical Techniques and Mechanisms: Neat versus Liquid-Assisted Grinding (LAG) 156 6.3 Oxidation and Reduction Using Mechanochemistry 160 6.3.1 Direct Oxidation of Organic Substrates Using Oxone 160 6.3.2 Mechanochemical Halogenations Aided by Oxone 162 6.3.3 Reduction Reactions by Mechanochemistry 163 6.4 Electrocyclic Reactions: Equilibrium and Templating in Mechanochemistry 165 6.4.1 The Diels–Alder Reaction: Mechanochemical Equilibrium in Reversible C—C Bond Formation 165 6.4.2 Photochemical [2+2] Cycloaddition during Grinding: Supramolecular Catalysis and Structure Templating 167 6.5 Recent Advances in Metal-CatalyzedMechanochemical Reactions 168 6.5.1 Copper-Catalyzed [2+3] Cycloaddition (Huisgen Coupling) 168 6.5.2 Olefin Metathesis by Ball Milling 169 6.5.3 Mechanochemical C—H Bond Activation 170 6.5.4 Cyclopropanation of Alkenes Using Silver Foil as a Catalyst Source 171 6.6 New Frontiers in Organic Synthesis Enabled by Mechanochemistry 171 6.6.1 Synthesis of Active Pharmaceutical Ingredients (APIs) 172 6.6.2 Reactivity Enabled or Facilitated by Mechanochemistry 173 6.6.3 Trapping Unstable Reaction Intermediates 175 6.7 Conclusion and Outlook 176 Acknowledgments 176 References 176 7 Palladium-Catalyzed Cross-Coupling in Continuous Flow at Room andMild Temperature 183Christophe Len 7.1 Introduction 183 7.2 Suzuki Cross-Coupling in Continuous Flow 184 7.3 Heck Cross-Coupling in Continuous Flow 192 7.4 Murahashi Cross-Coupling in Continuous Flow 199 7.5 Concluding Remarks 202 References 202 8 Catalysis for Environmental Applications 207Changseok Han, Endalkachew Sahle-Demessie, Afzal Shah, Saima Nawaz, Latif-ur-Rahman, Niall B.McGuinness, Suresh C. Pillai, Hyeok Choi, Dionysios, D. Dionysiou, andMallikarjuna N. Nadagouda 8.1 Introduction 207 8.2 Ferrate (FeO42−) forWater Treatment 208 8.3 Magnetically Separable Ferrite forWater Treatment 209 8.3.1 Magnetic Nanoparticles 209 8.3.2 Magnetic Recovery of Materials Used forWater Treatment 211 8.3.3 Ferrite Photocatalyst forWater Treatment 212 8.4 UV, Solar, and Visible Light-Activated TiO2 Photocatalysts for Environmental Application 212 8.5 Catalysis for Remediation of Contaminated Groundwater and Soils 215 8.5.1 Catalytic Oxidative Pathways 215 8.5.2 Catalytic Reductive Pathways 217 8.5.3 Prospects and Limitations 218 8.6 Novel Catalysis for Environmental Applications 218 8.6.1 Graphene and Graphene Composites 219 8.6.2 Perovskites and Perovskites Composites 221 8.6.3 Graphitic Carbon Nitride (g-C3N4) and g-C3N4 Composites 222 8.7 Summary and Conclusions 223 Acknowledgments 224 Disclaimer 224 References 224 9 Future Development in Room-Temperature Catalysis and Challenges in the Twenty-first Century 231Fannie P. Y. Lau, R. Luque, and Frank L. Y. Lam Case Study 1: Magnetic Pd Catalysts for Benzyl Alcohol Oxidation to Benzaldehyde 237Yingying Li, Frank L.-Y. Lam, and Xijun Hu 1.1 Introduction 237 1.2 Pd/MagSBA Magnetic Catalyst for Selective Benzyl Alcohol Oxidation to Benzaldehyde 239 1.2.1 Results and Discussion 239 1.2.1.1 Characterization 239 1.2.1.2 Effect of Reaction Temperature 240 1.2.1.3 Effect of Pd Loading 241 1.2.1.4 Recycling Test 246 1.3 Summary and Conclusions 246 References 247 Case Study 2: Development of Hydrothermally Stable Functional Materials for Sustainable Conversion of Biomass to Furan Compounds 251Amrita Chatterjee, Xijun Hu, and Frank L.-Y. Lam 2.1 Introduction 251 2.2 Metal–Organic-Framework as a Potential Catalyst for Biomass Valorization 254 2.3 Xylose Dehydration to Furfural Using Metal–Organic-Framework, MIL-101(Cr) 255 2.3.1 Xylose Dehydration Catalyzed by Organosilane Coated MIL-101(Cr) 255 2.3.2 Xylose to Furfural Transformation Catalyzed by Fly-Ash and MIL-101(Cr) Composite 258 2.3.3 Xylose to Furfural Transformation Catalyzed by Tin Phosphate and MIL-101(Cr) Composite 262 2.3.4 Role of Acid Sites, Textural Properties and Hydrothermal Stability of Catalyst in Xylose Dehydration Reaction 264 2.4 Conclusion 267 References 268 Index 273

Read more less

Book SynopsisEarly Main Group Metal Catalysis gives a comprehensive overview of catalytic reactions in the presence of group 1 and group 2 metals. Chapters are ordered to reaction type, contain educational elements and deal with concepts illustrated by examples that cover the main developments. After a short introduction on polar organometallic chemistry and synthesis of early main group metal complexes, a variety of catalytic reactions are described, e.g. polymerization of alkenes, hydroamination and phosphination reactions, hydrosilylation, hydroboration and hydrogenation catalysis, as well as enantioselective and Lewis-acid catalysis. The book addresses organic chemists and researchers in industry interested in the state-of-the-art and new possibilities of early main group metal catalysis as well as newcomers to the field. Written by a team of leaders in the field, it is a very welcome addition to the area of main group metal chemistry, and to the field of catalysis.Table of ContentsPreface xiii 1 Introduction to Early Main Group Organometallic Chemistry and Catalysis 1Sjoerd Harder 1.1 Introduction 1 1.2 s-Block Organometallics 1 1.2.1 Short History 1 1.2.2 Synthesis of Group 1 Organometallics 2 1.2.3 Synthesis of Group 2 Organometallics 4 1.2.4 Bonding and Structures of s-Block Organometallics 8 1.2.5 Dynamics of s-Block Organometallics in Solution 13 1.2.6 Low-Valent s-Block Chemistry 16 1.3 s-Block Organometallics in Catalysis 17 1.3.1 Working Principles in Lewis Acid Catalysis 17 1.3.2 Working Principles in s-Block Organometallic Catalysis 19 1.3.3 Substrate Activation by s-Block Metals 21 1.3.4 Future of Early Main Group Metal Catalysis 23 List of Abbreviations 24 References 24 2 Polymerization of Alkenes and Polar Monomers by Early Main Group Metal Complexes 31Sjoerd Harder 2.1 Introduction 31 2.2 Alkene Polymerization 32 2.2.1 Styrene Polymerization 33 2.2.2 Polymerization of Modified Styrene 40 2.2.3 Polymerization of Butadiene or Isoprene 43 2.3 Polymerization of Polar Monomers 45 2.3.1 Polymerization of Lactides 45 2.3.2 Copolymerization of Epoxides and CO2 50 2.4 Conclusions 53 List of Abbreviations 54 References 54 3 Intramolecular Hydroamination of Alkenes 59Sebastian Bestgen and Peter W. Roesky 3.1 Introduction 59 3.2 Hydroamination 60 3.2.1 Scope 62 3.3 s-Block Metal Catalysis 64 3.3.1 General Remarks 64 3.3.2 Mechanistic Aspects 65 3.3.3 Group 1-Based Catalysis 68 3.3.3.1 Concerted Reaction 68 3.3.3.2 Radical-Mediated Intramolecular Hydroamination 71 3.3.3.3 Reactions of N-Arylhydrazones and Ketoximes 72 3.3.4 Group 2 Metal-Mediated Catalysis 74 3.3.5 Group 2-Mediated Asymmetric Cyclohydroamination 83 3.3.6 Lewis Acidic Metal Cation Catalysis 84 3.3.7 Miscellaneous 85 3.4 Outlook 86 Acknowledgments 87 List of Abbreviations 87 References 88 4 Molecular s-Block Catalysts for Alkene Hydrophosphination and Related Reactions 93Yann Sarazin and Jean-François Carpentier 4.1 Introduction 93 4.2 General Considerations 95 4.3 Hydrophosphination of Alkenes 96 4.3.1 Precatalysts with Nitrogen-Based Ligands 97 4.3.2 Precatalysts with Oxygen-Based Ligands 110 4.4 Hydrophosphination of Carbodiimides 112 4.5 Miscellaneous Reactions 114 4.5.1 Hydrophosphinylation of Alkenes and Enones 114 4.5.2 Hydrophosphonylation of Aldehydes and Ketones 116 4.6 Summary and Conclusions 117 List of Abbreviations 118 References 118 5 H—Nand H—P Bond Addition to Alkynes and Heterocumulenes 123Sven Krieck and Matthias Westerhausen 5.1 Introduction 123 5.2 Hydroamination 124 5.2.1 Hydroamination with Secondary Amines 125 5.2.2 Hydroamination with Primary Amines 128 5.2.3 Proposed Mechanisms for the Hydroamination of Butadiynes 130 5.3 Hydrophosphanylation (Hydrophosphination) 134 5.4 Hydrophosphorylation and Hydrophosphonylation 138 5.5 Summary and Conclusions 143 5.6 Acknowledgments 146 5.7 Abbreviations 146 References 146 6 Early Main Group Metal-Catalyzed Hydrosilylation of Unsaturated Bonds 151Sjoerd Harder 6.1 Introduction 151 6.2 Historical Development 151 6.3 Nonprecious Metal Hydrosilylation Catalysts 153 6.4 C=C Bond Hydrosilylation with s-Block Metal Catalysts 155 6.5 C=O Bond Hydrosilylation with s-Block Metal Catalysts 161 6.6 C=N Bond Hydrosilylation with s-Block Metal Catalysts 167 6.7 Conclusions 170 References 171 7 Early Main Group Metal Catalyzed Hydrogenation 175Heiko Bauer and Sjoerd Harder 7.1 Introduction 175 7.2 Hydrogenation of C=C Double Bonds 178 7.3 Hydrogenation of C=N Double Bonds 187 7.4 Hydrogenation of C=O Double Bonds 191 7.5 Summary and Perspectives 194 References 197 8 Alkali and Alkaline Earth Element-Catalyzed Hydroboration Reactions 201Aaron D. Sadow 8.1 Introduction and Overview 201 8.2 Thermodynamic Considerations 203 8.2.1 Hydroboration, Hydrosilylation, and Hydrogenation 203 8.2.2 Thermochemistry of Metal–Oxygen Bonds and Element–Hydrogen Bonds 205 8.3 Group 1-Catalyzed Hydroboration Reactions 207 8.3.1 Overview 207 8.3.2 Base-Catalyzed Hydroborations 207 8.3.3 Alkali Metal Hydridoborate and Aluminate-Catalyzed Hydroboration 210 8.4 Group 2-Catalyzed Hydroboration Reactions 214 8.4.1 Overview 214 8.4.2 β-Diketiminate Magnesium-Catalyzed Hydroborations 215 8.4.3 Tris(4,4-dimethyl-2-oxazolinyl)phenylborato Magnesium-Catalyzed Hydroboration of Ester and Amides 217 8.4.4 Magnesium Triphenylborate-Catalyzed Hydroboration 221 8.4.5 Supported Catalysts for Hydroboration 221 8.5 Summary and Conclusions 222 References 222 9 Dehydrocoupling and Other Cross-couplings 225Merle Arrowsmith 9.1 Introduction 225 9.2 Early Main Group-Catalyzed Cross-DHC of Amines and Boranes 228 9.2.1 Early Stoichiometric Studies with s-Block Elements 228 9.2.2 s-Block-Catalyzed Cross-dehydrogenative Synthesis of Diaminoboranes 229 9.2.3 s-Block-Catalyzed DHC of DMAB 231 9.2.4 Calcium-Catalyzed Dehydrocoupling of tert-Butylamine Borane 235 9.2.5 s-Block-Catalyzed DHC of Amines and Monohydroboranes 235 9.3 s-Block-Catalyzed Cross-DHC of Amines and Silanes 238 9.3.1 Influence of Precatalysts and Substrates on Reactivity and Selectivity 238 9.3.2 Mechanistic and Computational Analysis 240 9.3.3 Application to the Synthesis of Oligo- and Polysilazanes 242 9.4 Other s-Block-Catalyzed Cross-DHC Reactions 243 9.4.1 Alkali Metal-Catalyzed DHC of Si—H and O—H Bonds 243 9.4.2 s-Block-Catalyzed DHC of Si—H and C—H Bonds 243 9.5 Early Main Group-Mediated Nondehydrogenative Cross-couplings 244 9.6 Conclusion and Outlook 245 References 246 10 Enantioselective Catalysis with s-Block Organometallics 251Philipp Stegner and Sjoerd Harder 10.1 Introduction 251 10.2 Lithium-Based Catalysts 252 10.2.1 Lithium Catalysts Based on Neutral Chiral Ligands 252 10.2.2 Lithium Catalysts Based on Monoanionic Chiral Ligands 255 10.2.3 Lithium Catalysts Based on Dianionic Chiral Ligands 257 10.3 Potassium-Based Catalysts 259 10.3.1 Potassium Catalysts Based on Monoanionic Chiral Ligands 260 10.4 Magnesium-Based Catalysts 262 10.4.1 Magnesium Catalysts Based on Monoanionic Chiral Ligands 263 10.4.2 Magnesium Catalysts Based on Dianionic Chiral Ligands 266 10.5 Calcium-Based Catalysts 269 10.5.1 Calcium Catalysts Based on Monoanionic Chiral Ligands 269 10.5.2 Calcium Catalysts Based on Dianionic Chiral Ligands 273 10.6 Conclusion and Outlook 275 List of Abbreviations 275 References 276 11 Early Main Group Metal Lewis Acid Catalysis 279Marian Rauser, Sebastian Schröder, and Meike Niggemann 11.1 Introduction 279 11.1.1 Lewis Acidity of s-Block Metal Cations 280 11.1.2 Interactions with More than One Lewis Base 281 11.1.3 Counter Anions 282 11.1.4 Solvation 283 11.1.5 Solubility and Aggregation 283 11.1.6 Water Tolerance 284 11.1.7 Relative Lewis Acid Activity of Alkaline and Alkaline Earth Metals 285 11.1.8 Hidden Brønsted Acid 287 11.2 Polarized Carbon–Heteroatom Double Bonds 287 11.2.1 Carboxylates: Anhydrides and Carbonates 288 11.2.2 Aldehydes, Ketones, and Formates 289 11.2.3 α,β-Unsaturated Carbonyl Compounds 291 11.2.4 Imines and Enamines 292 11.2.5 Mannich Reactions 294 11.2.6 Oxidation and Reduction 294 11.2.7 Donor–Acceptor Cyclopropanes 294 11.2.8 Diels–Alder Reaction and Cycloaddition 295 11.3 Activation of Polarized Single Bonds 296 11.3.1 Opening of Three-Membered Heterocycles 296 11.3.2 Leaving Groups 297 11.3.3 Ca2+-Catalyzed Dehydroxylation as a Special Case 299 11.4 Activation of Unpolarized Double Bonds 305 11.5 Summary and Conclusions 307 References 307 12 Enantioselective Group 2Metal Lewis Acid Catalysis 311Yasuhiro Yamashita, Tetsu Tsubogo, and Shū Kobayashi 12.1 Introduction 311 12.2 Catalytic Enantioselective Reactions Using Chiral Magnesium Complexes 313 12.2.1 Chiral Magnesium-Catalyzed Diels–Alder and 1,3-Dipolar Cycloaddition Reactions 313 12.2.2 Chiral Magnesium-Catalyzed 1,4-Addition Reactions 315 12.2.3 Chiral Magnesium-Catalyzed Addition Reactions to Carbonyl Compounds 318 12.2.4 Chiral Magnesium-Catalyzed Addition Reactions with Imines 319 12.2.5 Chiral Magnesium-Catalyzed Ring-Opening Reactions of Epoxide and Aziridine 321 12.2.6 Chiral Magnesium-Catalyzed α-Functionalization Reactions of Carbonyl Compounds 323 12.2.7 Various Chiral Magnesium-Catalyzed Reactions 324 12.3 Catalytic Enantioselective Reactions Using Chiral Calcium Complexes 324 12.3.1 Chiral Calcium-Catalyzed Addition Reactions to Carbonyl Compounds 324 12.3.2 Chiral Calcium-Catalyzed 1,4-Addition Reactions 326 12.3.3 Chiral Calcium-Catalyzed Addition Reactions with Imines 331 12.3.4 Chiral Calcium-Catalyzed α-Functionalization Reactions with Carbonyl Compounds 333 12.3.5 Chiral Calcium-Catalyzed Cycloaddition Reactions 334 12.3.6 Chiral Calcium-Catalyzed Hydroamination Reactions 334 12.3.7 Chiral Calcium-Catalyzed Epoxidation Reactions 336 12.3.8 Chiral Calcium-Catalyzed Aziridine Ring-Opening Reaction 337 12.4 Catalytic Enantioselective Reactions Using Chiral Strontium Complexes 337 12.4.1 Chiral Strontium-Catalyzed 1,4-Addition Reactions 337 12.4.2 Chiral Strontium-Catalyzed Addition Reactions with Imines 338 12.4.3 Chiral Strontium-Catalyzed Oxime Formation 339 12.5 Catalytic Enantioselective Reactions Using Chiral Barium Complexes 339 12.5.1 Chiral Barium-Catalyzed Addition Reactions to Carbonyl Compounds and Imines 339 12.5.2 Chiral Barium-Catalyzed 1,4-Addition Reactions 340 12.5.3 Chiral Barium-Catalyzed Diels–Alder Reactions 341 12.6 Summary and Outlook 341 References 342 13 Miscellaneous Reactions 347Michael S. Hill 13.1 Introduction 347 13.2 Privileged Substrates and s-Block Reactivity 347 13.3 Reactivity with Multiply Bonded Substrates 351 13.3.1 Tishchenko Dimerization of Aldehydes 351 13.3.2 Trimerization of Organic Isocyanates 352 13.3.3 Hydroalkoxylation of Alkynyl Alcohols 353 13.3.4 Catalytic Isomerization and C–C Coupling with Terminal Alkynes 354 13.3.5 Activation and Deoxygenation of C—O Multiple Bonds 358 13.4 Single-Electron Transfer Steps in s-Block-Centered Catalysis 361 13.5 “Beyond” Hydrofunctionalization and Dehydrocoupling 363 13.6 Conclusions and Conjecture 365 References 367 Index 373

Read more less

Book SynopsisThe book gives a unique overview of this rapidly developing research field, presenting structures and properties of flavin derivatives as well as their proven application as bioinspired catalysts in various organocatalytic, biocatalytic, and photocatalytic reactions.Table of ContentsStructure and properties of flavins Natural flavins: occurrence, role and non-canonical chemistry Spectral properties of flavins Modes of flavin-based catalysis Organocatalytic monooxygenations Flavin-based supramolecular and coupled catalytic systems Flavoprotein monooxygenases and halogenases Flavoprotein-dependent bioreduction Flavoprotein oxidases Benzylic photooxidation by flavins New applications of flavin photocatalysis Light-driven flavin-based biocatalysis

Read more less

Book SynopsisElectrocatalysis 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.Table of ContentsPreface xv Acknowledgments xix Part I Introduction 1 1 Introduction 3 References 5 Part II Natural Carbon Cycle 7 2 Natural Carbon Cycle and Anthropogenic Carbon Cycle 9 2.1 Definition and General Process 9 2.2 From Inorganic Carbon to Organic Carbon 10 2.3 From Organic Carbon to Inorganic Carbon 11 2.4 Anthropogenic Carbon Cycle 11 2.4.1 Anthropogenic Carbon Emissions 12 2.4.2 Capture and Recycle of CO2 from the Atmosphere 13 2.4.3 Fixation and Conversion of CO2 14 2.4.3.1 Photochemical Reduction 14 2.4.3.2 Electrochemical Reduction 15 2.4.3.3 Chemical/Thermo Reforming 16 2.4.3.4 Physical Fixation 16 2.4.3.5 Anthropogenic Carbon Conversion and Emissions Via Electrochemistry 17 References 18 Part III Electrochemical Catalysis Process 21 3 Electrochemical Catalysis Processes 23 3.1 Water Splitting 23 3.1.1 Reaction Mechanism 23 3.1.1.1 Mechanism of OER 23 3.1.1.2 Mechanism of ORR 24 3.1.1.3 Mechanism of HER 26 3.1.2 General Parameters to Evaluate Water Splitting 27 3.1.2.1 Tafel Slope 27 3.1.2.2 TOF 27 3.1.2.3 Onset/Overpotential 28 3.1.2.4 Stability 28 3.1.2.5 Electrolyte 28 3.2 Electrochemistry CO2 Reduction Reaction (ECDRR) 29 3.2.1 Possible Reaction Pathways of ECDRR 29 3.2.1.1 Formation of HCOO− or HCOOH 29 3.2.1.2 Formation of CO 30 3.2.1.3 Formation of C1 Products 30 3.2.1.4 Formation of C2 Products 31 3.2.1.5 Formation of CH3COOH and CH3COO− 33 3.2.1.6 Formation of n-Propanol (C3 Product) 33 3.2.2 General Parameters to Evaluate ECDRR 34 3.2.2.1 Onset Potential 34 3.2.2.2 Faradaic Efficiency 34 3.2.2.3 Partial Current Density 34 3.2.2.4 Environmental Impact and Cost 35 3.2.2.5 Electrolytes 35 3.2.2.6 Electrochemical Cells 36 3.3 Small Organic Molecules Oxidation 36 3.3.1 The Mechanism of Electrochemistry HCOOH Oxidation 36 3.3.2 The Mechanism of Electro-oxidation of Alcohol 37 References 40 Part IV Water Splitting and Devices 43 4 Water Splitting Basic Parameter/Others 45 4.1 Composition and Exact Reactions in Different pH Solution 45 4.2 Evaluation of the Catalytic Activity 47 4.2.1 Overpotential 47 4.2.2 Tafel Slope 48 4.2.3 Stability 49 4.2.4 Faradaic Efficiency 49 4.2.5 Turnover Frequency 50 References 50 5 H2O Oxidation 53 5.1 Regular H2O Oxidation 53 5.1.1 Noble Metal Catalysts 53 5.1.2 Other Transition Metals 64 5.1.3 Other Catalysts 72 5.2 Photo-Assisted H2O Oxidation 76 5.2.1 Metal Compound-Based Catalysts 76 5.2.2 Metal–Metal Heterostructure Catalysts 80 5.2.3 Metal–Nonmetal Heterostructure Catalysts 86 References 88 6 H2O Reduction and Water Splitting Electrocatalytic Cell 91 6.1 Noble-Metal-Based HER Catalysts 91 6.2 Non-Noble Metal Catalysts 93 6.3 Water Splitting Electrocatalytic Cell 96 References 99 Part V H2 Oxidation/O2 Reduction and Device 101 7 Introduction 103 7.1 Electrocatalytic Reaction Parameters 104 7.1.1 Electrochemically Active Surface Area (ECSA) 104 7.1.1.1 Test Methods 104 7.1.2 Determination Based on the Surface Redox Reaction 104 7.1.3 Determination by Electric Double-Layer Capacitance Method 105 7.1.4 Kinetic and Exchange Current Density (jk and j0) 105 7.1.4.1 Definition 105 7.1.4.2 Calculation 106 7.1.5 Overpotential HUPD 106 7.1.6 Tafel Slope 108 7.1.7 Halfwave Potentials 108 References 108 8 Hydrogen Oxidation Reaction (HOR) 111 8.1 Mechanism for HOR 111 8.1.1 Hydrogen Bonding Energy (HBE) 111 8.1.2 Underpotential Deposition (UPD) of Hydrogen 112 8.2 Catalysts for HOR 112 8.2.1 Pt-based Materials 112 8.2.2 Pd-Based Materials 120 8.2.3 Ir-Based Materials 121 8.2.4 Rh-Based Materials 121 8.2.5 Ru-Based Materials 121 8.2.6 Non-noble Metal Materials 122 References 130 9 Oxygen Reduction Reaction (ORR) 133 9.1 Mechanism for ORR 133 9.1.1 Battery System and Damaged Electrodes 133 9.1.2 Intermediate Species 134 9.2 Catalysts in ORR 134 9.2.1 Noble Metal Materials 134 9.2.1.1 Platinum/Carbon Catalyst 138 9.2.1.2 Pd and Pt 145 9.2.2 Transition Metal Catalysts 145 9.2.3 Metal-Free Catalysts 149 9.3 Hydrogen Peroxide Synthesis 154 9.3.1 Catalysts Advances 154 9.3.1.1 Pure Metals 154 9.3.1.2 Metal Alloys 156 9.3.1.3 Carbon Materials 157 9.3.1.4 Electrodes and Reaction Cells 158 References 161 10 Fuel Cell and Metal-Air Battery 167 10.1 H2 Fuel Cell 167 10.2 Metal-Air Battery 170 10.2.1 Metal-Air Battery Structure 171 References 181 Part VI Small Organic Molecules Oxidation and Device 183 11 Introduction 185 11.1 Primary Measurement Methods and Parameters 186 11.1.1 Primary Measurement Methods 186 11.1.2 Primary Parameter 193 References 197 12 C1 Molecule Oxidation 199 12.1 Methane Oxidation 199 12.1.1 Reaction Mechanism 199 12.1.1.1 Solid–Liquid–Gas Reaction System 199 12.1.2 Acidic Media 199 12.1.3 Alkaline or Neutral Media 201 12.2 Methanol Oxidation 203 12.2.1 Reaction Thermodynamics and Mechanism 203 12.2.2 Catalyst Advances 204 12.2.2.1 Pd-Based Catalysts 204 12.2.2.2 Pt-Based Catalysts 208 12.2.2.3 Platinum-Based Nanowires 208 12.2.2.4 Platinum-Based Nanotubes 210 12.2.2.5 Platinum-Based Nanoflowers 212 12.2.2.6 Platinum-Based Nanorods 214 12.2.2.7 Platinum-Based Nanocubes 215 12.2.3 Pt–Ru System 217 12.2.4 Pt–Sn Catalysts 218 12.3 Formic Acid Oxidation 219 12.3.1 Reaction Mechanism 219 12.3.2 Catalyst Advances 220 12.3.2.1 Pd-Based Catalysts 220 12.3.2.2 Pt-Based Catalysts 223 References 226 13 C2+ Molecule Oxidation 235 13.1 Ethanol Oxidation 235 13.1.1 Reaction Mechanism 235 13.1.2 Catalyst Advances 235 13.1.2.1 Pd-Based Catalysts 235 13.1.2.2 Pt-Based Catalysts 239 13.1.2.3 Pt–Sn System 243 13.2 Glucose Oxidase 250 13.3 Ethylene Glycol Oxidation 251 13.4 Glycerol Oxidation 251 References 254 14 Fuel Cell Devices 257 14.1 Introduction 257 14.2 Types of Direct Liquid Fuel Cells 258 14.2.1 Acid and Alkaline Fuel Cells 258 14.2.2 Direct Methanol Fuel Cells (DMFCs) 260 14.2.3 Direct Ethanol Fuel Cells (DEFCs) 261 14.2.4 Direct Ethylene Glycol Fuel Cells (DEGFCs) 261 14.2.5 Direct Glycerol Fuel Cells (DGFCs) 262 14.2.6 Direct Formic Acid Fuel Cells (DFAFCs) 262 14.2.7 Direct Dimethyl Ether Fuel Cells (DDEFCs) 263 14.2.8 Other DLFCs 263 14.2.9 Challenges of DLFCs 264 14.2.10 Fuel Conversion and Cathode Flooding 264 14.2.11 Chemical Safety and By-product Production 265 14.2.12 Unproven Long-term Durability 265 References 267 Part VII CO2 Reduction and Device 271 15 Introduction 273 15.1 Basic Parameters of the CO2 Reduction Reaction 276 15.1.1 The Fundamental Parameters to Evaluate the Catalytic Activity 276 15.1.1.1 Overpotential (𝜂) 276 15.1.1.2 Faradaic Efficiency (FE) 276 15.1.1.3 Current Density ( j) 277 15.1.1.4 Energy Efficiency (EE) 277 15.1.1.5 Tafel Slope 278 15.1.2 Factors Affecting ECDRR 278 15.1.2.1 Solvent/Electrolyte 278 15.1.2.2 pH 280 15.1.2.3 Cations and Anions 281 15.1.2.4 Concentration 282 15.1.2.5 Temperature and Pressure Effect 282 15.1.3 Electrode 283 15.1.3.1 Loading Method 283 15.1.3.2 Preparation 284 15.1.3.3 Experimental Process and Analysis Methods 284 References 285 16 Electrocatalysts-1 289 16.1 Heterogeneous Electrochemical CO2 Reduction Reaction 289 16.2 Thermodynamic and Kinetic Parameters of Heterogeneous CO2 Reduction in Liquid Phase 289 16.2.1 Bulk Metals 293 16.2.2 Nanoscale Metal and Oxidant Metal Catalysts 294 16.2.2.1 Gold (Au) 295 16.2.2.2 Silver (Ag) 296 16.2.2.3 Palladium (Pd) 297 16.2.2.4 Zinc (Zn) 298 16.2.2.5 Copper (Cu) 299 16.2.3 Bimetallic/Alloy 301 References 306 17 Electrocatalysts-2 309 17.1 Single-Atom Metal-Doped Carbon Catalysts (SACs) 309 17.1.1 Nickel (Ni)-SACs 309 17.1.2 Cobalt (Co)-SACs 311 17.1.3 Iron (Fe)-SACs 311 17.1.4 Zinc (Zn)-SACs 314 17.1.5 Copper (Cu)-SACs 314 17.1.6 Other 316 17.2 Metal Nanoparticles-Doped Carbon Catalysts 317 17.3 Porous Organic Material 320 17.3.1 Metal Organic Frameworks (MOFs) 320 17.3.2 Covalent Organic Frameworks (COFs) 321 17.3.3 Metal-Free Catalyst 322 17.4 Metal-Free Carbon-Based Catalyst 322 17.4.1 Other Metal-Free Catalyst 324 17.5 Electrochemical CO Reduction Reaction 324 17.5.1 The Importance of CO Reduction Study 324 17.5.2 Advances in CO Reduction 326 References 327 18 Devices 331 18.1 H-Cell 331 18.2 Flow Cell 333 18.3 Requirements and Challenges for Next-Generation CO2 Reduction Cell 338 18.3.1 Wide Range of Electrocatalysts 338 18.3.2 Fundamental Factor Influencing the Catalytic Activity for ECDRR 339 18.3.3 Device Engineering 340 References 342 Part VIII Computations-Guided Electrocatalysis 345 19 Insights into the Catalytic Process 347 19.1 Electric Double Layer 347 19.2 Kinetics and Thermodynamics 349 19.3 Electrode Potential Effects 350 References 352 20 Computational Electrocatalysis 355 20.1 Computational Screening Toward Calculation Theories 356 20.2 Reactivity Descriptors 358 20.2.1 d-band Theory Motivates Electronic Descriptor 359 20.2.2 Coordination Numbers Motives Structure Descriptor 361 20.3 Scaling Relationships: Applications of Descriptors 361 20.4 The Activity Principles and the Volcano Curve 363 20.5 DFT Modeling 366 20.5.1 CHE Model 367 20.5.2 Solvation Models 368 20.5.3 Kinetic Modeling 371 References 374 21 Theory-Guided Rational Design 377 21.1 Descriptors-Guided Screening 377 21.2 Scaling Relationship-Guided Trends 380 21.2.1 Reactivity Trends of ECR 380 21.2.2 Reactivity Trends of O-included Reactions 382 21.2.3 Reactivity Trends of H-included Reactions 385 21.3 DOS-Guided Models and Active Sites 386 References 388 22 DFT Applications in Selected Electrocatalytic Systems 391 22.1 Unveiling the Electrocatalytic Mechanism 391 22.1.1 ECR Reaction 393 22.1.2 OER Reaction 394 22.1.3 ORR Reaction 396 22.1.4 HER Reaction 397 22.1.5 HOR Reaction 398 22.1.6 CO Oxidation Reaction 400 22.1.7 FAOR Reaction 402 22.1.8 MOR Reaction 402 22.1.9 EOR Reaction 404 22.2 Understanding the Electrocatalytic Environment 406 22.2.1 Solvation Effects 406 22.2.2 pH Effects 409 22.3 Analyzing the Electrochemical Kinetics 410 22.4 Perspectives, Challenges, and Future Direction of DFT Computation in Electrocatalysis 413 References 414 Part IX Potential of In Situ Characterizations for Electrocatalysis 421 References 422 23 In Situ Characterization Techniques 423 23.1 Optical Characterization Techniques 423 23.1.1 Infrared Spectroscopy 423 23.1.2 Raman Spectroscopy 424 23.1.3 UV–vis Spectroscopy 426 23.2 X-Ray Characterization Techniques 427 23.2.1 X-Ray Diffraction (XRD) 429 23.2.2 X-Ray Absorption Spectroscopy (XAS) 429 23.2.3 X-Ray Photoelectron Spectroscopy (XPS) 431 23.3 Mass Spectrometric Characterization Techniques 431 23.4 Electron-Based Characterization Techniques 432 23.4.1 Transmission Electron Microscopy (TEM) 434 23.4.2 Scanning Probe Microscopy (SPM) 434 References 436 24 In Situ Characterizations in Electrocatalytic Cycle 441 24.1 Investigating the Real Active Centers 441 24.1.1 Monitoring the Electronic Structure 442 24.1.2 Monitoring the Atomic Structure 444 24.1.3 Monitoring the Catalyst Phase Transformation 446 24.2 Investigating the Reaction Mechanism 449 24.2.1 Through Adsorption/Activation Understanding 450 24.2.2 Through Intermediates In Situ Probing 451 24.2.3 Through Catalytic Product In Situ Detections 454 24.3 Evaluating the Catalyst Stability/Decay 457 24.4 Revealing the Interfacial-Related Insights 460 24.5 Conclusion 462 References 462 Part X Electrochemical Catalytic Carbon Cycle 465 References 466 25 Electrochemical CO2 Reduction to Fuels 467 References 479 26 Electrochemical Fuel Oxidation 483 References 495 27 Evaluation and Management of ECC 499 27.1 Basic Performance Index 499 27.2 CO2 Capture and Fuel Transport 500 27.3 External Management 500 27.4 General Outlook 502 References 505 Index 507

Read more less

Book SynopsisCatalysis in Confined Frameworks Understanding the synthesis and applications of porous solid catalysts Heterogeneous catalysis is a catalytic process in which catalysts and reactants exist in different phases. Heterogeneous catalysis with solid catalysts proceeds through the absorption of substrates and reagents which are liquid or gas, and this is largely dependent on the accessible surface area of the solid which can generate active reaction sites. The synthesis of porous solids is an increasingly productive approach to generating solid catalysts with larger accessible surface area, allowing more efficient catalysis. Catalysis in Confined Frameworks: Synthesis, Characterization, and Applications provides a comprehensive overview of synthesis and use of porous solids as heterogeneous catalysts. It provides detailed analysis of pore engineering, a thorough characterization of the advantages and disadvantages of porous solids as heterogeneous catalysts, and an extensive discussion of applications. The result is a foundational introduction to a cutting-edge field. Catalysis in Confined Frameworks: Synthesis, Characterization, and Applications readers will also find: An editorial team comprised of international experts with extensive experience Detailed discussion of catalyst classes including zeolites, mesoporous aluminosilicates, and more A special focus on size selective catalysis Catalysis in Confined Frameworks: Synthesis, Characterization, and Applications is an essential reference for catalytic chemists, organic chemists, materials scientists, physical chemists, and any researchers or industry professionals working with heterogeneous catalysis.Table of ContentsPreface xiii 1 Engineering of Metal Active Sites in MOFs 1 Carmen Fernández-Conde, María Romero-Ángel, Ana Rubio-Gaspar, and Carlos Martí-Gastaldo 1.1 Metal Node Engineering 2 1.1.1 Frameworks with Intrinsically Active Metal Nodes 3 1.1.1.1 Metal–Organic Frameworks with Only One Metal 3 1.1.1.2 Metal–Organic Frameworks with more than One Metal in its Cluster 6 1.1.2 Introducing Defectivity as a Powerful Tool to Tune Metal-node Catalytic Properties in MOFs 8 1.1.3 Incorporating Metals to Already-Synthetized Metal–Organic Frameworks: Isolating the Catalytic Site 12 1.1.4 Metal Exchange 14 1.1.5 Attaching Metallic Units to the MOF 14 1.1.6 Grafting of Organometallic Complexes into the MOF Nodes 18 1.2 Ligand Engineering 21 1.2.1 Ligands as Active Metal Sites 22 1.2.1.1 Creating Metal Sites in the Organic Linkers. Types of Ligands 22 1.2.1.2 Cooperation Between Single-Metal Sites and Metalloligands 28 1.2.1.3 Ligand Accelerated Catalysis (LAC) 28 1.2.2 Introduction of Metals by Direct Synthesis 31 1.2.2.1 In-situ Metalation 32 1.2.2.2 Premetalated Linker 32 1.2.2.3 Postgrafting Metal Complexes 33 1.2.3 Introduction of Metals by Post-synthetic Modifications 34 1.2.3.1 Post-synthetic Exchange or Solvent-Assisted Linker Exchange (sale) 34 1.2.3.2 Post-synthetic Metalation 36 1.3 Metal-Based Guest Pore Engineering 38 1.3.1 Encapsulation Methodologies in As-Made Metal–Organic Frameworks 39 1.3.1.1 Incipient Wetness Impregnation 39 1.3.1.2 Ship-in-a-Bottle 42 1.3.1.3 Metal–Organic Chemical Vapor Deposition (MOCVD) 42 1.3.1.4 Metal-Ion Exchange 46 1.3.2 In Situ Guest Metal–Organic Framework Encapsulations 47 1.3.2.1 Solvothermal Encapsulation or One Pot 47 1.3.2.2 Co-precipitation Methodologies 49 List of Abbreviations 52 References 53 2 Engineering the Porosity and Active Sites in Metal–Organic Framework 67 Ashish K. Kar, Ganesh S. More, and Rajendra Srivastava 2.1 Introduction 67 2.2 Active Sites in MOF 69 2.2.1 Active Sites Near Pores in MOF 69 2.2.2 Active Sites Near Metallic Nodes in MOF 70 2.2.3 Active Sites Near Ligand Center in MOF 70 2.3 Synthesis and Characterization 70 2.4 Engineering of Active Sites in MOF Structure for Catalytic Transformations 72 2.4.1 Pore Tunability 73 2.4.2 Metal Nodes 77 2.4.3 Ligand Centers 83 2.5 Conclusion 90 References 91 3 Characterization of Organic Linker-Containing Porous Materials as New Emerging Heterogeneous Catalysts 97 Ali R. Oveisi, Saba Daliran, and Yong Peng 3.1 Introduction 97 3.2 Microscopy Techniques 98 3.2.1 Scanning Electron Microscopy (SEM) 98 3.2.2 Transmission Electron Microscopy (TEM) 100 3.2.3 Atomic Force Microscopy (AFM) 103 3.3 Spectroscopy Techniques 104 3.3.1 X-ray Spectroscopy 104 3.3.1.1 X-ray Diffraction (XRD) 104 3.3.1.2 X-ray Photoelectron Spectroscopy (XPS) 105 3.3.1.3 X-ray Absorption Fine Structure (XAFS) Techniques 107 3.3.2 Nuclear Magnetic Resonance (NMR) 109 3.3.3 Electron Paramagnetic Resonance (EPR) 110 3.3.4 Ultraviolet-Visible Diffuse Reflectance Spectroscopy (UV–Vis DRS) 111 3.3.5 Inductively Coupled Plasma (ICP) Analysis 112 3.4 Other Techniques 114 3.4.1 Thermogravimetric Analysis (TGA) 114 3.4.2 N2 Adsorption 115 3.4.3 Density Functional Theory (DFT) Calculations 118 3.5 Conclusions 121 Acknowledgments 121 References 121 4 Mixed Linker MOFs in Catalysis 127 Mohammad Y. Masoomi and Lida Hashemi 4.1 Introduction 127 4.1.1 Introduction to Mixed Linker MOFs 127 4.2 Strategies for Synthesizing Mixed-Linker MOFs 128 4.2.1 IML Frameworks 128 4.2.2 HML Frameworks 129 4.2.3 TML Frameworks 130 4.3 Types of Mixed-Linker MOFs 131 4.3.1 Pillared-Layer Mixed-Linker MOFs 131 4.3.2 Cage-Directed Mixed-Linker MOFs 132 4.3.3 Cluster-Based Mixed-Linker MOFs 132 4.3.4 Structure Templated Mixed-Linker MOFs 132 4.4 Introduction to Catalysis with MOFs 133 4.5 Mixed-Linker MOFs as Heterogeneous Catalysts 133 4.5.1 Mixed-Linker MOFs with Similar Size/Directionality Linkers 134 4.5.2 Mixed-Linker MOFs with Structurally Independent Linkers 140 4.6 Conclusion 148 References 148 5 Acid-Catalyzed Diastereoselective Reactions Inside MOF Pores 151 Herme G. Baldoví, Sergio Navalón, and Francesc X. Llabrés I Xamena 5.1 Introduction 151 5.2 Diastereoselective Reactions Catalyzed by MOFs 154 5.2.1 Meerwein–Ponndorf–Verley Reduction of Carbonyl Compounds 154 5.2.2 Aldol Addition Reactions 158 5.2.3 Diels–Alder Reaction 162 5.2.4 Isomerization Reactions 164 5.2.5 Cyclopropanation 168 5.3 Conclusions and Outlook 176 Acknowledgments 176 References 176 6 Chiral MOFs for Asymmetric Catalysis 181 Kayhaneh Berijani and Ali Morsali 6.1 Chiral Metal–Organic Frameworks (CMOFs) 181 6.2 Synthesis Methods of CMOFs with Achiral and Chiral Building Blocks 184 6.2.1 Spontaneous Resolution 185 6.2.2 Direct Synthesis 187 6.2.3 Indirect Synthesis 190 6.3 Chiral MOF Catalysts 192 6.3.1 Brief History of CMOF-Based Catalysts 192 6.3.2 Designing CMOF Catalysts 193 6.4 Examples of Enantioselective Catalysis Using CMOF-Based Catalysts 194 6.4.1 Type I: Chiral MOFs in Simple Asymmetric Reactions 194 6.4.2 Type II: Chiral MOFs in Complex Asymmetric Reactions 206 6.5 Conclusion 210 References 210 7 MOF-Supported Metal Nanoparticles for Catalytic Applications 219 Danyu Guo, liyu Chen, and Yingwei li 7.1 Introduction 219 7.2 Synergistic Catalysis by MNP@MOF Composites 220 7.2.1 The Inorganic Nodes of MOFs Cooperating with Metal NPs 220 7.2.2 The Organic Linkers of MOFs Cooperating with Metal NPs 220 7.2.3 The Nanostructures of MOFs Cooperating with Metal NPs 221 7.3 Electrocatalysis Applications 221 7.3.1 Hydrogen Evolution Reaction 221 7.3.2 Oxygen Evolution Reaction 223 7.3.3 Oxygen Reduction Reaction 224 7.3.4 CO2 Reduction Reaction 224 7.3.4.1 CO 225 7.3.4.2 HCOOH 225 7.3.4.3 C2H4 225 7.3.5 Nitrogen Reduction Reaction 227 7.3.6 Oxidation of Small Molecules 228 7.4 Photocatalytic Applications 229 7.4.1 Photocatalytic Hydrogen Production 229 7.4.2 Photocatalytic CO2 Reduction 232 7.4.2.1 CO2 Photoreduction to CO 232 7.4.2.2 CO2 Photoreduction to CH3OH 233 7.4.2.3 CO2 Photoreduction to HCOO−/HCOOH 234 7.4.3 Photocatalytic Organic Reactions 235 7.4.3.1 Photocatalytic Hydrogenation Reactions 235 7.4.3.2 Photocatalytic Oxidation Reactions 235 7.4.3.3 Photocatalytic Coupling Reaction 236 7.4.4 Photocatalytic Degradation of Organic Pollutants 237 7.4.4.1 Degradation of Pollutants in Wastewater 237 7.4.4.2 Degradation of Gas-Phase Organic Compounds 239 7.5 Thermocatalytic Applications 239 7.5.1 Oxidation Reactions 239 7.5.1.1 Gas-Phase Oxidation Reactions 239 7.5.1.2 Liquid-Phase Oxidation Reactions 240 7.5.2 Hydrogenation Reactions 241 7.5.2.1 Hydrogenation of C=C and C≡C Groups 241 7.5.2.2 The Reduction of −NO2 Group 242 7.5.2.3 The Reduction of C=O Groups 244 7.5.3 Coupling Reactions 244 7.5.3.1 Suzuki–Miyaura Coupling Reactions 244 7.5.3.2 Heck Coupling Reactions 246 7.5.3.3 Glaser Coupling Reactions 246 7.5.3.4 Knoevenagel Condensation Reaction 246 7.5.3.5 Three-Component Coupling Reaction 247 7.5.4 CO2 Cycloaddition Reactions 247 7.5.5 Tandem Reactions 248 7.6 Conclusions and Outlooks 250 References 251 8 Confinement Effects in Catalysis with Molecular Complexes Immobilized into Porous Materials 273 Maryse Gouygou, Philippe Serp, and Jérôme Durand 8.1 Introduction 273 8.2 Immobilization of Molecular Complexes into Porous Materials 279 8.2.1 Confinement of Molecular Complexes in Mesoporous Silica 279 8.2.2 Confinement of Molecular Complexes in Zeolites 281 8.2.3 Confinement of Molecular Complexes in Covalent Organic Frameworks (COF) 282 8.2.4 Confinement of Molecular Complexes in Metal–Organic Frameworks (MOFs) 283 8.2.5 Confinement of Molecular Complexes in Carbon Materials 285 8.3 Characterization of Molecular Complexes Immobilized into Porous Materials 285 8.4 Catalysis with Molecular Complexes Immobilized into Porous Materials and Evidences of Confinement Effects 287 8.4.1 Hydrogenation Reactions 288 8.4.2 Hydroformylation Reactions 289 8.4.3 Oxidation Reactions 290 8.4.4 Ethylene Oligomerization and Polymerization Reactions 291 8.4.5 Metathesis Reactions 291 8.4.6 Miscellaneous Reactions on Various Supports 293 8.4.6.1 Zeolites 293 8.4.6.2 Mesoporous Silica 293 8.4.6.3 MOFs 294 8.4.7 Asymmetric Catalysis Reactions 295 8.5 Conclusion 298 References 299 9 Size-Selective Catalysis by Metal–Organic Frameworks 315 Amarajothi Dhakshinamoorthy and Hermenegildo García 9.1 Introduction 315 9.2 Friedel–Crafts Alkylation 319 9.3 Cycloaddition Reactions 320 9.4 Oxidation of Olefins 323 9.5 Hydrogenation Reactions 325 9.6 Aldehyde Cyanosilylation 326 9.7 Knoevenagel Condensation 328 9.8 Conclusions 329 References 330 10 Selective Oxidations in Confined Environment 333 Oxana A. Kholdeeva 10.1 Introduction 333 10.2 Transition-Metal-Substituted Molecular Sieves 334 10.2.1 Ti-Substituted Zeolites and H2O2 334 10.2.2 Co-Substituted Aluminophosphates and O2 337 10.3 Mesoporous Metal–Silicates 338 10.3.1 Mesoporous Ti-Silicates in Oxidation of Hydrocarbons 339 10.3.2 Mesoporous Ti-Silicates in Oxidation of Bulky Phenols 340 10.3.3 Alkene Epoxidation over Mesoporous Nb-Silicates 342 10.4 Metal–Organic Frameworks 343 10.4.1 Selective Oxidations over Cr- and Fe-Based MOFs 343 10.4.2 Selective Oxidations with H2O2 over Zr- and Ti-Based MOFs 347 10.5 Polyoxometalates in Confined Environment 349 10.5.1 Silica-Encapsulated POM 350 10.5.2 MOF-Incorporated POM 350 10.5.3 POMs Supported on Carbon Nanotubes 352 10.6 Conclusion and Outlook 353 Acknowledgments 354 References 354 11 Tailoring the Porosity and Active Sites in Silicoaluminophosphate Zeolites and Their Catalytic Applications 363 Jacky H. Advani, Abhinav Kumar, and Rajendra Srivastava 11.1 Introduction 363 11.2 Synthesis of SAPO-n Zeolites 365 11.3 Characterization of SAPO Zeolites 370 11.4 SAPO-Based Catalysts in Organic Transformations 370 11.4.1 Acid Catalysis 370 11.4.2 Reductive Transformations 374 11.4.2.1 Selective Catalytic Reduction (SCR) 374 11.4.2.2 Hydroisomerization 379 11.4.2.3 Hydroprocessing 383 11.4.2.4 CO2 Hydrogenation 385 11.5 Conclusion 387 References 388 12 Heterogeneous Photocatalytic Degradation of Pharmaceutical Pollutants over Titania Nanoporous Architectures 397 Surya Kumar Vatti and Parasuraman Selvam 12.1 Introduction 397 12.2 Advanced Oxidation Process 399 12.2.1 Ozonation 401 12.2.2 UV Irradiation (Photolysis) 401 12.2.3 Fenton and Photo-Fenton Process 402 12.2.4 Need for Green Sustainable Heterogeneous AOP 402 12.2.5 Heterogeneous Photocatalysis 402 12.3 Semiconductor Photocatalysis Mechanism 403 12.4 Factors Affecting Photocatalytic Efficiency 404 12.5 Crystal Phases of TiO2 404 12.6 Semiconductor/Electrolyte Interface and Surface Reaction 406 12.7 Visible-Light Harvesting 409 12.8 Photogenerated Charge Separation Strategies 412 12.8.1 TiO2/Carbon Heterojunction 412 12.8.2 TiO2/SC Coupled Heterojunction 412 12.8.3 TiO2/ TiO2 Phase Junction 414 12.8.4 Metal/ TiO2 Schottky Junction 415 12.9 Ordered Mesoporous Materials 415 12.10 Ordered Mesoporous Titania 417 12.10.1 Synthesis and Characterization 418 12.10.2 Photocatalytic Degradation Studies 420 12.10.3 Complete Mineralization Studies 424 12.10.4 Spent Catalyst 425 12.11 Conclusion 427 Acknowledgment 428 References 429 13 Catalytic Dehydration of Glycerol Over Silica and Alumina-Supported Heteropoly Acid Catalysts 433 Sekar Mahendran, Shinya Hayami, and Parasuraman Selvam 13.1 Introduction 433 13.2 Value Addition of Bioglycerol 434 13.3 Interaction Between HPA and Support 437 13.4 Bulk Heteropoly Acid 438 13.5 Silica-Supported HPA 439 13.5.1 Effect of Textural Properties of Support on Product Selectivity 439 13.5.2 Effect of Catalyst Loading 440 13.5.3 Effect of Acid Sites 440 13.5.4 Effect of Type of Heteropoly Acids 443 13.6 Tuning the Acidity 444 13.7 Conclusions 446 Acknowledgments 447 References 447 14 Catalysis with Carbon Nanotubes 451 Mohammad Y. Masoomi and Lida Hashemi 14.1 Introduction 451 14.1.1 Why CNT may be Suitable to be Used as Catalyst Supports? 451 14.1.1.1 From the Point of Structural Features 452 14.1.1.2 From the Point of Electronic Properties 455 14.1.1.3 From the Point of Adsorption Properties 455 14.1.1.4 From the Point of Mechanical and Thermal Properties 456 14.2 Catalytic Performances of CNT-Supported Systems 456 14.2.1 Different Approaches for the Anchoring of Metal-Containing Species on CNT 457 14.2.2 Different Approaches for the Confining NPs Inside CNTs and Their Characterization 457 14.2.2.1 Wet Chemistry Method 458 14.2.2.2 Production of CNTs Inside Anodic Alumina 459 14.2.2.3 Arc-Discharge Synthesis 459 14.2.3 Hydrogenation Reactions 459 14.2.4 Dehydrogenation Reactions 460 14.2.5 Liquid-Phase Hydroformylation Reactions 461 14.2.6 Liquid-Phase Oxidation Reactions 462 14.2.7 Gas-Phase Reactions 464 14.2.7.1 Syngas Conversion 464 14.2.7.2 Ammonia Synthesis and Ammonia Decomposition 464 14.2.7.3 Epoxidation of Propylene in DWCNTs 465 14.2.8 Fuel Cell Electro Catalyst 465 14.2.9 Catalytic Decomposition of Hydrocarbons 466 14.2.10 CNT as Heterogeneous Catalysts 466 14.2.11 Sulfur Catalysis 467 14.3 Metal-Free Catalysts of CNTs 467 14.4 Conclusion 468 References 469 Index 473

Read more less

Book SynopsisCO2 Conversion and Utilization Comprehensive overview of current development of various catalysts in CO2 conversion and utilization through photocatalytic and electrochemical methods CO2 Conversion and Utilization systematically summarizes the development of CO2 photo- and electro-conversion and utilization, especially the reaction mechanism, engineering and technology of testing, and preparation methods and physicochemical properties of various catalytic materials. The rational design and preparation of catalysts, development of characterization technologies, and in-depth understanding of catalytic mechanisms are systematically discussed. In particular, the various parameters influencing the photocatalytic and electrochemical CO2 reduction are emphasized. The underlying challenges and perspectives for the future development of efficient catalysts for CO2 reduction to specific chemicals and fuels are discussed at the end of the text. Written by a highly qualified author with significant experience in the field, CO2 Conversion and Utilization includes information on: Measurement systems and parameters for CO2 photo/electro-conversion, CO2 photo/electro-conversion mechanism, and Cu-based and Cu-free metal materials for electrocatalytic CO2 reduction Organic-inorganic, metal organic framework, and covalent organic framework hybrid materials for CO2 photo/electro-conversion Single/dual-atom catalysts, homogeneous catalysts, and high-entropy alloys for CO2 photo/electro-conversion Semiconductor composite and carbon-based materials for photocatalytic CO2 reduction, novel routes for CO2 utilization via metal-CO2 batteries, and CO2 conversion into long-chain compounds Providing comprehensive coverage of the subject, CO2 Conversion and Utilization is of high interest for scientific researchers as well as engineers and technicians in industry, including but not limited to photochemists, electrochemists, environmental chemists, catalytic chemists, chemists in industry, and inorganic chemists.Table of ContentsPreface xiii 1 Measurement Systems and Parameters for CO 2 Photo/Electro-Conversion 1 li li, Zhenwei Zhao, Xinyi Wang, and Zhicheng Zhang 1.1 Introduction 1 1.2 The Measurement Systems for CO 2 Photo/Electro-Conversion 1 1.2.1 The Measurement Systems of Photocatalytic CO 2 Reduction 1 1.2.1.1 CO 2 Reduction System Under Liquid-Phase Reaction System 2 1.2.1.2 CO 2 Reduction System in Gas-Phase Reaction System 2 1.2.1.3 Detection of CO 2 Reduction Products 3 1.2.2 The Measurement Systems of Electrocatalytic CO 2 Reduction 3 1.2.2.1 Electrocatalytic CO 2 Reduction Reaction Test in H-Cell 3 1.2.2.2 Electrocatalytic CO 2 Reduction Reaction Test in Flow Cell 5 1.2.2.3 Electrocatalytic CO 2 Reduction Reaction Test in MEA 5 1.2.3 The Measurement Systems of Photo-Electro-Catalytic CO 2 Reduction 6 1.2.3.1 Basic Device for Photocatalytic CO 2 Reduction Experiment 6 1.2.3.2 Other Devices for Photocatalytic CO 2 Reduction 7 1.2.3.3 Detection of CO 2 Reduction Reaction Products 7 1.3 The Parameters for CO 2 Photo-Conversion 7 1.3.1 The Parameters of Photocatalytic CO 2 Reduction 7 1.3.1.1 Evaluation Parameters of Photocatalytic CO 2 Reduction Activity 8 1.3.1.2 Evaluation Parameters of Photocatalytic CO 2 Reduction Selectivity 10 1.3.1.3 Evaluation Parameters of Photocatalytic CO 2 Reduction Stability 10 1.3.2 The Parameters of Electrocatalytic CO 2 Reduction 10 1.3.3 The Parameters of Photo-Electro-Catalytic CO 2 Reduction 12 1.3.3.1 Overpotential 12 1.3.3.2 Total Photocurrent Density (j ph) and Partial Photocurrent Density (j A) 12 1.3.3.3 Faraday Efficiency (FE) 13 1.3.3.4 Solar Energy Conversion Efficiency 13 1.3.3.5 Apparent Quantum Yield (AQY) 13 1.3.3.6 Electrochemical Active Area (ECSA) 14 1.3.3.7 Electrochemical Impedance (EIS) 14 1.3.3.8 Tafel Slope (Tafel) 14 1.3.3.9 Photocatalytic Stability 14 References 15 2 CO 2 Photo/Electro-Conversion Mechanism 17 Yalin Guo, Shenghong Zhong, and Jianfeng Huang 2.1 Introduction 17 2.2 CO 2 Photo-Conversion Mechanism 18 2.3 CO 2 Electro-Conversion Mechanism 25 2.3.1 Thermodynamics of CO 2 Reduction 25 2.3.2 Pathways of Electrochemical CO 2 Reduction 26 2.3.2.1 Electrochemical CO 2 Reduction to CO 27 2.3.2.2 Electrochemical CO 2 Reduction to Formate 28 2.3.2.3 Electrochemical CO 2 Reduction to Products Beyond CO 29 2.4 Summary and Perspectives 32 References 32 3 Cu-Based Metal Materials for Electrocatalytic CO 2 Reduction 37 Junjun Li, Yongxia Shi, Man Hou, and Zhicheng Zhang 3.1 Introduction 37 3.2 Cu-Based Metal Materials for Electrocatalytic CO 2 Reduction 39 3.2.1 Cu Materials for Electrocatalytic CO 2 Reduction 39 3.2.2 Cu-Based Bimetal Materials for Electrocatalytic CO 2 Reduction 40 3.2.2.1 Cu–Au 40 3.2.2.2 Cu–Ag 42 3.2.2.3 Cu–Pd 43 3.2.2.4 Cu–Sn 44 3.2.2.5 Cu–Bi 46 3.2.2.6 Cu–In 46 3.2.2.7 Cu–Al 49 3.2.2.8 Cu–Zn 49 3.2.3 Cu-Based Trimetallic Materials for Electrocatalytic CO 2 Reduction 50 3.3 Conclusion and Outlook 50 Acknowledgment 53 References 53 4 Cu-Free Metal Materials for Electrocatalytic CO 2 Conversion 61 Zhiqi Huang and Qingfeng Hua 4.1 Introduction 61 4.2 CO-Producing Metals 62 4.2.1 Au-Based Electrocatalysts 62 4.2.2 Ag-Based Electrocatalysts 66 4.2.3 Pd-Based Electrocatalysts 68 4.2.4 Zn-Based Electrocatalysts 70 4.3 HCOOH-Producing Metals 72 4.3.1 Sn-Based Electrocatalysts 72 4.3.2 Bi-Based Electrocatalysts 76 4.3.3 In-Based Electrocatalysts 78 References 80 5 Organic–Inorganic Hybrid Materials for CO 2 Photo/Electro-Conversion 93 Peilei He 5.1 Hybrid Materials for Photocatalytic CO 2 Reduction Reaction (co 2 Rr) 93 5.1.1 Photocatalytic CO 2 RR on p-type Semiconductor/Molecule Catalysts 93 5.1.2 Photocatalytic CO 2 RR on Carbon Nitride (C 3 N 4)-supported Molecular Catalysts 95 5.1.3 Photocatalytic CO 2 RR on Polyoxometalates (POMs)-based Catalysts 97 5.2 Hybrid Materials for Electrochemical CO 2 RR 98 5.2.1 Electrochemical CO 2 RR on Carbon-supported Molecular Catalysts 98 5.2.2 Electrochemical CO 2 RR on TiO 2 -based Hybrid Materials 103 5.3 Hybrid Materials for Photoelectrochemical (PEC) CO 2 RR 104 5.4 Challenge and Opportunity 106 References 107 6 Metal–Organic Framework Materials for CO 2 Photo-/Electro-Conversion 111 Bingqing Yao, Xiaoya Cui, and Zhicheng Zhang 6.1 Introduction 111 6.2 Photocatalysis 112 6.2.1 MOFs with Photoactive Organic Ligands 113 6.2.2 MOFs with Photoactive Metal Nodes 116 6.2.3 MOF-Based Hybrid System 117 6.3 Electrocatalysis 119 6.3.1 MOFs with Active Sites at Organic Ligands 120 6.3.2 MOFs with Active Sites at Metal Nodes 121 6.3.3 MOF-Based Hybrid System 125 6.4 Photoelectrocatalysis 128 6.5 Conclusion and Outlook 129 Acknowledgment 130 References 130 7 Covalent Organic Frameworks for CO 2 Photo/Electro-Conversion 137 Ting He 7.1 Introduction 137 7.2 COFs for Photocatalytic CO 2 Reduction 138 7.2.1 Imine-Linked COFs 138 7.2.2 Ketoenamine COFs 141 7.2.3 Carbon–Carbon Double Bond-Linked COFs 145 7.2.4 Dioxin-Linked COFs 147 7.2.5 Azine-Linked and Hydrazone-Linked COFs 147 7.3 COFs for Electrocatalytic CO 2 Reduction 148 7.3.1 Porphyrin-Based COFs 148 7.3.2 Phthalocyanine-Based COFs 151 7.3.3 Other COFs 152 7.4 Challenges and Perspectives 152 References 154 8 Single/Dual-Atom Catalysts for CO 2 Photo/Electro-Conversion 157 Honghui Ou and Yao Wang 8.1 Introduction 157 8.2 Synthetic Methods of Single/Dual-Atom Catalysts 158 8.2.1 Single-Atom Photocatalysts 158 8.2.2 Dual-Atom Photocatalysts 160 8.2.3 Single-Atom Electro-Catalysts 162 8.2.4 Dual-Atom Electro-Catalysts 164 8.3 CO 2 Photo-Conversion 165 8.4 CO 2 Electro-Conversion 169 8.5 Summary and Perspective 171 References 172 9 Homogeneous Catalytic CO 2 Photo/Electro-Conversion 177 Zhenguo Guo and Houjuan Yang 9.1 Introduction 177 9.2 Homogeneous Catalytic CO 2 Electro-Conversion 177 9.2.1 The Structure Homogeneous Electrocatalytic CO 2 Reduction System 177 9.2.2 Products in Homogeneous Electrocatalytic CO 2 Reduction 178 9.2.3 Characterizing the Performance of Molecular Electrocatalysts 178 9.2.3.1 Selectivity 178 9.2.3.2 Activity 178 9.2.3.3 Overpotential (η) 179 9.2.3.4 Stability 179 9.2.4 Catalysts for Homogeneous Electrocatalytic CO 2 Reduction 179 9.3 Homogeneous Photocatalytic CO 2 Reduction 180 9.3.1 Mechanism of Homogeneous Photocatalytic CO 2 Reduction 180 9.3.2 Characterizing the Performance of Photocatalysis 181 9.3.3 Photosensitizers Used in Homogeneous Photocatalytic CO 2 Reduction 181 9.3.4 Sacrificial Electron Donors in Homogeneous Photocatalytic CO 2 Reduction 181 9.3.5 Catalysts Used in Homogeneous Photocatalytic CO 2 Reduction 182 9.4 Summary and Perspective 186 Acknowledgments 187 References 187 10 High-Entropy Alloys for CO 2 Photo/Electro-Conversion 189 Fengqi Wang, Pei Liu, and Yuchen Qin 10.1 Introduction 189 10.2 Reaction Pathways and Evaluation Parameters of Electrochemical Co 2 Rr 191 10.2.1 Reaction Pathways of CO 2 RR 191 10.2.2 Evaluation Parameters of Electrochemical CO 2 RR 192 10.2.2.1 Faraday Efficiency 192 10.2.2.2 Current Density 193 10.2.2.3 Turnover Number (TON) 194 10.2.2.4 Turnover Frequency (TOF) 194 10.2.2.5 Overpotential 194 10.3 Characteristics and Synthesis of HEAs 194 10.3.1 Characteristics of HEAs 194 10.3.1.1 The Cocktail Effect 194 10.3.1.2 The Sluggish Diffusion Effect 195 10.3.1.3 The High-entropy Effect 195 10.3.1.4 The Lattice Distortion Effect 195 10.3.1.5 The Phase Structure 196 10.3.2 Synthesis of HEAs 196 10.3.2.1 Top-Down Method 196 10.3.2.2 Down–Top Method 198 10.4 High-Entropy Alloys for CO 2 RR 199 10.5 Summary and Outlook 204 References 205 11 Semiconductor Composite Materials for Photocatalytic CO 2 Reduction 215 Shengyao Wang and Bo Jiang 11.1 Introduction 215 11.2 TiO 2 -Based Composite Photocatalysts 216 11.2.1 Mixed-Phase TiO 2 Composites 217 11.2.2 Metal-Modified TiO 2 218 11.2.3 Nonmetallic-Modified TiO 2 219 11.2.4 Organic Photosensitizer-Modified TiO 2 219 11.2.5 Composited TiO 2 Catalyst 220 11.3 Metal Oxides/Hydroxides-Based Composite Photocatalysts 222 11.3.1 Binary Metal Oxide 222 11.3.2 Ternary Metal Oxide 222 11.3.3 Oxide Perovskite 224 11.3.4 Transition Metal Hydroxide 224 11.3.5 Layered Double Hydroxides (LDHs) 226 11.4 Metal Chalcogenides/Nitrides-Based Composite Photocatalysts 226 11.4.1 Metal Chalcogenides-Based Composite Photocatalysts 227 11.4.2 Metal Nitrides-Based Composite Photocatalysts 228 11.5 c 3 N 4 -Based composite Photocatalysts 229 11.5.1 Change the Morphology and Structure 230 11.5.2 Doped Elements and Other Structural Units 231 11.5.3 Influence of Cocatalyst 232 11.5.4 Constructing Heterojunction 233 11.6 MOFs-Derived Composite Photocatalysts 233 11.6.1 Tunable Frame Structure 234 11.6.2 High Specific Surface Area Enhances CO 2 Adsorption 234 11.6.3 MOFs-Derived Composite Photocatalysts 234 11.7 Nonmetal-Based Composite Photocatalysts 236 11.7.1 Graphene Oxide-Based Composite Photocatalysts 236 11.7.2 SiC-Based Composite Photocatalysts 237 11.7.3 BN-Based Composite Photocatalysts 237 11.7.4 Black Phosphorus-Based Composite Photocatalysts 238 11.7.5 COFs-Based Composite Photocatalysts 239 11.7.6 CMPs-Based Composite Photocatalysts 240 11.8 Conclusions and Perspectives 240 References 242 12 Carbon-Based Materials for CO 2 Photo/Electro-Conversion 251 Qing Qin and Lei Dai 12.1 Advances of Carbon-Based Materials 251 12.1.1 Heteroatom-Doped Carbon 251 12.1.2 Metal-Based Carbon Composites 252 12.1.3 Carbon–Carbon Composites 253 12.1.4 Pore Construction 254 12.2 Background of CO 2 Conversion 255 12.3 EC CO 2 Conversion 256 12.3.1 Heteroatom-Doped Carbon in EC CO 2 Conversion 257 12.3.2 Metal-Modified Carbon Materials in EC CO 2 Conversion 259 12.3.3 Carbon–Carbon Composites in EC CO 2 Conversion 261 12.3.4 Pore Engineering in EC CO 2 Conversion 262 12.4 PC CO 2 Reduction 264 12.4.1 Heteroatom-Doped Carbon in PC CO 2 Conversion 265 12.4.2 Metal-Based/Carbon Nanocomposites in PC CO 2 Conversion 266 12.4.3 Carbon–Carbon Composites in PC CO 2 Conversion 268 12.5 Carbon-Based Materials in PEC CO 2 Reduction 269 12.6 Challenge and Opportunity 270 References 272 13 Metal–CO 2 Batteries: Novel Routes for CO 2 Utilization 283 Xiangyu Zhang and Le Yu 13.1 Introduction 283 13.2 The Mechanism for Metal–CO 2 Electrochemistry 284 13.2.1 Discharge/Charge Mechanisms of Li–CO 2 Batteries 284 13.2.1.1 Discharge Mechanisms of Pure Li–CO 2 Batteries 284 13.2.1.2 Charge Mechanisms of Pure Li–CO 2 Batteries 285 13.2.2 Discharge/Charge Mechanisms of Zn–CO 2 Batteries 286 13.3 The Electrocatalysts for Metal–CO 2 Batteries 286 13.3.1 Carbonaceous Materials 286 13.3.2 Noble Metal-based Materials and Transition Metal-based Materials 287 13.4 The Electrolytes for Metal–CO 2 Batteries 290 13.4.1 Nonaqueous Aprotic Liquid Electrolytes for Pure Li–CO 2 Electrochemistry 290 13.4.2 Solid-State Electrolytes for Pure Li–CO 2 Electrochemistry 290 13.5 Conclusion and Outlook 292 References 293 14 CO 2 Conversion into Long-Chain Compounds 297 Tingting Zheng and Chuan Xia 14.1 Introduction 297 14.2 Photobiochemical Synthesis (PBS) 299 14.2.1 Principles in Designing the PBS System 299 14.2.2 Multicarbon Compounds Produced from PBS 301 14.2.3 Challenges and Prospects for PBS 304 14.3 Microbial Electrosynthesis (MES) 306 14.3.1 Extracellular Electron Transfer (EET) 306 14.3.2 Approaches to Optimize MES 309 14.3.2.1 Metabolic Pathways 309 14.3.2.2 Metabolic Engineering 309 14.3.2.3 Culture 311 14.3.2.4 Biocathode 312 14.3.3 Multicarbon Products Derived from MES 313 14.3.4 The Status Quo and Challenges of MES 316 14.4 Decoupling Biotic and Abiotic Processes 318 14.5 Conclusions and Perspectives 322 References 324 15 Conclusions and Perspectives 335 Haiqing Wang 15.1 New CO 2 RR Catalyst 335 15.2 New CO 2 RR Mechanism 336 15.3 Industrial CO 2 RR Perspectives 337 Index 339

Read more less

a huge range and FREE tracked UK delivery on ALL orders.

Read more less

Book SynopsisFrom the contents: Robert H Crabtree: Introduction and History. - Montserrat Diéguez, Oscar Pàmies and Carmen Claver: Iridium-catalysed hydrogenation using phosphorous ligands. - David H. Woodmansee and Andreas Pfaltz: Iridium Catalyzed Asymmetric Hydrogenation of Olefins with Chiral N,P and C,N Ligands. - Ourida Saidi and Jonathan M J Williams: Iridium-catalyzed Hydrogen Transfer Reactions. - John F. Bower and Michael J. Krische: Formation of C-C Bonds via Iridium Catalyzed Hydrogenation and Transfer Hydrogenation. - Jongwook Choi, Alan S. Goldman: Ir-Catalyzed Functionalization of CH Bonds. - Mark P. Pouy and John F. Hartwig: Iridium-Catalyzed Allylic Substitution. - Daniel Carmona and Luis A. Oro: Iridium-catalyzed 1.3-dipolar cycloadditions.Trade ReviewFrom the reviews:“Chapters cover a range of types of reactions … that are of strong interest in organic synthesis, and provide extensive up-to-date coverage of both the scope and limitations of the catalysts. … Overall, ‘Iridium Catalysis’ will serve as a useful up-to-date resource for both those entering the field and those experienced chemists who may not be aware of the advances that have been made. … Readers will be stimulated to find new applications for iridium in catalysis after they examine this book.” (William D. Jones, Platinum Metals Review, Vol. 56 (1), 2012)Table of ContentsRobert H Crabtree: Introduction and History.- Montserrat Diéguez, Oscar Pàmies and Carmen Claver: Iridium-catalysed hydrogenation using phosphorous ligands.- David H. Woodmansee and Andreas Pfaltz: Iridium Catalyzed Asymmetric Hydrogenation of Olefins with Chiral N,P and C,N Ligands.- Ourida Saidi and Jonathan M J Williams: Iridium-catalyzed Hydrogen Transfer Reactions.- John F. Bower and Michael J. Krische: Formation of C-C Bonds via Iridium Catalyzed Hydrogenation and Transfer Hydrogenation.- Jongwook Choi, Alan S. Goldman: Ir-Catalyzed Functionalization of CH Bonds.- Mark P. Pouy and John F. Hartwig: Iridium-Catalyzed Allylic Substitution.- Luis A. Oro and Daniel Carmona: Iridium-catalysed 1.3-dipolar cycloadditions.

Read more less

Book SynopsisThe importance of solid base catalysts has come to be recognized for their environmentally benign qualities, and much significant progress has been made over the past two decades in catalytic materials and solid base-catalyzed reactions. The book is focused on the solid base. Because of the advantages over liquid bases, the use of solid base catalysts in organic synthesis is expanding. Solid bases are easier to dispose than liquid bases, separation and recovery of products, catalysts and solvents are less difficult, and they are non-corrosive. Furthermore, base-catalyzed reactions can be performed without using solvents and even in the gas phase, opening up more possibilities for discovering novel reaction systems. Using numerous examples, the present volume describes the remarkable role solid base catalysis can play, given the ever increasing worldwide importance of "green" chemistry. The reader will obtain an overall view of solid base catalysis and gain insight into the versatility of the reactions to which solid base catalysts can be utilized. The concept and significance of solid base catalysis are discussed, followed by descriptions of various methods for the characterization of solid bases, including spectroscopic methods and test reactions. The preparation and properties of base materials are presented in detail, with the two final chapters devoted to surveying the variety of reactions catalyzed by solid bases.Table of ContentsIntroduction.- Characterization of Solid Base Catalysts.- Preparation and Catalytic Properties of Solid Base Catalysts - Metal Oxides.- Preparation and Catalytic Properties of Solid Base Catalysts - Specific Materials for Solid Bases.- Reactions Catalyzed by Solid Bases.- Solid Base Catalysts for Specific Subjects.

Read more less

Book SynopsisVon kuriosen Phänomenen bis zur wissenschaftlichen Deutung und industriellen Anwendung der Katalyse.- Begriffe und Definitionen in der heterogenen Katalyse.- Katalysatorklassifizierung, -vorauswahl und -präparation.- Grundlagen der heterogenen Katalyse.- Methoden zur Bestimmung der Katalysatorparameter.- Methoden zur Bestimmung der Katalysatorleistung.- Kinetik heterogen katalysierter Reaktionen und Reaktionsmechanismen.- Theoretische Konzepte in der heterogenen Kalatyse.- Katalyse an Metallen und Metalloxiden in Hydrierreaktionen.- Katalyse an Metallen und Metalloxiden in Oxidationsreaktionen.- Säure-Base-Katalyse.- Bifunktionelle Katalyse.- Elektro-, Photo- und Biokatalyse.

Read more less

Book Synopsis

Read more less

Book SynopsisThis book is indexed in Chemical Abstracts Service Green Chemistry has evolved in response to several environmental issues in the second half of the last century, mostly due to the almost freely expanding chemical, petrochemical, and pharmaceutical industries. During the past two decades Green Chemistry grew rapidly and we can now consider this area as a mature and powerful field. Tremendous development has taken place in many important areas including renewable energy and resources, reaction environments, catalysis, synthesis, chemical biology, green polymers, and facile recycling. The combination of Green Chemistry with engineering, biology, toxicology, and physics will lead to novel interdisciplinary systems, which can now lift Green Chemistry to the next, advanced level.The editors have assembled authors among the best specialists of this growing area of research. This collection of reviews and perspectives provides an exciting vision of the more recent developments in Green Chemistry. The contents of this book illustrate the breath of the field and its role to address environmental issues. This volume will serve as a book of reference showing a panoramic view of the field and a preview of its future direction, as well as a book of inspiration for those aiming to further advance its frontiers. This volume emphasizes on the most recent developments in green catalysis, bio-sourced polymers and the study of continental organic matter for a better understanding of the carbon geochemical cycle.Table of ContentsGreen and Sustainable Chemistry (István T Horváth); Pd-Catalyzed Sequential Reactions Involving C–H Bond Activation: A Green and Sustainable Tool for Natural and Industrial Product Synthesis (Elena Motti, Nicola Della Ca', Giovanni Maestri and Max Malacria); Photoredox Catalysis, an Opportunity for Sustainable Radical Chemistry (Christophe Lévêque, Etienne Levernier, Vincent Corcé, Louis Fensterbank, Max Malacria and Cyril Ollivier); Brønsted Acid as Efficient Catalyst for Synthesis of Biologically Active Natural Products (Guillaume Levitre and Géraldine Masson); Bio-Sourced Polymers: Recent Advances (Henri Cramail, Boris Bizet, Océane Lamarzelle, Pierre-Luc Durand, Geoffrey Hibert and Etienne Grau); Insight into Continental Organic Matter: A Chemist View (Katell Quénéa, Sylvie Derenne and Marc F Benedetti);

Read more less

Book SynopsisThis book is indexed in Chemical Abstracts Service 'The present book displays the continuing broad interest in the area of Supramolecular Catalysis. It provides an excellent update to previous contributions in the field and will be highly beneficial reading for all students and researchers interested in the challenges faced in this domain of Supramolecular Chemistry.'Jean-Marie LehnNobel Laureate The construction of catalysts by supramolecular forces has recently become a powerful tool and the role of noncovalent interactions can assist in designing new tools for the construction of effective and selective catalytic systems. It is unquestionably, vastly important to understand how different noncovalent interactions can be controlled or manipulated under appropriate reaction conditions. Supramolecular catalysts have had a tremendous impact on the syntheses of both chemical commodities and fine chemicals over the last 50 years, leading to the discovery of new reactions that were previously deemed impossible. This means that supramolecular chemistry plays a predominant role in accelerating or understanding chemical reactions.This book which addresses the above points is written by some of the leading contributors in this field and is intended for graduate students, researchers and academics working in supramolecular chemistry, organic chemistry, inorganic chemistry, and physical chemistry as well as researchers with an interest in the area of catalysis. The authors give examples illustrating the growth of the field, especially with special emphasis on new results published over the last decade. They also provide an explanation of fundamentals and topical research.Table of ContentsGeneral Strategies in Modulating Reactivity within Well-Defined Supramolecular Nanospaces (Xiao-Yu Hu, Kaiya Wang, Jacobs H Jordan, Chengyong Su and Leyong Wang); Supramolecular Catalysts Based on Crown Ethers and Polyethers (Zibin Zhang, Yuan-Guang Shao, Shijun Li, Juli Jiang and Leyong Wang); Cyclodextrins Based Supramolecular Catalysis (Frédéric Hapiot and Eric Monflier); Systems Based on Calixarenes for the Creation of Catalysts (Zheng-Yi Li, Tangxin Xiao, Ke Yang, Yuan Chen and Leyong Wang); Cucurbit[n]urils Based Supramolecular Catalysis (Fengbo Liu and Simin Liu); Functional Interlocked Molecules: Applications of Rotaxanes, Catenanes and Molecular Knots in Supramolecular Catalysis (Jochen Niemeyer); Porphyrin Metal–Organic Frameworks in Heterogeneous Supramolecular Catalysis (Li Zhang, Jiewei Liu and Cheng-Yong Su); Supramolecular Coordination Cages as Nano Reactors (Mei Pan, Xuezhao Li, Yu-Lin Lu, Cheng He and Cheng-Yong Su); Assembly of Organometallics: Application in Catalysis and Molecular Recognition (Qingshu Zheng and Tao Tu); Supramolecular Chiral Photochemistry (Wanhua Wu and Cheng Yang); Artificial Photosynthesis by MOFs: Water Splitting and CO₂ Conversion (Yuanxing Fang and Xinchen Wang); Water Splitting in Natural and Artificial Photosynthesis (Wangyin Wang and Can Li); Artificial Photosynthesis at Lipid Bilayers (Andrea Pannwitz and Sylvestre Bonnet); Bio-Inspired Supramolecular Catalysis (Harsh Vardhan and Shengqian Ma);

Read more less

Book SynopsisThis book provides an overview of plasticizers, from the latest global research developments to the laws and regulations applied to their use. In addition the book details the author's recently developed methodology for a catalytic hydrogenation of phthalate plasticizers. It presents insights into the development of the catalytic phthalate hydrogenation from the reaction mechanism and catalyst characterization to pilot tests and its industrialization. Given its scope, the book will appeal to a broad readership, particularly professionals at universities and scientific research institutes, as well as practitioners in industry.Table of ContentsIntroduction.- Plasticizer Laws and Evolution in Different Regions.- Current Status of Plasticizer Research.- Inventions and Patents in Different Regions.- Catalytic Ring Hydrogenation of Phthalate Plasticizers.- Pilot Demonstrations and Industrialization.

Read more less

Book SynopsisThis book introduces readers to the preparation of metal nanocrystals and its applications. In this book, an important point highlighted is how to design noble metal nanocrystals at the atomic scale for energy conversion and storage. It also focuses on the controllable synthesis of water splitting electrode materials including anodic oxygen evolution reaction (OER) and cathode hydrogen evolution reaction (HER) at the atomic level by defect engineering and synergistic effect. In addition, in-situ technologies and theoretical calculations are utilized to reveal the catalytic mechanisms of catalysts under realistic operating condition. The findings presented not only enrich research in the nano-field, but also support the promotion of national and international cooperation.Table of ContentsOverviews of noble metal nanocrystals.- Advanced synthesis methods of noble metal nanocrystals.- Characterization methods for noble metal nanocrystals.- Applications of noble metal nanocrystals.- Electrocatalytic water splitting technology.- Conclusions.

Read more less

Book SynopsisThis book describes the development of two kinds of continuous-flow transformation using heterogeneous catalysts, and explains how they can be applied in the multistep synthesis of active pharmaceutical ingredients. It demonstrates and proves that fine chemicals can be synthesized under continuous-flow conditions using heterogeneous catalysis alone. Importantly, the book also proposes a general concept and strategy for achieving multistep flow synthesis and developing heterogeneous catalysts, and shows that commercially available anion exchange resin can be used as a water-tolerant strong base catalyst for various types of continuous-flow aldol-type reaction. Reviewing the state of the art in heterogeneous catalysis in flow chemistry – a “hot topic” and rapidly developing area of organic synthesis – the book will provide readers with a deeper understanding of fine chemical flow synthesis and its future prospects. Table of Contents1. Introduction and Strategy.- 2. Synthesis of Nitro-containing Compounds through Multistep Continuous-flow with Heterogeneous Catalysts.- 3. Polysilane-Supported Pd Catalysts for Continuous-flow Hydrogenations.- 4. Anion Exchange Resins as Catalysts for Direct Aldol-type Reactions of Ketones, Esters and Nitriles under Continuous-flow.- 5. Multistep Continuous-flow Synthesis of APIs Based on Aldol-hydrogenation Strategy.- 6. Summary.- 7. Experimental Section.

Read more less

Book SynopsisThe Proceedings of the 24th International Solvay Conference on Chemistry comprise contributed short personal statements and transcripts of in-depth discussions on 'Catalysis in Chemistry and Biology' from a by-invitation-only select group of 48 eminent scientists, including four Nobel Laureates, from all parts of the world. The theme of the conference was presented in six sessions, along which the Proceedings are organized. The first session on 'Homogeneous Catalysis,' chaired by Professor Robert Grubbs, is devoted to basic research on catalysis in homogeneous solutions and applications thereof. 'Heterogeneous Catalysis and Characterization of Catalyst Surfaces,' chaired by Professor Gerhard Ertl, includes extensive references to industrial applications of catalysis on solid supports, and discussions on the experimental techniques used in this field. 'Catalysis by Microporous Materials,' chaired by Professor Mark E. Davis, is devoted to a detailed characterization of this particular class of solid support catalysts, with special emphasis on model analysis of the processes catalyzed by these materials. 'Catalysis under Extreme Conditions: Studies at High Pressure and High Temperatures — Relations with Processes in Nature,' chaired by Professor Henk N W Lekkerkerker, broadens the scope of the two preceding sessions with exciting illustrations. The sessions on 'Catalysis by Protein Enzymes,' chaired by Prof. JoAnne Stubbe, and 'Catalysis by Ribozymes in Molecular Machines,' chaired by Prof. David Lilley, present at the same time an exciting extension of and a contrast to the initial four sessions. The combination of the six sessions provides an impressive overview, giving innovative insights into relationships between catalysis in chemical processes and in biological systems, and a unique outlook to anticipated developments in the coming years and the more distant future.

Read more less