Catalysis Books

Book SynopsisVolume 5 in the Catalysts for Fine Chemical Synthesis series describes new procedures for the regio- and stereo-controlled transformations of compounds involving oxidation or reduction reactions. It describes a wide range of catalysts, including organometallic systems, biocatalysts and biomimetics.Table of ContentsCHAPTER 1: Industrial Catalysts for Regio- or Stereo- selective Oxidations and Reductions. A Review of Key Technologies and Targets. J. Whittall CHAPTER 2: Asymmetric Hydrogenation of Alkenes, Enones, Ene-esters and Ene-Acids 2.1: (S)-2,2'- Bis{[di(4-methoxyphenyl)phosphinyl]oxy}-5,5',6,6',7,7',8,8'-octahydro-1,1'-binaphthyl as a Ligand for Rhodium-Catalysed Asymmetric Hydrogenation I. Gergely, C. Hegeds and J. Bakos. 2.2: Synthesis and Application of Phosphinite Oxazoline Iridium Complexes for the Asymmetric Hydrogenation of Alkenes F. Menges and A. Pfaltz. 2.3: Synthesis and Application of Heterocyclic Phosphine Oxazoline (HetPHOX) Iridium Complexes for the Asymmetric Hydrogenation of Alkenes F. Menges and P.G. Cozzi. 2.4: (R)-2,2',6,6'- Tetramethoxy-bis[di(3,5-dimethylphenyl)phosphino]-3,3'-bipyridine [(R)-Xyl-P-Phos] as a Ligand for Rhodium-Catalysed Asymmetric Hydrogenation of a-Dehydroamino Acids J. Wu and A.S.C. Chan. 2.5: (R,R)-2,3-Bis(tert-butylmethylphosphine)quinoxaline (Quinox P*) as a Ligand for Rhodium-Catalysed Asymmetric Hydrogenation of Prochiral Amino Acid and Amine Derivatives T. Imamoto and A. Koide. 2.6: Rhodium-Catalysed Asymmetric Hydrogenation of Indoles R. Kuwano and M. Sawamura. CHAPTER 3: Asymmetric Reduction of Ketones 3.1: (R,R)-Bis(diphenylphosphino)-1,3-diphenylpropane as a Versatile Ligand for Enantioselective Hydrogenations N. Dubrovina and A. Borner. 3.2: Synthesis of Both Enantiomers of 1-Phenylethanol by Reduction of Acetophenone with Geotrichum candidum IFO 5767 K. Nakamura, M. Fujii and Y. Ida. 3.3: Titanocene-Catalysed Reduction of Ketones in the Presence of Water. A Convenient Procedure for the Synthesis of Alcohols by Free-Radical Chemistry A. Rosales, J.M. Cuerva and J.E. Oltra. 3.4: Xyl-TetraPHEMP: A Highly Efficient Biaryl Ligand in the [Diphosphine RuCl2-diamine]-Catalysed Hydrogenation of Simple Aromatic Ketones P.H. Moran, J.P. Henschke, A. Zanotti-Gerosa and I C. Lennon. 3.5: N-Arenesulfonyl- and N-Alkylsulfamoyl-1,2-diphenylethylenediamine Ligands for Ruthenium-Catalysed Asymmetric Transfer Hydrogenation of Activated Ketones M.S. Stephan and B. Mohar. 3.6: The Synthesis and Application of BrXUPHOS: A Novel Monodentate Phosphorus Ligand for the Asymmetric Hydrogenation of Ketones M. Wills, Y. Xu, G. Docherty and G. Woodward. 3.7: In Situ Formation of Ligand and Catalyst: Application in Ruthenium-Catalysed Enantioselective Reduction of Ketones J. Wettergren and H. Adolfsson. 3.8: SYNPHOS and DIFLUORPHOS as Ligands for Ruthenium-Catalysed Hydrogenation of Alkenes and Ketones S. Jeulin, V. Ratovelomanana-Vidal and J-P. Genet. 3.9: An Arene Ruthenium Complex with Polymerizable Side-chains for the Synthesis of Immobilised Catalysts E. Burri, S.B. Wendicke, K. Severin. 3.10: Selective Reduction of Carbonyl Group in beta, gamma- Unsaturated alpha- Ketoesters by Transfer Hydrogenation with Ru-(para-cymene) (TsDPEN) M. Guo, D. Li, Y. Sun and Z. Zhang. 3.11: Preparation of Polymer-Supported Ru-TsDPEN Catalysts and their Use for the Enantioselective Synthesis of (S)-Fluoxetine L. Chai, Y. Li and Q. Wang. 3.12: Polymer-Supported Chiral Sulfonamide-Catalysed Reduction of B-Keto Nitrile: a Practical Synthesis of (R)-Fluoxetine G.Wang and G. Zhao. CHAPTER 4: Imine Reduction and Reductive Amination 4.1: Metal-Free Reduction of Imines: Enantioselective Bronsted Acid-Catalysed Transfer Hydrogenation using Chiral BINOL-Phosphates as Catalysts M. Rueping, E. Sugiono, C. Azap and T. Theissmann. 4.2: Metal-Free Bronsted Acid-Catalysed Transfer Hydrogenation: Enantioselective Synthesis of Tetrahydroquinolines M. Rueping , T. Theissmann and A. P. Antonchick. 4.3: A Highly Stereoselective Synthesis of 3a-Amino-23,24-bisnor-5a-cholane via Reductive Amination S. N. Khan, N.J. Cho and H-S. Kim. CHAPTER 5: Oxidation of Primary and Secondary Alcohols 5.1: Copper (II)-Catalysed Oxidation of Primary Alcohols to Aldehydes with Atmospheric Oxygen S. Jammi and T. Punniyamurthy. 5.2: Solvent-free Dehydrogenation of Secondary Alcohols in the Absence of Hydrogen Abstractors using Robinson's Catalyst G.B.W.L. Ligthart, R.H. Meijer, J. v. Buijtenen, J. Meuldijk, J.A.J.M. Vekemans and L. A. Hulshof. 5.3: 2-Iodoxybenzoic Acid (IBX)/ n-Bu4NBr/ CH2Cl2-H2O: a Mild System for the Selective Oxidation of Secondary Alcohols K. Kittigowittana, M. Pohmakotr, V. Reutrakul and C. Kuhakarn. CHAPTER 6: Hydroxylation, Epoxidation and Related Reactions 6.1: Proline-Catalysed a-Aminoxylation of Aldehydes and Ketones Y. Hayashi and M. Shoji. 6.2: Ru/ Silica* Cat* TEMPO(c)-Mediated Oxidation of Alkenes to a-Hydroxyacids R. Ciriminna and M. Pagliaro. 6.3: Catalytic Enantioselective Epoxidation of trans-Disubstituted and Trisubstituted Alkenes with Arabinose-Derived Ulose T.K. M. Shing, G.Y.C. Leung and T. Luk. 6.4: VO(acac)2/ TBHP-Catalysed Epoxidation of 2-(2-Alkenyl)phenols. Highly Regio- and Diastereo-selective Oxidative Cyclisation to 2,3-Dihydrobenzofuranols and 3-Chromanols A. Lattanzi and A. Scettri. 6.5: An Oxalolidinone Ketone Catalyst for the Asymmetric Epoxidation of cis-Olefins D. Goeddel and Y. Shi. 6.6: a-Fluorotropinone Immobilised on Silica: a New Stereoselective Heterogeneous Catalyst for Epoxidation of Alkenes with Oxone G. Sartori, A. Armstrong, R. Maggi, A. Mazzacani, R. Sartorio, F. Bigi and B. Dominguez-Fernandez. 6.7: Asymmetric Epoxidation Catalysed by Novel Azacrown Ether-Type Chiral Quaternary Ammonium Salts under Phase-Transfer Catalytic Conditions K. Hori, K. Tani, and Y. Tohda. 6.8: Enantioselective Epoxidation of Olefins using Phase-Transfer Conditions and [6-N-((S)-1,2,2-Trimethylpropyl)-5H-dibenz[c,e]azepinium] [rac-TRISPHAT] Salt as Catalyst J. Vachon, C. Perollier, A. Martinez and J. Lacour. 6.9: Catalytic Asymmetric Epoxidation of a,Unsaturated Esters Promoted by a Yttrium-Biphenyldiol Complex M. Shibasaki, H. Kakei and S. Matsunaga.. 6.10: Catalytic Enantioselective Epoxidation of a, -Enones with a BINOL-Zinc Complex A. Minatti and K.H. Dotz 6.11: Asymmetric Epoxidation of Phenyl 2-(3'-Pyridylvinyl) Sulfone using Polyleucine/ Hydrogen Peroxide Gel M. Pitts and J. Whittall. CHAPTER 7: Oxidation of Ketones to Lactones or Enones 7.1: Synthesis of 2-(Phosphinophenyl)pyridine Ligand and its Application to Palladium-Catalysed Asymmetric Baeyer- Villiger Oxidation of Prochiral Cyclobutanones K. Ito and T. Katsuki. 7.2: (D)-Codeinone from (D)-Dihydrocodeinone via the Use of Modified o-Iodoxybenzoic Acid (IBX) P. Mather and J. Whittall. CHAPTER 8: Oxidative C-C Coupling 8.1: Enantioselective Oxidative Coupling of 2-Naphthols Catalysed by a Novel Chiral Vanadium Complex N-S. Xie, Q-Z. Liu, Z-B. Luo, L-Z. Gong, A-Q. Mi and Y-Z. Jiang. 8.2: Catalytic Oxidative Cross-Coupling Reaction of 2-Naphthol Derivatives S. Habaue and T. Temma. 8.3: Oxidative Coupling of Benzene with a,-Unsaturated Aldehydes by Pd(OAc)2/ HPMoV/ O2 System T. Yamada, S. Sakaguchi and Y. Ishii. CHAPTER 9: Oxidation of Sulfides and Sulfoxides 9.1: The First Example of Direct Oxidation of Sulfides to Sulfones by an Osmate- Molecular Oxygen System B.M. Choudary, C. Reddy, V. Reddy, B.V. Prakash, M.L. Kantam and B. Sreedhar. 9.2: Selective Oxidation of Sulfides to Sulfoxides and Sulfones using Hydrogen Peroxide (H2O2) in the Presence of Zirconium Tetrachloride K. Bahrami. 9.3: WO3-30% H2O2-Cinchona Alkaloids: a New Heterogeneous Catalytic System for Asymmetric Oxidation and Kinetic Resolution of Racemic Sulfoxides V. V. Thakur and A. Sudalai. 9.4: Benzyl-4,6-isopropylidene-a-(D)-glucopyranoside, 2-deoxy-2-[[(2-hydroxy-3,5-di-tert-butylphenyl)methylene]amine] as a Ligand for Vanadium-Catalysed Asymmetric Oxidation of Sulfides R. Del Litto, G. Roviello and F. Ruffo. 9.5: Asymmetric Sulfoxidation of Aryl Methyl Sulfides with H2O2 in Water A. Scarso and G. Strukul

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Book SynopsisBringing together current advances and in-depth reviews of bio-based industrial products and agricultural biotechnology, Biocatalysis and Molecular Engineering examines the recent energy and food crises and points out the importance of using bio-based products from renewable resources and agricultural biotechnology.Table of ContentsPreface. Contributors. Section I. Improvement of Agronomic and Microbial Traits. 1.Insights into the Structure and Function of Acyl-CoA: Diacylglycerol Acyltransferase (Rodrigo M.P. Siloto, Qin Liu, Randall J. Weselake, Xiaohua He, and Thomas McKeon). 2. Improving Enzyme Character by Molecular Breeding: Preparation of Chimeric Genes (Kiyoshi Hayashi, Motomitsu Kitaoka, and Mamoru Nishimoto). 3. Production and Accumulation of Unusual Fatty Acids in Plant Tissues (D. Hildebrand, J.R, Thoguru, S. Rao, R Li, and T. Hatanaka). 4. Preparation of Oleaginous Yeast by Genetic Modification and Its Potential Applications (Yasushi Kamisaka). 5. Improving Value of Oil Palm Using Genetic Engineering (Ghulam Kadir Admad Parveez, Abrizah Othman, Umi Salamah Ramli, Ravigadevi Sambanthamurthi, Abdul Masani Mat Yunus, Ahmad Tarmizi Hashim, Ahmad Kushairi Din, and Mohd Basri Wahid). 6. Potential in Using Arabidopsis Acyl-Coenzyme-A-Binding Proteins in Engineering Stress-Tolerant Plants (Mee-Len Chye, Shi Xiao, Qin-Fang Chen, and Wei Gao). 7. Modification of Lipid Composition by Genetic Engineering in Oleaginous Marine Microorganism, Thraustochytrid (Tsunehiro Aki, Hiroaki Iwasaka, Hirofumi Adachi, Maya Nanko, Hiroko Kawasaki, Seiji Kawamoto, Toshihide Kakizono, and Kazuhisa Ono). 8. Integrated Approaches to Manage Tomato Yellow Leaf Curl Viruses (R. C, de la Peña, P. Kadirvel, S. Venkatesan, L. Kenyon, and J. Hughes). 9. Carbohydrate Acquisition During Legume Seed Development (Jocelyn A. Ozga, Dennis M. Reinecke, and Pankaj K. Bhowmik). 10. Biotechnology Enhancement of Phytosterol Biosynthesis in Seed Oils (Qilin Chen and Jitao Zou). Section II: Functional Foods and Biofuels. 11. Dietary Phosphatidylinositol in Metabolic Syndrome (Bungo Shirouchi, Koji Nagao, and Teruyoshi Yanagita). 12. Biotechnological Enrichment of Cereals with Polyunsaturated Fatty Acids (Milan Certik, Zuzana Adamechova, and Lucia Slavikova). 13. Lipophilic Ginsenoside Derivatives Production (Jiang-Ning Hu and Ki-Teak Lee). 14. Brown Seaweed Lipids as Possible Source for Nutraceuticals and Functonal Foods (M. Airanthi K. Widjaja-Adhi, Takayuki Tsukui, Masashi Hosokawa, and Kazuo Miysahita). 15. Processes for Production of Biodiesel Fuel (Yomi Watanabe and Yuji Shimada). 16. Noncatalytic Alcoholysis Process for Production of Biodiesel Fuel: Its Potential in Japan and Southeast Asia (Hiroshi Nabetani, Shoji Hagiwara, and Mitsutoshi Nakajima). 17. Use of Coniochaeta ligniaria to Detoxify Fermentation Inhibitors Present in Cellulosic Sugar Streams (Nancy N. Nichols, Bruce S. Dien, Maria J. López, and Joaquín Moreno). 18. Omics Applications to Biofuel Research (Tzi-Yuan Wang, Hsin-Liang Chen, Wen-Hsiung Li, Huang-Mo Sung, and Ming-Che Shih). Section III: Renewable Bioproducts. 19. Biotechnological Uses of Phospholipids (Jeong Jun Han, Jae Kwang Song, Joon Shick Rhee, and Suk Hoo Yoon). 20. Application of Partition Chromatographic Theory on the Routine Analysis of Lipid Molecular Species (Koretaro Takahashi and Tsugihiko Hirano). 21. Dehydrogenase-Catalyzed Synthesis of Chiral Intermediates for Drugs (Ramesh N. Patel). 22. Engineering of Bacterial Cycochrome P450 Monooxygenase as Biocatalysts for Chemical Synthesis and Environmental Bioremedication (Jun Ogawa, Quin-Shan Li, Sakayu Shimizu, Vlada Urlancher, and Rolf D. Schmid). 23. Glycosynthases from Inverting Hydrolases (Motomitsu Kitaoka). 24. Molecular Species of Diacylglycerols and Triacylglycerols Containing Dihydroxy Fatty Acids in Castor Oil (Jiann-Tsyh Lin). 25. Biocatalytic Production of Lactobionic Acid (Hirofumi Nakano, Takaaki Kiryu, Taro Kiso, and Hiromi Murakami). 26. Recent Advances in Aldolase-Catalyzed Synthesis of Unnatural Sugars and Iminocyclitols (Masakazu Sugiyama, Zhangyong Hong, William A. Greenberg, and Chi-Huey Wong). 27, Production of Value-Added Products by Lactic Acid Bacteria (Siqing Liu, Kenneth M. Bischoff, Yebo Li, Fengjie Cui, Hassan Azaizeh, and Ahmed Tafesh). 28. Enzymatic Synthesis of Glycosides Using Alpha-Amylase Family Enzymes (Kazuhisa Sugimoto, Takahisa Nishimura, Koji Nomura, Hiromi Nishiura, and Takashi Kuriki). 29. Biological Synthesis of Gold and Silver Nanoparticles Using Plant Leaf Extracts and Antimicrobial Application (Beom Soo Kim and Jae Yong Song). 30. Potential Approach of Microbial Conversion to Develop New Antifungal Products of Omega-3 Fatty Acids (Vivek K. Bajpai, Sun-Chul Kang, Hak-Ryul Kim, and Ching T. Hou). Index.

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Book SynopsisHomogeneous catalysis by soluble metal complexes has gained considerable attention due to its unique applications and features such as high activity and selectivity. Catalysis of this type has demonstrated impressive achievements in synthetic organic chemistry and commercial chemical technology. Homogeneous Catalysis with Metal Complexes: Kinetic Aspects and Mechanisms presents a comprehensive summary of the results obtained over the last sixty years in the field of the kinetics and mechanisms of organic and inorganic reactions catalyzed with metal complexes. Topics covered include: Specific features of catalytic reaction kinetics in the presence of various mono- and polynuclear metal complexes and nanoclusters Multi-route mechanisms and the methods of their identification, as well as approaches to the kinetics of polyfunctional catalytic systems Principles and features of the dynamic behavior of nonlinear kinetic models The potTable of ContentsNotations and Abbreviations xi Preface to English Edition xvii Preface xix Acknowledgments xxi About the Author xxiii Introduction 1 1 State-of-the-Art in the Theory of Kinetics of Complex Reactions 21 1.1 Main concepts of the Horiuti–Temkin theory of steady-state reactions 21 1.1.1 Reaction mechanism: Stoichiometry and routes 22 1.1.2 Kinetics: Reaction rates with respect to substances and over routes 32 1.1.3 Kinetic polynomial 42 1.1.4 Determining the number of independent parameters in a kinetic model. The problem of identifiability of parameters 44 1.2 Quasi-steady-state and quasi-equilibrium approximations in chemical kinetics 47 1.2.1 Theoretical criteria of quasi-steady-state intermediate concentrations and quasi-equilibrium steps 49 1.2.2 Experimental criteria of applicability of quasi-steady-state approximation in various systems 60 1.3 Methods of graph theory in chemical kinetics and in theory of complex reaction mechanisms 62 1.3.1 Linear mechanisms 62 1.3.2 Nonlinear mechanisms 71 1.3.3 Other fields of application of kinetic and bipartite graphs in chemical kinetics and in theory of complex reaction mechanisms 76 1.4 Elementary steps – Selection rules 79 1.4.1 Main postulates, laws, and principles 79 1.4.2 Energy selection rules for elementary steps 88 1.4.3 Quantum-chemical selection rules for elementary steps 92 1.4.4 Topological selection rules for elementary steps 108 References 113 2 Complexity Functions of Catalysts and Reactants in Reactions Involving Metal Complexes 121 2.1 Mononuclear metal complexes 122 2.1.1 Complexity functions: variants I and II 134 2.1.2 Complexity functions: variants III and IV 149 2.1.3 General problems and recommendations 165 2.2 Polynuclear complexes in homogeneous catalytic and noncatalytic reactions 167 2.2.1 Systems with formation of associates 168 2.2.2 Systems with mononuclear and polynuclear complexes of various types 182 2.3 Catalysis with polynuclear copper(I) halide complexes in superconcentrated solutions 193 2.3.1 Copper(I) chloride complexes in solution and in crystalline state 194 2.3.2 Kinetics of catalytic reactions of alkynes in concentrated NH4Cl–CuCl aqueous solutions at constant complexity functions FCu and FCl 203 2.3.3 Determination of compositions of catalytically active copper(I) complexes in various reactions 210 2.3.4 Studying π and σ complexes of copper(I) with alkynes in crystalline state and in solution 216 2.3.5 Mechanisms of acetylene dimerization and hydrocyanation reactions. Crystallochemical aspects 227 References 231 3 Multi-Route Mechanisms in Reactions Involving Metal Complexes 239 3.1 Factors accounting for the appearance and kinetic features of multi-route mechanisms 239 3.2 Analysis of multi-route reaction kinetics 246 3.3 Conjugation nodes and artificial multi-route character 271 3.4 Conjugate processes 304 3.4.1 Classical approach 305 3.4.2 Kinetic and thermodynamic conjugation in consecutive reactions 309 3.4.3 Conjugation in chain reactions 317 3.4.4 Conclusions 323 References 328 4 Polyfunctional Catalytic Systems 335 4.1 Oxidation reactions of organic and inorganic compounds 341 4.1.1 Oxidation of alkenes 341 4.1.2 Oxidation of 1,3-dienes 356 4.1.3 Oxidation of alkynes and arenes 366 4.1.4 Oxidation of inorganic compounds 369 4.2 Reactions of chlorination and oxidative chlorination of organic compounds 372 4.2.1 Oxidative chlorination of alkynes 372 4.2.2 Oxidative chlorination of 1,3-dienes 384 4.2.3 Polyfunctional catalytic systems in chlorination reactions 386 4.3 Oxidative carbonylation of organic compounds 389 4.3.1 Oxidative carbonylation of HY molecules (Y = OR, OPh, NR2, Ar, Alk) 390 4.3.2 Oxidative carbonylation of alkenes, dienes, and alkynes 400 4.4 Additive carbonylation of alkynes, alkenes, dienes, and alcohols 408 4.5 Substitution and addition reactions in alkyne chemistry 412 4.6 General problems in PFCS theory and practice 423 4.6.1 PFCSs and principles of their functioning 423 4.6.2 Kinetic and chemical functions of p-benzoquinone and other quinones in PFCSs 426 4.6.3 Variants of association of catalytic reactions and catalytic systems 436 References 442 5 Mechanisms of Formation of Catalytically Active Metal Complexes 453 5.1 Main stages of catalytic process 454 5.2 Chemical reactions involved in the formation of active centers 457 5.3 Mechanisms of active center formation in particular processes 468 5.3.1 Mechanisms of active metal complex formation in PdBr2 –LiBr–P(OPh)3–HBr–n-C4H9OH catalytic system for acrylate synthesis 468 5.3.2 Carbene metal complexes in metathesis of olefins and analogous processes 471 5.3.3 Mechanisms of 1-butene isomerization in Ni[P(OEt)3]4–H2SO4 –MeOH system 488 5.3.4 Features of the formation and decay of active centers in acrylic derivatives synthesis by the Reppe Method 490 5.3.5 Protecting active centers by catalytic process from destruction 492 5.3.6 Mechanism of active center formation in Pd(OAc)2 –PPh3 –p-benzoquinone–MeOH catalytic system for alkyne oxidative carbonylation at ≡C–H bond 494 5.3.7 Catalysis with small palladium(I) halide and carbonyl halide clusters 499 5.3.8 Mechanisms of formation of large cluster complexes and microheterogeneous nanoparticles 507 5.3.9 Synthesis and characterization of giant palladium clusters 512 5.3.10 Approaches to identification of the nature of catalytically active species in solutions of metal complexes 513 5.4 Examples of chain mechanisms and chain carriers of various natures 518 5.5 Classification of mechanisms of real catalytic processes 528 References 536 6 Nonlinear Effects (Critical Phenomena) in Reaction Dynamics in Homogeneous Catalysis with Metal Complexes 545 6.1 Historical notes 548 6.2 Physicochemical factors responsible for the critical phenomena in homogeneous reactions 551 6.2.1 Thermodynamic features of nonequilibrium processes near and far from equilibrium 552 6.2.2 Dynamic behavior of systems with linear mechanisms in open reactors with complete mixing 565 6.2.3 Nonlinearity of kinetic models 570 6.2.4 Main principles and methods of analysis of the dynamic behavior of nonlinear systems 573 6.3 Analysis of simple nonlinear kinetic models 582 6.4 Mechanisms of oscillatory catalytic reactions 630 6.4.1 Belousov–Zhabotinskii reaction (BZ reaction) 630 6.4.2 Liquid-phase oxidation of organic compounds by oxygen in Co(OAc)2–Br–CH3COOH system 640 6.4.3 Oxidative carbonylation of alkynes in solutions of palladium complexes 644 References 658 7 Rational Strategy for Designing Kinetic Models and Studying Complex Reaction Mechanisms 665 7.1 Stages in the development of chemical kinetics and methodological aspects of the strategy of studying complex reaction mechanisms 666 7.2 Alternative strategies for studying complex reaction mechanisms and designing kinetic models 669 7.2.1 Traditional strategy 669 7.2.2 Rational strategy 671 7.3 Hypothesis generation methods and examples 674 7.4 Hypothesis generation programs: Application examples and related problems 677 7.4.1 Combinatorics on kinetic graphs 677 7.4.2 ChemComb (Comb 1) program 686 7.4.3 MECHEM program 691 7.4.4 NetGen program 694 7.4.5 TAMREAC program 697 7.4.6 ChemNet program 697 7.4.7 Large reaction networks and problems in discrimination of hypotheses and construction of compact kinetic models 713 References 733 8 Effect of Medium on Reaction Rates in Homogeneous Catalysis with Metal Complexes 741 8.1 Effect of electrolytes on the activity coefficients of reaction medium components 743 8.2 Effect of electrolytes on the solubility of nonelectrolytes (gases and organic compounds) 748 8.3 Effect of electrolytes on the rates of elementary reactions between ions and uncharged substrates 752 8.4 Kinetics of catalytic reactions in concentrated aqueous electrolyte (HCl) solutions 754 8.5 Organic solvents in homogeneous catalysis with metal complexes 760 8.5.1 Main physical and chemical properties of solvents 760 8.5.2 Association of solvents and formation of molecular complexes 763 8.5.3 Metal complexes in organic and aqueous-organic solvents 765 8.5.4 Ion association, ion pairs, and specific salt effect in organic solvents 771 8.6 Strong protonic acids in organic solvents and kinetics of catalytic reactions with metal complexes in these media 775 8.6.1 Structure and properties of strong acid solutions in organic solvents 776 8.6.2 Kinetics of catalytic reactions in HCl–NMP, HCl–C2H5OH, and HCl–C2H5OH–CH3CN systems 783 8.7 Ionic liquids in catalytic chemistry 787 References 791 Conclusion 797 Subject Index 801 Index of Metals 803 Index of Reactions 805

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Book SynopsisOver the last decade, the area of homogeneous catalysis with transition metal has grown in great scientific interest and technological promise, with research in this area earning three Nobel Prizes and filing thousands of patents relating to metallocene and non-metallocene single site catalysts, asymmetric catalysis, carbon-carbon bond forming metathesis and cross coupling reactions. This text explains these new developments in a unified, cogent, and comprehensible manner while also detailing earlier discoveries and the fundamentals of homogeneous catalysis. Serving as a self-study guide for students and all chemists seeking to gain entry into this field, it can also be used by experienced researchers from both academia and industry for referring to leading state of the art review articles and patents, and also as a quick self-study manual in an area that is outside their immediate expertise. The book features: Topics including renewable feed stocks (biofuel, glycerol), carTable of Contents1. Chemical Industry and Homogeneous Catalysis1.1 Feed Stocks, Fuels and Catalysts1.2 Crude Oil to Gasoline and Basic Building Blocks by Heterogeneous catalysts1.3 Basic Building Blocks to Downstream Products by Homogeneous Catalysis1.4 Comparison among Different Types of Catalysis1.5 Catalyst Recovery1.6 Environmental IssuesProblemsBibliography2. Basic Chemical Concepts2.1 Ligands2.2 Metals2.3 Important Reaction TypesProblemsBibliography3. Methods of Investigation3.1 Catalytic cycle and intermediates3.2 Spectroscopic Studies3.3 Kinetic Studies3.4 Model Compounds3.5 Computational Techniques (Theoretical Calculation)3.6 Asymmetric CatalysisProblemsBibliography4. Carbonylation and Related Reactions4.1 Introduction4.2 Carbonylation and Manufacture of Acetic Acid4.3 Carbonylation of Other Alcohols4.4 Carbonylation of Methyl Acetate4.5 Carbonylation of Alkynes4.6 Other carbonylation and hydrocarboxylation reactions4.7 C1-Chemistry4.8 Engineering AspectsProblemsBibliography5. Hydrogenation and Other Hydrogen Based Catalytic Reactions5.1 Hydrogenation5.2 Hydroformylation5.3 Other Hydroformylation reactions5.4 Asymmetric Hydroformylation5.5 Hydrosilylation5.6 Hydrocyanation5.7 HydroaminationProblemsBibliography6. Polymerization and Selective Oligomerization of Alkenes6.1 Introduction6.2 Early Catalysts for Polyethylene and Polypropylene6.3 Modern Ziegler-Natta Catalyst6.4 Mechanistic Studies6.5 Single Site Catalysts6.6 Ethylene Polymerization with Polar comonomers6.7 Polymers of Other Alkenes6.8 Oligomerization of Ethylene6.9 Engineering AspectsProblemsBibliography7. Selective C-C Bond Forming Reactions With Alkenes7.1 Introduction7.2 Di-, Tri-, Tetramerization and Codimerization reactions7.3 Metathesis Reactions7.4 Pd-Catalyzed Cross Coupling Reactions7.5 Metal catalyzed Cyclopropanation and CycloadditionProblemsBibliography8. Oxidation8.1 Introduction8.2 Wacker Oxidation8.3 Metal-Catalyzed Liquid-Phase Autoxidation8.4 Polymers from Autoxidation Products8.5 Selective Oxidations8.6 Engineering and Safety ConsiderationsProblemsBibliography

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Book SynopsisOpens the door to the sustainable production of pharmaceuticals and fine chemicals Driven by both public demand and government regulations, pharmaceutical and fine chemical manufacturers are increasingly seeking to replace stoichiometric reagents used in synthetic transformations with catalytic routes in order to develop greener, safer, and more cost-effective chemical processes. This book supports the discovery, development, and implementation of new catalytic methodologies on a process scale, opening the door to the sustainable production of pharmaceuticals and fine chemicals. Pairing contributions from leading academic and industrial researchers, Sustainable Catalysis focuses on key areas that are particularly important for the fine chemical and pharmaceutical industries, including chemo-, bio-, and organo-catalytic approaches to C?H, C?N, and C?C bond-forming reactions. Chapters include academic overviews of current innovations and industrial case stuTrade Review“In brief, I have read this book with pleasure and I recommend it to all chemists working or getting started in the field of catalysis.” (Angew. Chem. Int. Ed., 1 October 2014) Table of ContentsForeword vii Preface ix Contributors xi Abbreviations xiii 1 Catalytic Reduction of Amides Avoiding LiAlH4 or B2H6 1 Deborah L. Dodds and David J. Cole-Hamilton 2 Hydrogenation of Esters 37 Lionel A. Saudan 3 Synthesis of Chiral Amines Using Transaminases 63 Nicholas J. Turner and Matthew D. Truppo 4 Development of a Sitagliptin Transaminase 75 Jacob M. Janey 5 Direct Amide Formation Avoiding Poor Atom Economy Reagents 89 Benjamin M. Monks and Andrew Whiting 6 Industrial Applications of Boric Acid and Boronic Acid-Catalyzed Direct Amidation Reactions 111 Joanne E. Anderson, Jannine Cobb, Roman Davis, Peter J. Dunn, Russ N. Fitzgerald, and Alan J. Pettman 7 OH Activation for Nucleophilic Substitution 121 Jonathan M.J. Williams 8 Application of a Redox-Neutral Alcohol Amination in the Kilogram-Scale Synthesis of a GlyT1 Inhibitor 139 Martin A. Berliner 9 Olefin Metathesis: From Academic Concepts to Commercial Catalysts 163 Justyna Czaban, Christian Torborg, and Karol Grela 10 Challenge and Opportunity in Scaling-up Metathesis Reaction: Synthesis of Ciluprevir (BILN 2061) 215 Nathan Yee, Xudong Wei, and Chris Senanayake 11 C–H Activation of Heteroaromatics 233 Koji Hirano and Masahiro Miura 12 The Discovery of a New Pd/Cu Catalytic System for C–H Arylation and Its Applications in a Pharmaceutical Process 269 Jinkun Huang, Xiang Wang, and Johann Chan 13 Diarylprolinol Silyl Ethers: Development and Application as Organocatalysts 287 Hiroaki Gotoh and Yujiro Hayashi 14 Organocatalysis for Asymmetric Synthesis: From Lab to Factory 317 Feng Xu 15 Catalytic Variants of Phosphine Oxide-Mediated Organic Transformations 339 Stephen P. Marsden 16 Formation of C–C Bonds Via Catalytic Hydrogenation and Transfer Hydrogenation 363 Joseph Moran and Michael J. Krische Index 409

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Book SynopsisServing as a user''s manual for synthetic organic and catalytic chemists, this book guides chemists in the design and choice of ligands to catalyze organic reactions and apply the results for more efficient, green, and practical synthesis. Focuses on the role of ligands in metal complexes that catalyze green organic transformations: a hot topic in the area of organic synthesis and green chemistry Offers a comprehensive resource to help readers design and choose ligands and understand selectivity/reactivity characteristics Addresses a gap by taking novel ligand approaches and including up-to-date discussion on hydrogen transfers and reactions Presents important industrial perspective and provides rational explanations of ligand effects, impacts, and noveltyTable of ContentsPreface ix Abbreviation xi Part I N-Heterocyclic Carbene Ligands in Transition Metal Catalyzed Hydrogen Transfer and Dehydrogenative Reactions 1 1 Oxidation and Hydrogenation Reactions Catalyzed by Transition Metal Complexes Bearing N-Heterocyclic Carbene Ligands 3 1.1 Introduction, 3 1.2 Oxidation of Alcohols Based on Hydrogen Transfer, 3 1.3 Oxidation of Alcohols Based on Dehydrogenation, 10 1.4 Hydrogenation and Transfer Hydrogenation of Carbon–Heteroatom Unsaturated Bonds, 12 1.5 Other Related Hydrogenative Reactions, 21 References, 25 2 Bond-Forming Reactions Catalyzed by Transition Metal Complexes Bearing N-Heterocyclic Carbene Ligands 27 2.1 Introduction, 27 2.2 Carbon–Carbon Bond Formation Based on Hydrogen Transfer, 27 2.3 Carbon–Nitrogen Bond Formation Based on Hydrogen Transfer and Dehydrogenation, 37 2.4 Carbon–Oxygen Bond Formation Based on Hydrogen Transfer and Dehydrogenation, 46 References, 52 Part ii η4-Cyclopentadienone/η5-Hydroxycyclopentadienyl and Related Ligands in Transition Metal Catalyzed Hydrogen Transfer and Dehydrogenative Reactions 55 3 Oxidation and Hydrogenation Catalyzed by Transition Metal Complexes Bearing η4-Cyclopentadienone/η5-Hydroxycyclopentadienyl and Related Ligands 57 3.1 Introduction, 57 3.2 Oxidation of Alcohol Based on Hydrogen Transfer and Dehydrogenation, 59 3.3 Oxidation of Amine Based on Hydrogen Transfer, 68 3.4 Hydrogenation and Transfer Hydrogenation of Carbonyl Compounds, 71 3.5 Hydrogenation and Transfer Hydrogenation of Imines and Related Compounds, 79 References, 84 4 Bond-Forming Reactions Catalyzed by Transition Metal Complexes Bearing η4-Cyclopentadienone/η5-Hydroxycyclopentadienyl and Related Ligands 87 4.1 Introduction, 87 4.2 Carbon–Nitrogen Bond-Forming Reactions Based on Hydrogen Transfer and Dehydrogenation, 88 4.3 Carbon–Oxygen Bond-Forming Reactions Based on Hydrogen Transfer and Dehydrogenation, 97 4.4 Carbon–Carbon Bond-Forming Reactions Based on Hydrogen Transfer and Dehydrogenation, 102 References, 105 Part iii Pincer Ligands in Transition Metal Catalyzed Hydrogen Transfer and Dehydrogenative Reactions 107 5 Dehydrogenation of Alkanes Catalyzed by Transition Metal Complexes Bearing Pincer Ligands 109 5.1 Introduction, 109 5.2 Conversion of Alkanes into Alkenes Based on Hydrogen Transfer, 109 5.3 Dehydroaromatization of Alkanes Based on Hydrogen Transfer, 115 5.4 Alkane Metathesis by Tandem Alkane Dehydrogenation and Alkene Metathesis, 118 5.5 Conversion of Alkanes into Alkenes Based on Dehydrogenation, 121 References, 126 6 Oxidation and Hydrogenation Reactions Catalyzed by Transition Metal Complexes Bearing Pincer Ligands 128 6.1 Introduction, 128 6.2 Oxidation of Alcohols Based on Hydrogen Transfer and Dehydrogenation, 128 6.3 Dehydrogenation of Amines, 137 6.4 Hydrogenation and Transfer Hydrogenation of Carbon–Heteroatom Unsaturated Bonds, 141 References, 157 7 Bond-Forming Reactions Catalyzed by Transition Metal Complexes Bearing Pincer Ligands 159 7.1 Introduction, 159 7.2 Carbon–Carbon Bond Formation Based on Hydrogen Transfer, 159 7.3 Carbon–Nitrogen Bond Formation Based on Hydrogen Transfer and Dehydrogenation, 161 7.4 Carbon–Oxygen Bond Formation Based on Hydrogen Transfer and Dehydrogenation, 173 References, 182 Part iv Bidentate and Miscellaneous Ligands in Transition Metal Catalyzed Hydrogen Transfer and Dehydrogenative Reactions 183 8 Oxidation and Dehydrogenation of Alcohols and Amines Catalyzed by Well-Defined Transition Metal Complexes Bearing Bidentate and Miscellaneous Ligands 185 8.1 Introduction, 185 8.2 Oxidation of Alcohols Based on Hydrogen Transfer with Oxidant, 185 8.3 Dehydrogenative Oxidation of Alcohols without Oxidant, 209 8.4 Oxidation of Amines Based on Hydrogen Transfer and Dehydrogenation, 220 References, 224 9 Hydrogenation and Transfer Hydrogenation of Carbon–Heteroatom Unsaturated Bonds Catalyzed by Well-Defined Transition Metal Complexes Bearing Bidentate and Miscellaneous Ligands 228 9.1 Introduction, 228 9.2 Hydrogenation and Transfer Hydrogenation of Carbonyl and Related Compounds, 229 9.3 Hydrogenation and Transfer Hydrogenation of Imines and Related Compounds, 263 References, 274 10 Bond-Forming Reactions Based on Hydrogen Transfer Catalyzed by Well-Defined Transition Metal Complexes Bearing Bidentate and Miscellaneous Ligands 278 10.1 Introduction, 278 10.2 Carbon–Carbon Bond-Forming Reactions Based on Hydrogen Transfer, 279 10.3 Carbon–Nitrogen Bond-Forming Reactions Based on Hydrogen Transfer, 296 10.4 Carbon–Oxygen Bond-Forming Reactions Based on Hydrogen Transfer, 321 References, 330 Index 335

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Book SynopsisPhotocatalytic water splitting is a promising strategy for capturing energy from the sun by coupling light harvesting and the oxidation of water, in order to create clean hydrogen fuel. Thus a deep knowledge of the water oxidation catalysis field is essential to be able to come up with useful energy conversion devices based on sunlight and water splitting. Molecular Water Oxidation Catalysis: A Key Topic for New Sustainable Energy Conversion Schemes presents a comprehensive and state-of-the-art overview of water oxidation catalysis in homogeneous phase, describing in detail the most important catalysts discovered today based on first and second row transition metals. A strong emphasis is placed on the description of their performance, as well as how they work from a mechanistic perspective. In addition, a theoretical description of some of the most relevant catalysts based on DFT are presented, as well as a description of related natural systems, such as the oxygen evoTable of ContentsList of Contributors xi Preface xv 1. Structural Studies of Oxomanganese Complexes for Water Oxidation Catalysis 1 Ivan Rivalta, Gary W. Brudvig, and Victor S. Batista 1.1 Introduction 1 1.2 Structural Studies of the OEC 2 1.3 The Dark-Stable State of the OEC 4 1.4 Biomimetic Oxomanganese Complexes 6 1.5 Base-Assisted O–O Bond Formation 7 1.6 Biomimetic Mn Catalysts for Artificial Photosynthesis 8 1.7 Conclusion 11 Acknowledgments 12 References 12 2. O–O Bond Formation by a Heme Protein: The Unexpected Efficiency of Chlorite Dismutase 15 Jennifer L. DuBois 2.1 Introduction 15 2.2 Origins of O2-Evolving Chlorite Dismutases (Clds) 15 2.3 Major Structural Features of the Proteins and their Active Sites 16 2.4 Efficiency, Specificity, and Stability 20 2.5 Mechanistic Insights from Surrogate Reactions with Peracids and Peroxide 22 2.6 Possible Mechanisms 23 2.7 Conclusion 25 Acknowledgements 25 References 25 3. Ru-Based Water Oxidation Catalysts 29 Laia Francàs, Roger Bofill, Jordi García-Antón, Lluis Escriche, Xavier Sala and Antoni Llobet 3.1 Introduction 29 3.2 Proton-Coupled Electron Transfer (PCET) and Water Oxidation Thermodynamics 31 3.3 O–O Bond Formation Mechanisms 33 3.4 Polynuclear Ru Water Oxidation Catalysts 34 3.5 Mononuclear Ru WOCs 40 3.6 Anchored Molecular Ru WOCs 42 3.7 Light-Induced Ru WOCs 43 3.8 Conclusion 45 Acknowledgments 46 References 46 4. Towards the Visible Light-Driven Water Splitting Device: Ruthenium Water Oxidation Catalysts with Carboxylate-Containing Ligands 51 Lele Duan, Lianpeng Tong, and Licheng Sun 4.1 Introduction 51 4.2 Binuclear Ru Complexes 52 4.3 Mononuclear Ru Complexes 54 4.3.1 Ru–O2N–N3 Analogs 55 4.3.2 Ru–O2N2–N2 Analogs 57 4.4 Homogeneous Light-Driven Water Oxidation 68 4.4.1 The Three-Component System 68 4.4.2 The Supramolecular Assembly Approach 69 4.5 Water Oxidation Device 72 4.5.1 Electrochemical Water Oxidation Anode 72 4.5.2 Photo-Anode for Water Oxidation 74 4.6 Conclusion 75 References 75 5. Water Oxidation by Ruthenium Catalysts with Non-Innocent Ligands 77 Tohru Wada, Koji Tanaka, James T. Muckerman, and Etsuko Fujita 5.1 Introduction 77 5.2 Water Oxidation Catalyzed by Dinuclear Ruthenium Complexes with NILs 81 5.3 Water Oxidation by Intramolecular O–O Coupling with [RuII2 (𝜇-Cl)(bpy)2(btpyan)]3+ 85 5.4 Mononuclear Ru–Aqua Complexes with a Dioxolene Ligand 91 5.4.1 Structural Characterization 91 5.4.2 Theoretical and Electrochemical Characterization 96 5.5 Mechanistic Investigation of Water Oxidation by Dinuclear Ru Complexes with NILs: Characterization of Key Intermediates 101 References 107 6. Recent Advances in the Field of Iridium-Catalyzed Molecular Water Oxidation 113 James A. Woods, Stefan Bernhard, and Martin Albrecht 6.1 Introduction 113 6.2 Bernhard 2008 [11] 114 6.3 Crabtree 2009 115 6.4 Crabtree 2010 116 6.5 Macchioni 2010 117 6.6 Albrecht/Bernhard 2010 117 6.7 Hetterscheid/Reek 2011 118 6.8 Crabtree 2011 119 6.9 Crabtree 2011 120 6.10 Lin 2011 120 6.11 Macchioni 2011 122 6.12 Grotjahn 2011 123 6.13 Fukuzumi 2011 123 6.14 Lin 2012 124 6.15 Crabtree 2012 125 6.16 Albrecht/Bernhard 2012 125 6.17 Crabtree 2012 126 6.18 Beller 2012 127 6.19 Lin 2012 128 6.20 Lloblet and Macchioni 2012 129 6.21 Analysis 130 References 131 7. Complexes of First Row d-Block Metals: Manganese 135 Philipp Kurz 7.1 Background 135 7.2 Oxidation States of Manganese in an Aqueous Environment 137 7.3 Dinuclear Manganese Complexes: Syntheses and Structures 138 7.4 Redox and Acid–Base Chemistry of Mn2-𝜇-WDL Systems 139 7.5 Mn2 Systems: Oxygen Evolution (but not Water Oxidation) Catalysis 142 7.6 Mn2 Complexes/the OEC/Ru2 Catalysts: A Comparison 144 7.7 Heterogeneous Water Oxidation Catalysis by Mn>2 Systems 146 7.8 Conclusion 148 Acknowledgements 148 References 149 8. Molecular Water Oxidation Catalysts from Iron 153 W. Chadwick Ellis, Neal D. McDaniel, and Stefan Bernhard 8.1 Introduction 153 8.2 Fe-Tetrasulfophthalocyanine 154 8.3 Fe-TAML 155 8.4 Fe-mcp 157 8.5 Fe2O3 as a Microheterogeneous Catalyst 158 8.6 Conclusion 160 References 161 9. Water Oxidation by Co-Based Oxides with Molecular Properties 163 Marcel Risch, Katharina Klingan, Ivelina Zaharieva, and Holger Dau 9.1 Introduction 163 9.2 CoCat Formation 164 9.3 Structure and Structure–Function Relations 166 9.4 Functional Characterization 173 9.5 Directly Light-Driven Water Oxidation 175 References 180 10. Developing Molecular Copper Complexes for Water Oxidation 187 Shoshanna M. Barnett, Christopher R. Waidmann, Margaret L. Scheuermann, Jared C. Nesvet, Karen Goldberg and James M. Mayer 10.1 Introduction 187 10.2 A Biomimetic Approach 188 10.2.1 Thermochemistry: Developing Oxidant/Base Combinations as PCET Reagents 189 10.2.2 Copper Complexes with Alkylamine Ligands 190 10.2.3 Copper Complexes with Anionic Ligands 195 10.2.4 Lessons Learned: Thermochemical Insights and Oxidant/Base Compatibility 198 10.3 An Aqueous System: Electrocatalysis with (bpy)Cu(II) Complexes 198 10.3.1 System Selection: bpy + Cu 199 10.3.2 Observing Electrocatalysis 199 10.3.3 Catalyst Turnover Number and Turnover Frequency 201 10.3.4 Catalyst Speciation: Monomer, Dimer, or Nanoparticles? 203 10.4 Conclusion 206 Acknowledgement 206 References 207 11. Polyoxometalate Water Oxidation Catalytic Systems 211 Jordan M. Sumliner, James W. Vickers, Hongjin Lv, Yurii V. Geletii, and Craig L. Hill 11.1 Introduction 211 11.2 Recent POM WOCs 214 11.3 Assessing POM WOC Reactivity 220 11.4 The Ru(bpy)3 2+ ∕S2O8 2-System 221 11.5 Ru(bpy) 3 3+ as an Oxidant for POM WOCs 222 11.6 Additional Aspects of WOC System Stability 224 11.7 Techniques for Assessing POM WOC Stability 224 11.8 Conclusion 227 Acknowledgments 228 References 228 12. Quantum Chemical Characterization of Water Oxidation Catalysts 233 Pere Miró, Mehmed Z. Ertem, Laura Gagliardi, and Christopher J. Cramer 12.1 Introduction 233 12.2 Computational Details 235 12.2.1 Density Functional Theory Calculations 235 12.2.2 Multiconfigurational Calculations 236 12.3 Methodology 237 12.3.1 Solvation and Standard Reduction Potentials 237 12.3.2 Multideterminantal State Energies 238 12.4 Water Oxidation Catalysts 238 12.4.1 Ruthenium-Based Catalysts 238 12.4.2 Cobalt-Based Catalysts 245 12.4.3 Iron-Based Catalysts 248 12.5 Conclusion 251 References 252 Index 257

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Book SynopsisFour decades of landmark discoveries in heterogeneous catalysis Presenting an historical record of four decades of landmark research, this book draws together an important collection of heterogeneous catalysis papers published by Professor Eli Ruckenstein and his colleagues. One of the most prolific leaders in the field of heterogeneous catalysis today, Dr. Ruckenstein has pioneered methods in catalysis, surface chemistry, and materials science that are now used to develop new chemicals, energy sources, and materials. Heterogeneous Catalysis offers new insights into the underlying mechanisms and chemistry of heterogeneous catalysis. Moreover, the book will help readers develop new applications for both basic research and industry. Coverage includes: Catalysts in various reactions including methane CO2 reforming, methane partial oxidation, and catalytic combustion Applications of materials such as zeolites, meTable of Contents1 Catalytic conversion of methane to synthesis gas by CO2 reforming 1 2 Catalytic conversion of methane to synthesis gas by partial oxidation 79 3 Catalytic combustion of clean as well as nitrogen bound fuels over transitional metal oxides 139 4 Zeolites and their applications as catalysts and/or catalyst supports 223 5 Synthesis of mesoporous V-Mg-O oxides and their applications as catalysts 365 6 Synthesis of polymer supported catalysts and polymer-coated silica supports and their applications in catalysis 404 7 Metal sintering during heating in various atmospheres 473 8 Heterogeneous catalysis – a theoretical approach 667

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Book SynopsisThis book gradually brings the reader, through illustrations of the most crucial discoveries, into the modern world of chemical catalysis. Readers and experts will better understand the enormous influence that catalysis has given to the development of modern societies. Highlights the field''s onset up to its modern days, covering the life and achievements of luminaries of the catalytic era Appeals to general audience in interpretation and analysis, but preserves the precision and clarity of a scientific approach Fills the gap in publications that cover the history of specific catalytic processesTable of ContentsPreface ix 1 From the Onset to the First Large-Scale Industrial Processes 1 1.1 Origin of the Catalytic Era 1 1.2 Berzelius and the Affinity Theory of Catalysis 4 1.3 Discovery of the Occurrence of Catalytic Processes in Living Systems in the Nineteenth Century 6 1.4 Kinetic Interpretation of Catalytic Processes in Solutions: The Birth of Homogeneous Catalysis 8 1.5 Onset of Heterogeneous Catalysis 18 1.6 First Large-Scale Industrial Processes Based on Heterogeneous Catalysts 26 1.6.1 Sulfuric Acid Synthesis 26 1.6.2 Ammonia Problem 29 1.6.3 Ammonia Oxidation Process 32 1.6.4 Ammonia Synthesis 33 1.7 Fischer–Tropsch Catalytic Process 40 1.8 Methanol Synthesis 44 1.9 Acetylene Production and Utilization 46 1.10 Anthraquinone Process for Hydrogen Peroxide Production 47 References 49 2 Historical Development of Theories of Catalysis 59 2.1 Heterogeneous Catalysis 59 2.2 Chemical Kinetics and the Mechanisms of Catalysis 62 2.3 Electronic Theory of Catalysis: Active Sites 72 References 76 3 Catalytic Processes Associated with Hydrocarbons and the Petroleum Industry 83 3.1 Petroleum and Polymer Eras 83 3.2 Catalytic Cracking, Isomerization, and Alkylation of Petroleum Fractions 84 3.3 Reforming Catalysts 91 3.4 Hydrodesulfurization (HDS) Processes 93 3.5 Hydrocarbon Hydrogenation Reactions with Heterogeneous Catalysts 94 3.6 Olefin Polymerization: Ziegler–Natta, Metallocenes, and Phillips Catalysts 98 3.7 Selective Oxidation Reactions 109 3.7.1 Alkane Oxidation 109 3.7.2 Olefin Oxidation 110 3.7.3 Aromatic Compounds Oxidation 111 3.8 Ammoximation and Oxychlorination of Olefins 113 3.9 Ethylbenzene and Styrene Catalytic Synthesis 117 3.10 Heterogeneous Metathesis 118 3.11 Catalytic Synthesis of Carbon Nanotubes and Graphene from Hydrocarbon Feedstocks 119 References 121 4 Surface Science Methods in the Second Half of the Twentieth Century 131 4.1 Real Dispersed Catalysts versus Single Crystals: A Decreasing Gap 131 4.2 Physical Methods for the Study of Dispersed Systems and Real Catalysts 132 4.3 Surface Science of Single-Crystal Faces and of Well-defined Systems 139 References 147 5 Development of Homogeneous Catalysis and Organocatalysis 155 5.1 Introductory Remarks 155 5.2 Homogeneous Acid and Bases as Catalysts: G. Olah Contribution 156 5.3 Organometallic Catalysts 161 5.4 Asymmetric Epoxidation Catalysts 175 5.5 Olefin Oligomerization Catalysts 179 5.6 Organometallic Metathesis 180 5.7 Cross-Coupling Reactions 186 5.8 Pd(II)-Based Complexes and Oxidation of Methane to Methanol 190 5.9 Non-transition Metal Catalysis, Organocatalysis, and Organo-Organometallic Catalysis Combination 191 5.9.1 Metal-Free Hydrogen Activation and Hydrogenation 192 5.9.2 Amino Catalysis 193 5.10 Bio-inspired Homogeneous Catalysts 194 References 195 6 Material Science and Catalysis Design 205 6.1 Metallic Catalysts 205 6.2 Oxides and Mixed Oxides 208 6.2.1 SiO2 and SiO2-Based Catalysts and Processes 209 6.2.2 Al2O3 and Al2O3-Based Catalysts and Processes 211 6.2.3 SiO2–Al2O3− and SiO2–Al2O3-Based Catalysts and Processes 211 6.2.4 MgO− and MgO-Based Catalysts and Processes 212 6.2.5 ZrO2 and ZrO2-Based Catalysts and Processes 212 6.3 Design of Catalysts with Shape and Transition-State Selectivity 213 6.4 Zeolites and Zeolitic Materials: Historical Details 214 6.5 Zeolites and Zeolitic Materials Structure 218 6.6 Shape-Selective Reactions Catalyzed by Zeolites and Zeolitic Materials 221 6.6.1 Alkanes- and Alkene-Cracking and Isomerization 222 6.6.2 Aromatic Ring Positional Isomerizations 223 6.6.3 Synthesis of Ethyl Benzene, Cumene, and Alkylation of Aromatic Molecules 224 6.6.4 Friedel–Crafts Acylation of Aromatic Molecules 225 6.6.5 Toluene Alkylation with Methanol 225 6.6.6 Asaki Process for Cyclohexanol Synthesis 226 6.6.7 Methanol-to-Olefins (MTO) Process 226 6.6.8 Nitto Process 227 6.6.9 Butylamine Synthesis 227 6.6.10 Beckman Rearrangements on Silicalite Catalyst 227 6.6.11 Partial Oxidation Reactions Using Titanium Silicalite 227 6.6.12 Nylon-6 Synthesis: The Role of Zeolitic Catalysts 229 6.6.13 Pharmaceutical Product Synthesis 229 6.7 Organic–Inorganic Hybrid Zeolitic Materials and Inorganic Microporous Solids 230 6.7.1 Organic–Inorganic Hybrid Zeolitic Materials 230 6.7.2 ETS-10: A Microporous Material Containing Monodimensional TiO2 Chains 231 6.7.3 Hydrotalcites: Microporous Solids with Exchangeable Anions 232 6.8 Microporous Polymers and Metal–Organic Frameworks (MOFs) 232 6.8.1 Microporous Polymers 232 6.8.2 Metal–organic Frameworks 234 References 235 7 Photocatalysis 243 7.1 Photochemistry and Photocatalysis: Interwoven Branches of Science 243 7.2 Photochemistry Onset 245 7.3 Physical Methods in Photochemistry 249 7.4 Heterogeneous and Homogeneous Photocatalysis 251 7.5 Natural Photosynthesis as Model of Photocatalysis 253 7.6 Water Splitting, CO2 Reduction, and Pollutant Degradation: The Most Investigated Artificial Photocatalytic Processes 256 7.6.1 Water Splitting 257 7.6.2 CO2 Photoreduction 261 7.6.3 Photocatalysis in Environmental Protection 263 References 264 8 Enzymatic Catalysis 269 8.1 Early History of Enzymes 269 8.2 Proteins and Their Role in Enzymatic Catalysis 273 8.3 Enzymes/Coenzymes Structure and Catalytic Activity 284 8.4 Mechanism of Enzyme Catalysis 288 8.5 Biocatalysis 294 References 295 9 Miscellanea 299 9.1 Heterogeneous and Homogeneous Catalysis in Prebiotic Chemistry 299 9.2 Opportunities for Catalysis in the Twenty-First Century and the Green Chemistry 312 References 317 Index 321

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Book SynopsisThe development of new asymmetric catalytic methods is of fundamental importance to industrial synthetic chemistry. The demand for optically pure synthetic intermediates and the drive to adopt greener methods of synthesis have stimulated a growing interest in biocatalysis as a selective and environmentally benign synthetic technique. Practical Biotransformations: A Beginner''s Guide provides an introduction to microbes and enzymes and demonstrates their practical applications in synthetic organic chemistry. Designed as a laboratory manual, this user-friendly guide discusses standard laboratory techniques, with appropriate advice on aspects of microbial practice and associated safety. Topics covered include: An introduction to equipment in a biotransformations laboratory An overview of biocatalyst sources Maintenance and growth of biocatalysts Example biotransformations using commerciaTrade Review?The book provides a good overview and appropriately conceived outline of this complex topic, enabling the interested reader to begin work with enzymes quickly and without unnecessary complications.? (Angewandte Chemie, October 2009) ?Gogan presents a beginner's guide to microbes and enzymes and how to use them for synthetic organic reactions in the laboratory.? ( Book News, September 2009) ?This book is easy to read and well organized and can be dipped in and out of, depending on your level of experience in different areas. ? Overall and excellent, interesting and user-friendly manual/textbook.? (Chemistry World, August 2009) Table of ContentsChapter 1: Biotransformations, Microbes and Enzymes. 1.1 Introduction. 1.2 Biotransformations. 1.3 Microorganisms. 1.4 Organism nomenclature. 1.5 Enzymes. 1.6 Types of Enzymatic reactions. 1.7 Enzymatic Cofactors. 1.8 Some Basic Characteristics of Enzyme Catalysis. 1.9 Types of Biocatalyst - Biotransformations by ‘whole cells’ or isolated enzymes. 1.10. Conclusion. Chapter 2: An overview of biocatalyst sources and web-based information. 2.1 Introduction. 2.2 Microbial culture collections. 2.3 Obtaining organisms from other research groups. 2.4 Selective Enrichments. 2.5 Metagenomics. 2.6 Enzyme Suppliers and Biocatalyst Development Companies. 2.7 Genome mining for biocatalysts. 2.8 Obtaining amino acid and gene sequence information on biocatalysts. 2.9 Obtaining DNA templates for cloning. 2.10 Custom Gene Synthesis. 2.11 Other interesting web resources for biocatalysis. 2.12 Conclusion. Chapter 3: Setting up a laboratory for biotransformations. 3.1 Introduction. 3.2 Microbiological Containment. 3.3 On containment issues and genetically-modified organisms. 3.4 Equipment for handling microorganisms. 3.5 Techniques and terms in microbiology - Sterility, Asepsis and Aseptic Technique. 3.6 Disposal of viable microbial waste and disinfection of reusable equipment. 3.7 Equipment for enzymology and molecular biology. 3.8 General reagents and chemicals in a Biotransformations Laboratory. 3.9 Conclusion. Chapter 4: A beginner’s guide to preparative whole-cell microbial biotransformations. 4.1 Introduction. 4.2 Storage, maintenance and growth of microorganisms. 4.3 General Microbiological Methods. 4.4 Examples of Whole-cell Biotransformations using Bacteria. 4.5 Biotransformation by filamentous fungi and yeasts. 4.6 Whole-cell Biotransformations by recombinant strains of E. coli. 4.7 Conclusion. Chapter 5: A beginner’s guide to biotransformations by commercially available isolated enzymes. 5.1 Introduction. 5.2 Lipases. 5.3 Hydrolytic Reactions using lipases. 5.4 Using lipases for acylation reactions. 5.5 Other hydrolases. 5.6 Commercially available Coenzyme-dependent Enzymes. 5.7 Carbon-carbon bond forming reactions. 5.8 Conclusion. Chapter 6: A beginner’s guide to the isolation and analysis and use of home-grown enzyme biocatalysts. 6.1 Introduction. 6.2 Cell growth and harvesting. 6.3 Cell disruption. 6.4 A typical procedure for making a cell extract from a recombinant strain of E. coli. 6.5 Purification of enzymes - a brief guide. 6.6 Techniques for Protein Purification. 6.7 Isolation of recombinant enzymes using histidine tags. 6.8 Estimation of protein concentration. 6.9 Concentrating protein samples by centrifugation. 6.10 Analysis of protein samples by sodium dodecylsulfate polyacrylamide gel electrophoresis (SDS-PAGE). 6.11 Examples of enzyme assays. 6.12 Using home-grown enzymes for biotransformations ? Some recent examples. 6.13 Conclusion. Chapter 7: An introduction to basic gene cloning for the production of designer biocatalysts. 7.1 Introduction. 7.2 Background to gene cloning. 7.3 Gene amplification by polymerase chain reaction (PCR). 7.4 DNA fragment analysis by agarose electrophoresis. 7.5 Gene cloning. 7.6 Analysis by DNA sequencing. 7.7 Troubleshooting the gene amplification and cloning process. 7.8 Ligation-Independent Cloning. 7.9 Gene Expression in E. coli. 7.10 Conclusion. Chapter 8: Engineering Enzymes. 8.1 Introduction. 8.2 Site-directed or targted mutagenesis as a tool for investigating enzyme mechanism or altering catalytic attributes. 8.3 A site-directed mutagenesis experiment. Considerations and practise. 8.4 Engineering using random mutagenesis. Directed Evolution of Enzymes. 8.5 Combining rational and random mutagenesis for biocatalyst improvement. 8.6 Exploiting catalytic promiscuity for creating new enzyme activities. 8.7 Designing enzymes in silico. 8.8 Conclusion. Appendices. 1. Structures of the proteinogenic amino acids. 2. Structures of bases found in nucleic acids. 3. The Genetic Code. 4. Recipes for Microbiological Growth Media. 5. Biological buffers. 6. Ammonium sulphate fractionation table. 7. Restriction enzymes and restriction sites.

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Book SynopsisFor more than a century, bioactive heterocycles have formed one of the largest areas of research in organic chemistry. They are important from a biological and industrial point of view as well as to the understanding of life processes and efforts to improve the quality of life. Heterogeneous Catalysis: A Versatile Tool for the Synthesis of Bioactive Heterocycles highlights the recent methodologies used in the synthesis of such bioactive systems and focuses on the role of heterogeneous catalysis in the design and synthesis of various biologically active heterocyclic compounds of pharmacological interest. Topics include: Synthetic protocols for the construction of heterocyclic systems employing silica-bound catalysts Recent advances in heterogeneous copper-catalyzed reactions for the synthesis of bioactive heterocycles Features of silica-based heterogeneous catalysts, such as abundance, ease of use, and stabilityTable of ContentsSynthesis of Bioactive Heterocyclic Systems Promoted by Silica-Supported Catalysts. Eco-Benign Synthesis of Indole Derivatives Employing Diverse Heterogeneous Catalysts. Solid Heterogeneous Catalysts Based on Sulfuric Acid and Transition-Metal Salts: Synthesis of Bioactive Heterocycles. Heterogeneous Copper-Catalyzed Synthesis of Bioactive Heterocycles. Silica Sulfuric Acid: A Simple and Powerful Heterogeneous Catalyst in Organic Synthesis. Application of Silica-Based Heterogeneous Catalysis for the Synthesis of Bioactive Heterocycles. Application of Organometallic Compounds as Heterogeneous Catalysts in Organic Synthesis. Ultrasound: An Efficient Tool for the Synthesis of Bioactive Heterocycles. Nano–Zinc Oxide: An Efficient Heterogeneous Catalyst for the Synthesis of Heterocyclic Compounds. Application of Heterogeneous Catalysts for the Synthesis of Bioactive Coumarins. Silver: A Versatile Heterogeneous Catalyst for Heterocyclic Synthesis. Mesoporous Materials from Novel Silica Source as Heterogeneous Catalyst.

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Book Synopsis

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Book SynopsisThe chemical or biological process whereby the presence of an external compound, a catalyst, serves as an agent to cause a chemical reaction to occur or to improve reaction performance without altering the external compound. Catalysis is a very important process from an industrial point of view since the production of most industrially important chemicals involve catalysis. Catalysis research is a major field in applied science, and involves many fields of chemistry and physics. The new book brings together leading research in this vibrant field.

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Book SynopsisThe chemical or biological process whereby the presence of an external compound, a catalyst, serves as an agent to cause a chemical reaction to occur or to improve reaction performance without altering the external compound. Catalysis is a very important process from an industrial point of view since the production of most industrially important chemicals involve catalysis. Research into catalysis is a major field in applied science, and involves many fields of chemistry and physics. The book brings together leading research in this vibrant field.

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Book SynopsisThe chemical or biological process whereby the presence of an external compound, a catalyst, serves as an agent to cause a chemical reaction to occur or to improve reaction performance without altering the external compound. Catalysis is a very important process from an industrial point of view since the production of most industrially important chemicals involve catalysis. Research into catalysis is a major field in applied science, and involves many fields of chemistry and physics. The new book brings together leading research in this vibrant field.

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Book SynopsisCatalysis is a multidisciplinary subject. This book introduces the chemical, materials, and engineering principles of catalysis so that both MSc and PhD students with a basic but not extensive knowledge of chemistry and physics and those with a basic understanding of chemical engineering can learn more about catalysis. Examples are taken from catalytic reactions and catalysts used in the energy, petroleum, and base-chemicals industry.The second edition differs from the first edition in the way basic topics are integrated with catalytic applications. The authors introduce two new chapters: 'Cleaning of Fuels by Hydrotreating' and 'Electrocatalysis'. Hydrotreating is a very important industrial process and offers the opportunity to discuss metal sulfide catalysts. Electrocatalysis gains more and more attention because it can be used to minimize the anthropogenic CO₂ emissions. Solar, wind, and hydroelectricity can drive water electrolysis and CO₂ electroreduction and, therefore, excess renewable electricity can be stored in chemicals.Introduction to Heterogeneous Catalysis (Second Edition) is intended for a one-semester course for master and PhD students who want to learn more about the principles of catalysis. This must-read textbook will enable students to read catalysis literature without much difficulty and presents not only the basic concepts of catalysis but integrates the chemical, materials, and engineering aspects of catalysis with industry examples.

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Book SynopsisCatalysis is a multidisciplinary subject. This book introduces the chemical, materials, and engineering principles of catalysis so that both MSc and PhD students with a basic but not extensive knowledge of chemistry and physics and those with a basic understanding of chemical engineering can learn more about catalysis. Examples are taken from catalytic reactions and catalysts used in the energy, petroleum, and base-chemicals industry.The second edition differs from the first edition in the way basic topics are integrated with catalytic applications. The authors introduce two new chapters: 'Cleaning of Fuels by Hydrotreating' and 'Electrocatalysis'. Hydrotreating is a very important industrial process and offers the opportunity to discuss metal sulfide catalysts. Electrocatalysis gains more and more attention because it can be used to minimize the anthropogenic CO₂ emissions. Solar, wind, and hydroelectricity can drive water electrolysis and CO₂ electroreduction and, therefore, excess renewable electricity can be stored in chemicals.Introduction to Heterogeneous Catalysis (Second Edition) is intended for a one-semester course for master and PhD students who want to learn more about the principles of catalysis. This must-read textbook will enable students to read catalysis literature without much difficulty and presents not only the basic concepts of catalysis but integrates the chemical, materials, and engineering aspects of catalysis with industry examples.

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Book SynopsisHeterogeneous catalysis has developed over the past two centuries as a technology driven by the needs of society, and is part of Nobel Prize-winning science. This book describes the spectacular increase in molecular understanding of heterogenous catalytic reactions in important industrial processes. Reaction mechanism and kinetics are discussed with a unique focus on their relation with the inorganic chemistry of the catalyst material. An introductory chapter presents the development of catalysis science and catalyst discovery from a historical perspective. Five chapters that form the thrust of the book are organized by type of reaction, reactivity principles, and mechanistic theories, which provide the scientific basis to structure-function relationships of catalyst performance. Present-day challenges to catalysis are sketched in a final chapter. Written by one of the world's leading experts on the topic, this definitive text is an essential reference for students, researchers and engineers working in this multibillion-dollar field.

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Book SynopsisThere are many mononuclear iron containing enzymes in nature that utilize molecular oxygen and transfer one or both oxygen atoms of O2 to substrates. These enzymes catalyze many processes including the biosynthesis of hormones, the metabolism of drugs, DNA and RNA base repair and, the biosynthesis of antibiotics. Therefore, mononuclear iron containing enzymes are important intermediates in bioprocesses and have great potential in the commercial biosynthesis of specific products since they often catalyze reactions regioselectively or stereospecifically. Understanding their mechanism and function is important and will assist in searches for commercial exploitation. In recent years, advances in experimental as well as theoretical methodologies have made it possible to study the mechanism and function of these enzymes and much information on their properties has been gained. This book highlighting recent developments in the field is, therefore, a timely addition to the literature and will interest a broad readership in the fields of biochemistry, inorganic chemistry and computational chemistry. The Editors, leaders in the field of nonheme and heme iron containing monoxygenases, have filled the book with topical review chapters by leaders in the various sub-disciplines.Table of ContentsNonheme iron(IV)-oxo oxidants in enzymes: Spectroscopic properties and reactivity patterns; Heme iron(IV)-oxo oxidants in enzymes: Spectroscopic properties and reactivity patterns; Mechanism and function of taurine/ -ketoglutarate dioxygenase enzymes, an update; Mechanism and function of cysteine dioxygenase enzymes; Mechanism and function of heme peroxidase enzymes; Mechanism and function of cytochrome P450 enzymes Biomimetic studies of mononuclear nonheme iron containing oxidants; Biomimetic studies of mononuclear porphyrin containing oxidants; Density functional calibration studies on iron-containing systems; Density functional theory studies on isomerisation reactions catalyzed by cytochrome P450 enzymes Quantum mechanics/molecular mechanics studies of peroxidase enzymes; Theoretical modelling of nonheme iron containing oxidants

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Book Synopsis

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Book SynopsisThis book provides a comprehensive overview of the field of plasma catalysis, regarded as a promising alternative to thermal processes for energy and environmental applications. It bridges the gap between the plasma and catalysis research communities, covering both the fundamentals of plasma catalysis and its application in environmental and energy research. The first section of the book offers a broad introduction to plasma catalysis, covering plasma-catalyst systems, interactions, and modeling. The core of the book then focuses on different applications, describing a wide range of plasma-catalytic processes in catalyst synthesis, environmental clean-up, greenhouse gas conversion and synthesis of materials for energy applications. Chapters cover topics ranging from removal of NOx and VOCs to conversion of methane, carbon dioxide and the reforming of ethanol and methanol.Written by a group of world-leading researchers active in the field, the book forms a valuable resource for scientists, engineers and students with different research backgrounds including plasma physics, plasma chemistry, catalysis, energy, environmental engineering, electrical engineering and material engineering.Table of Contents

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Book SynopsisCatalysis is at the heart of the chemical industry, which uses solid catalysts for the large-scale production of commodity chemicals. Catalysis at surfaces is also the basis for the ongoing transition to a sustainable energy supply, which requires molecules such as hydrogen, ammonia or methanol to store energy in chemical bonds, and environmental protection equally relies on heterogeneous catalysis. Catalysis at surfaces is a truly interdisciplinary field, which requires profound knowledge from chemistry, physics and engineering as provided by this textbook. All essential tools are described ranging from the synthesis and modification of porous solids over bulk- and surface-sensitive characterization techniques to currently applied theoretical methods. A close-up to the important aspects of surface catalysis is provided, which comprises the established knowledge about mechanisms and active sites, promotors and poisons in redox and acid-base catalysis. This advanced textbook is recommended for Master and PhD students, for whom it provides the fundamentals and all relevant aspects of catalyst synthesis, characterization and application in suitable reactors. It is not only thermal catalysis that is covered in depth, but also photo- and electrocatalysis as emerging fields in the Energiewende.

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Book SynopsisThis book provides the reader with a comprehensive introduction to the topic of organometallic chemistry. With an easy to follow structure covering both nontransition metals and transition metals as well as the applications of organometallic reagents in organic synthesis, this book is a must-have for the organometallic chemist.

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Book SynopsisThe increase of renewable electricity production and the resulting surplus lead us to ask: how to improve energy efficiency through the use of hydrogen? This 2nd Edition of Power-to-Gas covers the global energy issues (generation, distribution, consumption, markets), the production of hydrogen via electrolysis, its transportation and storage or conversion in another form. It takes account of the new energy challenges facing the world and the development of experimentations by adding new projects and realisations.

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Book SynopsisThis textbook is a concise introduction to heterogeneous catalysis, focusing on the fundamentals and industrial implementation. It is written in a clear manner using language that is easily accessible to undergraduate students in chemical engineering and industrial chemistry. The textbook includes exercise problems and practice software. New in this edition are sections on catalyst preparation and manufacture, kinetic parameter estimation, and catalytic transport-line reactors. Solutions to all the example problems are now provided.

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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.

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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

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Book SynopsisWritten by an excellent, highly experienced and motivated team of lecturers, this textbook is based on one of the most successful courses in catalysis and as such is tried-and-tested by generations of graduate and PhD students, i.e. the Catalysis-An-Integrated-Approach (CAIA) course organized by NIOK, the Dutch Catalysis research school. It covers all essential aspects of this important topic, including homogeneous, heterogeneous and biocatalysis, but also kinetics, catalyst characterization and preparation, reactor design and engineering. The perfect source of information for graduate and PhD students in chemistry and chemical engineering, as well as for scientists wanting to refresh their knowledgeTable of ContentsPreface xiii 1 Introduction 1Leon Lefferts, Ulf Hanefeld, and Harry Bitter 1.1 A FewWords at the Beginning 1 1.2 Catalysis in a Nutshell 1 1.3 History of Catalysis 3 1.3.1 Industrial Catalysis 4 1.3.2 Environmental Catalysis 5 1.4 Integration Homo–Hetero-Biocatalysis 5 1.5 Research in Catalysis 10 1.5.1 S-Curve, Old Processes Improvement Is Knowledge Intensive 10 1.5.2 Interdependence with Other Fields 11 1.5.3 Recent and Future Issues 12 1.6 Catalysis and Integrated Approach or How to Use this Book 14 References 14 2 Heterogeneous Catalysis 15Leon Lefferts, Emiel Hensen, and Hans Niemantsverdriet 2.1 Introduction 15 2.1.1 Concept of Heterogeneous Catalysis 15 2.1.2 Applications of Heterogeneous Catalysis 16 2.1.3 Catalytic Cycle 23 2.2 Adsorption on Surfaces 23 2.2.1 Physisorption and Chemisorption 24 2.2.2 Adsorption Isotherms 26 2.2.3 Chemisorption and Chemical Bonding 28 2.2.4 Connecting Kinetic andThermodynamic Formulations 33 2.3 Surface Reactions 35 2.3.1 Reaction Mechanism and Kinetics 35 2.4 Types of Heterogeneous Catalysts 41 2.4.1 Supported Metals 41 2.4.2 Oxides and Sulfides 51 2.4.3 Solid Acid Catalysts 62 Question 1 69 Question 2 69 References 70 3 Homogeneous Catalysis 73Elisabeth Bouwman,Martin C. Feiters, and Robertus J. M. Klein Gebbink 3.1 Framework and Outline 73 3.1.1 Outline of this Chapter 73 3.1.2 Definitions and Terminology 74 3.2 Coordination and Organometallic Chemistry 75 3.2.1 Coordination Chemistry: d Orbitals, Geometries, Crystal Field Theory 75 3.2.2 σ and π donors and back-donation: CO, alkene, phosphane, H2 77 3.2.3 Organometallics: Hapticity, Metal–Alkyl/Allyl, Agostic Interaction, Carbenes 80 3.2.4 Electron Counting: Ionogenic or Donor-Pair versus Covalent or Neutral-Ligand 81 3.2.5 Effect of Binding on Ligands andMetal Ions, Stabilization of Oxidation States 83 3.3 Elementary Steps in Homogeneous Catalysis 84 3.3.1 Formation of the Active Catalyst Species 84 3.3.2 Oxidative Addition and Reductive Elimination 85 3.3.3 Migration and Elimination 87 3.3.4 Oxidative Coupling and Reductive Cleavage 90 3.3.5 Alkene or Alkyne Metathesis and σ-Bond Metathesis 90 3.3.6 Nucleophilic and Electrophilic Attack 92 3.4 Homogeneous Hydrogenation 95 3.4.1 Background and Scope 95 3.4.2 H2 DihydrideMechanism:Wilkinson’s Catalyst 96 3.4.3 H2 Monohydride Mechanism and Heterolytic Cleavage 97 3.4.4 Asymmetric Homogeneous Hydrogenation 98 3.4.5 Transfer Hydrogenation with 2-Propanol 100 3.4.6 Other Alkene Addition Reactions 102 3.5 Hydroformylation 104 3.5.1 Scope and Importance of the Reaction and Its Products 104 3.5.2 Cobalt-Catalyzed Hydroformylation 105 3.5.3 Rhodium-Catalyzed Hydroformylation 107 3.5.4 Asymmetric Hydroformylation 110 3.6 Oligomerization and Polymerization of Alkenes 112 3.6.1 Scope and Importance of Oligomerization and Polymerization 112 3.6.2 Oligomerization of Ethene (Ni, Cr) 113 3.6.3 Stereochemistry and Mechanism of Propene Polymerization 115 3.6.4 Metallocene Catalysis 117 3.6.5 Polymerization with Non-Metallocenes (Pd, Ni, Fe, Co) 118 3.7 Miscellaneous Homogeneously Catalyzed Reactions 118 3.7.1 Cross-Coupling Reactions: Pd-Catalyzed C–C Bond Formation 118 3.7.2 Metathesis Reactions 120 Question 1 (total 20 points) 122 Question 2 (total 20 points) 122 References 123 Further Reading 124 4 Biocatalysis 127Guzman Torrelo, Frank Hollmann, and Ulf Hanefeld 4.1 Introduction 127 4.2 Why Are Enzymes So Huge? 129 4.3 Classification of Enzymes 137 4.3.1 Oxidoreductases (EC 1) 139 4.3.2 Transferases (EC 2) 147 4.3.3 Hydrolases (EC 3) 147 4.3.4 Lyases (EC 4) 157 4.4 Concepts and Methods 157 4.4.1 Cofactor Regeneration Systems 158 4.4.2 Methods to Shift Unfavorable Equilibria 159 4.4.3 Two-Liquid-Phase Systems (and Related) 164 4.4.4 (Dynamic) Kinetic Resolutions and Desymmetrization 164 4.4.5 Enantiomeric Ratio E 168 4.5 Applications and Case Studies 169 4.5.1 Oxidoreductases (E.C. 1) 169 4.5.2 Transferases (EC 2) 177 4.5.3 Hydrolases (EC 3) 179 4.5.3.1 Lipases and Esterases (EC 3.1.1) 179 4.5.4 Lyases (EC 4) 181 Question 1 186 Question 2 186 Question 3 187 Question 4 188 Further Reading 188 5 Chemical Kinetics of Catalyzed Reactions 191Freek Kapteijn, Jorge Gascon, and T. Alexander Nijhuis 5.1 Introduction 191 5.2 Rate Expressions – Quasi-Steady-State Approximation and Quasi-Equilibrium Assumption 193 5.3 Adsorption Isotherms 198 5.3.1 One-Component Adsorption 198 5.3.2 Multicomponent Adsorption 199 5.3.3 Dissociative Adsorption 200 5.4 Rate Expressions – Other Models and Generalizations 200 5.5 Limiting Cases – Reactant and Product Concentrations 202 5.6 Temperature and Pressure Dependence 206 5.6.1 Transition-StateTheory 207 5.6.2 Forward Reaction – Temperature and Pressure Dependence 208 5.6.3 Forward Reaction – Limiting Cases 209 5.7 Sabatier Principle – Volcano Plot 213 5.8 Concluding Remarks 214 Notation 216 Greek 217 Subscripts 217 Superscripts 217 Question 1 217 Question 2 218 Question 3 218 References 219 6 Catalytic Reaction Engineering 221Freek Kapteijn, Jorge Gascon, and T. Alexander Nijhuis 6.1 Introduction 221 6.2 Chemical Reactors 222 6.2.1 Balance and Definitions 222 6.2.2 Batch Reactor 224 6.2.2.1 Multiple Reactions 226 6.2.3 Continuous Flow Stirred Tank Reactor (CSTR) 228 6.2.4 Plug-Flow Reactor (PFR) 231 6.2.5 Comparison between Plug-flow and CSTR reactor 233 6.3 Reaction and Mass Transport 236 6.3.1 External Mass Transfer 237 6.3.2 Internal Mass Transport 242 6.3.3 Gas–Liquid Mass Transfer 248 6.3.4 Heat Transfer 254 6.4 Criteria to Check for Transport Limitations 257 6.4.1 Numerical Checks 257 6.4.2 Experimental Checks 260 Notation 264 Greek symbols 265 Subscripts 265 Question 1 265 Question 2 266 Question 3 267 References 269 7 Characterization of Catalysts 271Guido Mul, Frank de Groot, Barbara Mojet-Mol, and Moniek Tromp 7.1 Introduction 271 7.1.1 Importance of Characterization of Catalysts 271 7.1.2 Overview of the Various Techniques 271 7.2 Techniques Based on Probe Molecules 273 7.2.1 Temperature-Programmed Techniques 273 7.2.2 Physisorption and Chemisorption 275 7.3 Electron Microscopy Techniques 280 7.4 Techniques from Ultraviolet up to Infrared Radiation 283 7.4.1 UV/Vis Spectroscopy 283 7.4.2 Infrared Spectroscopy 286 7.4.3 Raman Spectroscopy 289 7.5 Techniques Based on X-Rays 291 7.5.1 Introduction 291 7.5.2 Interaction of X-Rays with Matter 293 7.5.3 X-Ray Photoelectron Spectroscopy (XPS) 294 7.5.4 X-ray Absorption Spectroscopy (XAS) 295 7.5.5 X-Ray Scattering 299 7.5.6 X-Ray Microscopy 302 7.6 Ion Spectroscopies 303 7.7 Magnetic Resonance Spectroscopy Techniques 304 7.7.1 NMR 304 7.7.2 EPR 306 7.8 Summary 310 Question 1 310 Question 2 311 Question 3 312 References 313 8 Synthesis of Solid Supports and Catalysts 315Petra de Jongh and Krijn de Jong 8.1 Introduction 315 8.2 Support Materials 317 8.2.1 Mesoporous Metal Oxides 318 8.2.2 Ordered Microporous Materials 326 8.2.3 Carbon Materials 331 8.2.4 Shaping 333 8.3 Synthesis of Supported Catalysts 333 8.3.1 Colloidal Synthesis Routes 334 8.3.2 Chemical Vapor Deposition 335 8.3.3 Ion Adsorption 338 8.3.4 Deposition Precipitation 341 8.3.5 Co-Precipitation 345 8.3.6 Impregnation and Drying 349 Question 1 357 Question 2 357 Question 3 358 References 358 Index 361

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Book SynopsisDiscover the latest research in photocatalysis combined with foundational topics in basic physical and chemical photocatalytic processes In Heterogeneous Photocatalysis: From Fundamentals to Applications in Energy Conversion and Depollution, distinguished researcher and editor Jennifer Strunk delivers a rigorous discussion of the two main topics in her field—energy conversion and depollution reactions. The book covers topics like water splitting, CO2 reduction, NOx abatement and harmful organics degradation. In addition to the latest research on these topics, the reference provides readers with fundamental information about elementary physical and chemical processes in photocatalysis that are extremely practical in this interdisciplinary field. It offers an excellent overview of modern heterogeneous photocatalysis and combines concepts from different viewpoints to allow researchers with backgrounds as varied as electrochemistry, material science, and semiconductor physics to begin developing solutions with photocatalysis. In addition to subjects like metal-free photocatalysts and photocarrier loss pathways in metal oxide absorber materials for photocatalysis explored with time-resolved spectroscopy, readers will also benefit from the inclusion of: Thorough introductions to kinetic and thermodynamic considerations for photocatalyst design and the logic, concepts, and methods of the design of reliable studies on photocatalysis Detailed explorations of in-situ spectroscopy for mechanistic studies in semiconductor photocatalysis and the principles and limitations of photoelectrochemical fuel generation Discussions of photocatalysis, including the heterogeneous catalysis perspective and insights into photocatalysis from computational chemistry Treatments of selected aspects of photoreactor engineering and defects in photocatalysis Perfect for photochemists, physical and catalytic chemists, electrochemists, and materials scientists, Heterogeneous Photocatalysis will also earn a place in the libraries of surface physicists and environmental chemists seeking up-to-date information about energy conversion and depollution reactions.Table of ContentsKinetic and Thermodynamic Considerations for Photocatalyst Design Design of Reliable Studies on Photocatalysis: Logic, Concepts and Methods In-Situ Spectroscopy for Mechanistic Studies in Semiconductor Photocatalysis Principles and Limitations of Photoelectrochemical Fuel Generation Photocatalysis - The Heterogeneous Catalysis Perspective Insights into Photocatalysis from Computational Chemistry Selected Aspects of Photoreactor Engineering Defects in photocatalysis Photocarrier Loss Pathways in Metal Oxide Absorber Materials for Photocatalysis Explored with Time-Resolved Spectroscopy: The Case of BiVO4 Metal-Free Photocatalysts Photocatalytic water splitting: Fundamentals and current concepts Photocatalytic CO2 reduction and beyond Photocatalytic NOx Abatement Photoactive Nanomaterials: Applications in Wastewater Treatment and their Environmental Fate

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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

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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

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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

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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

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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.

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Book SynopsisTransformation and Utilization of Carbon Dioxide shows the various organic, polymeric and inorganic compounds which result from the transformation of carbon dioxide through chemical, photocatalytic, electrochemical, inorganic and biological processes. The book consists of twelve chapters demonstrating interesting examples of these reactions, depending on the types of reaction and catalyst. It also includes two chapters dealing with the utilization of carbon dioxide as a reaction promoter and presents a wide range of examples of chemistry and chemical engineering with carbon dioxide. Transformation and Utilization of Carbon Dioxide is a collective work of reviews illustrative of recent advances in the transformation and utilization of carbon dioxide. This book is interesting and useful to a wide readership in the various fields of chemical science and engineering.Bhalchandra Bhanage is a professor of industrial and engineering chemistry at Institute of Chemical Technology, India.Masahiko Arai is a professor of chemical engineering at Hokkaido University, Japan.Table of ContentsPart I Chemical Reactions.- Addition of CO2 with molecular catalysts (metal complexes).- Addition of CO2 with molecular catalysts (other catalysts).- Direct CO2 fixation over heterogeneous catalysts.- Indirect CO2 fixation over heterogeneous catalysts (using urea and others).- Hydrogenation of CO2 with molecular catalysts (to alcohol, formate and others).- Hydrogenation of CO2 with heterogeneous catalysts (to alcohol, formate and others).- Dry CO2 reforming.- Polymerization.- Part II Photocatalytic, Electrochemical and Inorganic Reactions.- Photocatalytic reaction.- Electrochemical reaction.- Inorganic reaction (including CO2 storage).- Part III Biological Reactions.- Biological reaction.- Part IV Utilization as Reaction Promoter.- Application of CO2 as a reaction promoter in organic synthetic reaction.

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Book SynopsisThis multi-authored book provides a comprehensive overview of the latest developments in porous CO2 capture materials, including ionic liquid–derived carbonaceous adsorbents, porous carbons, metal-organic frameworks, porous aromatic frameworks, micro porous organic polymers. It also reviews the sorption techniques such as cyclic uptake and desorption reactions and membrane separations. In each category, the design and fabrication, the comprehensive characterization, the evaluation of CO2 sorption/separation and the sorption/degradation mechanism are highlighted. In addition, the advantages and remaining challenges as well as future perspectives for each porous material are covered.This book is aimed at scientists and graduate students in such fields as separation, carbon, polymer, chemistry, material science and technology, who will use and appreciate this information source in their research. Other specialists may consult specific chapters to find the latest, authoritative reviews.Dr. An-Hui Lu is a Professor at the State Key Laboratory of Fine Chemicals, School of Chemical Engineering, Faculty of Chemical, Environmental and Biological Science and Technology, Dalian University of Technology, China.Dr. Sheng Dai is a Corporate Fellow and Group Leader in the Chemical Sciences Division at Oak Ridge National Laboratory (ORNL) and a Professor of Chemistry at the University of Tennessee, USA.Table of ContentsIonic Liquid-Derived Carbonaceous Adsorbents for CO2 Capture.- Porous Carbons for Carbon Dioxide Capture.- Metal-Organic Frameworks (MOFs) for CO2 Capture.- Carbon Dioxide Capture in Porous Aromatic Frameworks.- Microporous Organic Polymers for Carbon Dioxide Capture.- CO2 capture via cyclic calcination and carbonation reactions.- Functionalized inorganic membranes for high temperature CO2/N2 separation.

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Book SynopsisThis book illustrates the broad field of enantioselective catalysis by highlighting a few topics, out of myriads, with the double aim to typify selected synthetic achievements and future challenges. Eleven research groups have highlighted topics of interest in either organo- or organometallic catalysis, related to their own expertise. For mature fields, these short chapters, far from being exhaustive, show updated overviews including major recent advances and disclose a few prospects. Other chapters focus on upcoming topics in enantioselective catalysis, i.e. on classes of reactions or families of catalysts that are expected to provide appealing synthetic tools when suitably mastered. For all these areas, recent studies demonstrate highly promising perspectives.

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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.

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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.

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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.

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