Reaction Mechanisms in Carbon Dioxide Conversion (eBook)

Michele Aresta, Angela Dibenedetto, Eugenio Quaranta (Autoren)

eBook Download: PDF

2015 | 1st ed. 2016
XVIII, 409 Seiten
Springer Berlin (Verlag)
978-3-662-46831-9 (ISBN)

Infos

This book provides an analysis of the reaction mechanisms relevant to a number of processes in which CO2 is converted into valuable products. Several different processes are considered that convert CO2 either in specialty chemicals or in bulk products or fuels. For each reaction, the mechanism is discussed and the assessed steps besides the dark sites of the reaction pathway are highlighted. From the insertion of CO2 into E-X bonds to the reduction of CO2 to CO or other C1 molecules or else to C2 or Cn molecules, the reactions are analysed in order to highlight the known and obscure reaction steps. Besides well known reaction mechanisms and energy profiles, several lesser known situations are discussed. Advancing knowledge of the latter would help to develop efficient routes for the conversion of CO2 into valuable products useful either in the chemical or in the energy industry. The content of this book is quite different from other books reporting the use of CO2. On account of its clear presentation, 'Reaction Mechanisms in Carbon Dioxide Conversion' targets in particular researchers, teachers and PhD students.

Inhalt

Preface 8
Contents 12
About the Authors 18
Chapter 1: The Carbon Dioxide Molecule 20
1.1 Introduction 20
1.2 Electronic Properties of CO2 21
1.2.1 Ground State of Carbon Dioxide 21
1.2.2 Lowest Excited States of Carbon Dioxide 25
1.3 Main Features of Carbon Dioxide Reactivity 27
1.3.1 Carbon Dioxide as O-Nucleophile 28
1.3.2 Carbon Dioxide as C-Electrophile 29
1.3.3 Amphoteric Reactivity of Carbon Dioxide 30
1.4 Carbon Dioxide Radical Anion, CO2- 31
1.5 Carbon Dioxide Radical Cation, CO2+ 38
1.6 Spectroscopic Techniques Applied to the CO2 States 39
1.6.1 IR Spectroscopy 39
1.6.2 UV Spectrum of Carbon Dioxide 41
1.6.3 Nuclear Magnetic Resonance (NMR) Spectroscopy 45
References 46
Chapter 2: CO2 Coordination to Metal Centres: Modes of Bonding and Reactivity 54
2.1 Mode of Bonding of Carbon Dioxide to Transition-Metal Centres 54
2.2 XRD Structure of eta2-C,O Mononuclear Metal Complexes 56
2.3 XRD Structural Data for eta1-C Metal Complexes 60
2.4 XRD Structural Characterization of O-End-On Complexes 62
2.5 Multinuclear Complexes 62
2.5.1 Side-On Bonded Complexes 62
2.5.2 O-End-On Bonded Complexes 63
2.6 Spectroscopic (IR and 13C-NMR) Data for the Complexes Correlated to the Various Modes of Bonding of CO2 66
2.6.1 Infrared Data Relevant to Transition Metal Complexes 66
2.6.2 NMR Data for Transition Metal Complexes 68
2.7 Fluxionality of the CO2 Molecule Coordinated to Transition Metal Systems 70
2.8 Interaction of CO2 with Metal Atoms in Low-Temperature Solid-Inert-Gas Matrices 74
2.9 Interaction of Metal Cations with CO2 in the Gas Phase 76
2.10 Reactions of Coordinated CO2 77
2.10.1 Reaction of Coordinated CO2 with Electrophiles and O-Transfer from CO2 to Produce CO 78
2.10.2 Reactions of Coordinated CO2 with Nucleophiles 82
2.11 Conclusions 83
References 83
Chapter 3: Interaction of CO2 with Electron-Rich Moieties 89
3.1 Reaction with the Hydride Ion 89
3.2 Reaction with Hydroxide and Alkoxide Species 90
3.3 Reaction with Carbanions 91
3.4 Reaction with Amines 92
References 100
Chapter 4: Insertion of CO2 into E-X Bonds 103
4.1 Carbon Dioxide Insertion into M-H Bonds 103
4.2 CO2 Insertion into M-OH Bonds 109
4.3 CO2 Insertion into M-C Bonds 113
4.4 CO2 Insertion into M-OR Bonds 115
4.5 Insertion into M-O2 Bonds 116
4.6 CO2 Insertion into M-N Bonds 120
4.6.1 Insertion into Transition Metal Amides 120
4.6.2 Insertion into Main Group and Post-Transition Metal Amides 126
4.6.3 Insertion into Amides of Non-Metallic Elements 130
4.7 CO2 Insertion into M-P Bonds 133
4.8 CO2 Insertion into C-C Bonds 135
4.9 CO2 Insertion into C-N Bonds 138
4.10 Insertion into Other E-X Bonds 145
4.10.1 Insertion into M-M Bonds 145
4.10.2 Insertion into Si-H Bonds 146
4.10.3 Insertion into C-H Bonds 147
4.11 Conclusions 149
References 149
Chapter 5: Interaction of CO2 with C-C Multiple Bonds 160
5.1 Introduction 160
5.2 Oxidative Coupling with CO2 161
5.3 Carboxylation of Olefins 164
5.4 Carboxylation of Alkynes 173
5.5 Carboxylation of Allenes 181
5.6 Carboxylation of Conjugated Dienes 186
References 193
Chapter 6: Reaction Mechanisms in the Direct Carboxylation of Alcohols, Polyols, Cyclic Ethers, and Cyclic Amines to Afford Mo... 200
6.1 Utilization of Organic Carbonates and Conventional Synthetic Routes 200
6.2 Direct Carboxylation of Alcohols 202
6.2.1 Thermodynamic and Kinetic Issues 202
6.2.2 Reaction Mechanism 204
6.2.2.1 Homogeneous and Heterogenized Catalysts 205
6.2.2.2 Heterogeneous Catalysts 211
6.2.2.2.1 Water Removal Techniques 217
6.2.2.3 Organic Promoters 218
6.2.2.4 Urea as an Active Form of CO2 225
6.3 Direct Carboxylation of Diols and Polyols 227
6.4 Oxidative Carboxylation of Olefins to Afford Cyclic Carbonates 230
6.5 Carboxylation of Cyclic Ethers 233
6.5.1 Synthesis of Monomeric Cyclic Carbonates 234
6.5.2 Synthesis of Polycarbonates 238
6.6 Formation of Polyurethanes: Carboxylation of Cyclic Amines 240
6.7 Conclusions 242
References 243
Chapter 7: Carbon Dioxide Conversion in High Temperature Reactions 253
7.1 Introduction 253
7.2 CO2 as Oxidant 254
7.2.1 OCM Promoted by CO2 254
7.2.1.1 Catalytic Systems for CO2-OCM 255
7.2.1.2 Reaction Mechanism for CO2-OCM 257
7.2.2 Oxidative Dehydrogenation of Alkanes 259
7.2.2.1 Catalytic Systems for CO2-ODH of Alkanes 260
7.2.2.2 Reaction Mechanism for CO2-ODH of Alkanes 264
7.2.2.2.1 Redox Mechanism 264
7.2.2.2.2 Surface Reactions for Removal of Hydrogen via RWGS 266
7.2.3 Oxidative Dehydrogenation of Ethylbenzene to Styrene 270
7.2.3.1 Catalytic Systems for CO2-ODE to Styrene 272
7.2.3.2 Reaction Mechanism for CO2-ODE to Styrene 274
7.2.4 CO2 (Dry) Reforming of Methane 281
7.2.4.1 Catalytic Systems for the DRM Process 283
7.2.4.2 Reaction Mechanism for the DRM Process 287
7.2.4.2.1 Methane Activation 288
7.2.4.2.2 CO2 Activation 290
7.2.4.3 Kinetic Modeling for the DRM Process 292
7.3 Hydrogenation of CO2 293
7.3.1 Reverse Water Gas Shift Reaction (RWGS) 294
7.3.2 CO2 Hydrogenation to Methanol and DME 294
7.3.2.1 Methanol 294
7.3.2.2 DME 295
7.3.3 Catalytic Systems for CO2 Hydrogenation 296
7.3.4 Reaction Mechanism for CO2 Hydrogenation 301
7.3.4.1 Reaction Mechanism for RWGS 301
7.3.4.1.1 Surface Redox Mechanism 301
7.3.4.1.2 Dissociative Mechanism 302
7.3.4.2 Reaction Mechanism for Methanol Synthesis 303
7.3.4.3 Reaction Mechanism for DME Synthesis 309
7.4 Conclusions 311
References 312
Chapter 8: One- and Multi-electron Pathways for the Reduction of CO2 into C1 and C1+ Energy-Richer Molecules: Some Thermodynam... 327
8.1 Introduction 327
8.2 Key Steps and Aspects in CO2 Reduction 328
8.3 One-Electron Transfer to CO2 vs Multi-electron Transfer 337
8.4 Competitive Coordination of CO2 and H+ to a Catalytic Centre and Their Reduction 338
8.5 Sequential ``One-Electron Plus One-Proton´´ Pathways in Multi-electron Reduction of Bound CO2 342
8.6 Photochemical and Photoelectrochemical Reduction of CO2 348
8.7 Perspective Electrochemical, Photochemical and Photoelectrochemical Reduction of CO2 355
References 356
Chapter 9: Enzymatic Conversion of CO2 (Carboxylation Reactions and Reduction to Energy-Rich C1 Molecules) 362
9.1 Introduction 362
9.2 CO2 Fixation in Biosynthesis 363
9.2.1 Calvin-Benson-Bassham-Cycle 364
9.2.2 Reductive TCA (Arnon-Buchanan) Cycle 365
9.2.3 Reductive Acetyl-CoA (Wood-Ljungdahl) Pathway 365
9.2.4 Acyl-CoA Carboxylation Pathways 366
9.3 Carboxylation Reactions 368
9.3.1 Bio-Carboxylation of Aromatic and Hetero-Aromatic Compounds 368
9.3.2 Bio-Carboxylation of Epoxides 372
9.4 Reduction Reactions 373
9.4.1 Carbon Monoxide Dehydrogenases 373
9.4.2 Formate Dehydrogenases 375
9.4.3 Formaldehyde Dehydrogenase 375
9.4.4 Alcohol Dehydrogenases 376
9.4.5 Production of Acetic Acid 376
9.4.6 Reduction of CO2 to Carbon Monoxide or Formate 377
9.4.7 Bioconversion of Carbon Dioxide into Methanol 379
References 381
Chapter 10: Thermodynamics and Applications of CO2 Hydrates 387
10.1 Introduction 387
10.2 Structure of Gas Hydrates 390
10.2.1 Formation of Gas Hydrates from a Microscopic Perspective 390
10.2.2 Crystal Structures of Gas Hydrates 392
10.2.3 Characteristics of CO2 Hydrates 395
10.3 Physical Properties of CO2 Hydrates 396
10.3.1 Mechanical Properties 398
10.3.2 Thermal Properties 398
10.3.3 Other Physical Properties 400
10.4 Phase Equilibrium of CO2 Hydrate 400
10.4.1 Experimental Methods to Study Hydrate Phase Equilibria 400
10.4.1.1 Temperature Search Method 401
10.4.1.2 Pressure Search Method 401
10.4.1.3 Isochoric P-T Cycle 401
10.4.1.4 Calorimetric Method 402
10.4.2 Pressure-Temperature Phase Diagram of CO2+H2O System 403
10.5 Applications of CO2 Hydrates 404
10.5.1 Formation of CO2 Hydrate 404
10.5.2 Dissociation of CO2 Hydrate 405
10.5.3 CO2 Capture and Sequestration 406
10.5.4 Replacement of CH4 by CO2 in Naturally Occurring Hydrates 409
10.5.5 CO2 Hydrates in Refrigeration Processes 410
References 413
Index 417

Produkt-Details

• Erscheint lt. Verlag: 7.11.2015
• Zusatzinfo: XVIII, 409 p. 288 illus., 67 illus. in color.
• Verlagsort: Berlin
• Sprache: englisch
• Themenwelt: Naturwissenschaften ► Chemie ► Organische Chemie
• Themenwelt: Naturwissenschaften ► Physik / Astronomie
• Themenwelt: Technik
• Schlagworte: Carbon dioxide molecular orbitals • climate change • CO2 coordination to metal centres • CO2 electrochemical reduction • CO2 enzymatic conversion • CO2 insertion into 11-X • CO2 photocatalytic reduction • CO2 spectroscopic techniques • Michele Aresta
• ISBN-10: 3-662-46831-X / 366246831X
• ISBN-13: 978-3-662-46831-9 / 9783662468319