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Carbon Dioxide as Chemical Feedstock

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Preface . List of Contributors . 1 Carbon Dioxide: Utilization Options to Reduce its Accumulation in the Atmosphere ( Michele Aresta ). 1.1 Carbon Dioxide Emission . 1.2 The Accumulation of CO 2 in the Atmosphere, and the Effects that We Fear . 1.3 Technologies to Reduce CO 2 Accumulation in the Atmosphere . 1.4 The Utilization of CO 2 . 1.5 Conditions for Using CO 2 . 1.6 CO 2 : Sources and Prices . 1.7 The Potential for CO 2 Utilization, and the Content of This Book . 1.8 The Need for Research to Speed an Exploitation of the Utilization Option . References . 2 Utilization of Dense Carbon Dioxide as an Inert Solvent for Chemical Syntheses ( Alessandro Galia and Giuseppe Filardo ). 2.1 Introduction . 2.2 Dense Carbon Dioxide as Solvent Medium for Chemical Processes . 2.3 Enzymatic Catalysis in Dense Carbon Dioxide . 2.4 Other Reactions in Dense Carbon Dioxide . 2.5 Polymer Synthesis in Supercritical Carbon Dioxide . 2.6 Conclusions . Acknowledgments . References . 3 Autotrophic Carbon Fixation in Biology: Pathways, Rules, and Speculations ( Ivan A. Berg, Daniel Kockelkorn, W. Hugo Ramos-Vera, Rafael Say, Jan Zarzycki, and Georg Fuchs ). 3.1 Introduction . 3.2 The Mechanisms of CO 2 Fixation . 3.3 Rules to Explain the Diversity . 3.4 Evolutionary Aspects . 3.5 Chemical Aspects of CO 2 Fixation . Acknowledgments . References . 4 Carbon Dioxide Coordination Chemistry and Reactivity of Coordinated CO 2 ( Joelle Mascetti ). 4.1 Introduction . 4.2 Carbon Dioxide Bonding to Metals . 4.3 Synthesis and Structure of CO 2 Complexes . 4.4 Reactivity of CO 2 Complexes . 4.5 CO 2 Complexes as Reaction Intermediates in CO 2 Utilization Processes . 4.6 Conclusions . Acknowledgments . References . 5 Main Group Element- and Transition Metal-Promoted Carboxylation of Organic Substrates (Alkanes, Alkenes, Alkynes, Aromatics, and Others) ( Thomas Zevaco and Eckhard Dinjus ). 5.1 Introduction . 5.2 Formation of Aromatic Carboxylic Acids: The Kolbe-Schmitt Synthesis . 5.3 Reactive Organometallic Derivatives in the Synthesis of Carboxylic Acids . 5.4 Palladium (0)-Catalyzed Telomerization of Butadiene with CO 2 : Synthesis of delta-Lactone . References . 6 The Chemistry of N-CO 2 Bonds: Synthesis of Carbamic Acids and Their Derivatives, Isocyanates, and Ureas ( Eugenio Quaranta and Michele Aresta ). 6.1 Introduction . 6.2 Synthesis of Carbamic Acids and Alkylammonium Carbamates . 6.3 Synthesis of Carbamate Esters . 6.4 Synthesis of Isocyanates . 6.5 Synthesis of Ureas . 6.6 Conclusions . References . 7 Synthesis of Linear and Cyclic Carbonates ( Danielle Ballivet-Tkatchenko and Angela Dibenedetto ). 7.1 Introduction . 7.2 Acyclic Organic Carbonates . 7.3 Synthesis of Organic Cyclic Carbonates . 7.4 Transesterification Reactions . References . 8 Polymers from Carbon Dioxide: Polycarbonates, Polythiocarbonates, and Polyurethanes ( Donald J. Darensbourg, Jeremy R. Andreatta, and Adriana I. Moncada ). 8.1 Introduction . 8.2 Historical Perspective . 8.3 Metal Catalysts for the Copolymerization of Epoxides and CO 2 . 8.4 Metal Catalysts for the Copolymerization of Oxetanes and CO 2 . 8.5 Physical Methods for the Characterization of Copolymers Produced from Epoxides or Oxetane and Carbon Dioxide . 8.6 Copolymer Isolation and Catalyst Recycling . 8.7 Copolymerization of Carbon Disulfi de and Epoxides and Episulfides . 8.8 Copolymers from Aziridines and Carbon Dioxide . 8.9 Concluding Remarks . Acknowledgments . References . 9 In-Situ Study of Carbon Deposition during CO 2 Reforming of Methane for Synthesis Gas Production, Using the Tapered Element Oscillation Microbalance ( Wie Pan and Chunshan Song ). 9.1 Introduction . 9.2 Thermodynamic Analysis of Carbon Formation from CH 4 or CO . 9.3 Thermodynamic Analysis of Carbon Formation in CO 2 Reforming of Methane . 9.4 TEOM Measurement of Carbon Formation in CO 2 Reforming of Methane . 9.5 TPO Analysis of Carbon Formation in CO 2 Reforming . 9.6 TEM Analysis on Carbon Formed on Catalysts After CO 2 Reforming of Methane . 9.7 Kinetic Study of Carbon Formation on P CH4 and P CO in CO 2 Reforming . 9.8 H 2 O Effect on Carbon Formation in CO 2 Reforming . 9.9 Conclusions . Acknowledgments . References . Appendix A9.1 . 10 Utilization of Carbon Dioxide through Nonthermal Plasma Approaches ( Ji-Jun Zou and Chang-Jun Liu ). 10.1 Introduction . 10.2 Nonthermal Plasma Phenomena . 10.3 CO and/or H 2 Production from CO 2 . 10.4 Hydrocarbons Synthesis from CO 2 . 10.5 Oxygenates Synthesis from CO 2 . 10.6 Combination of Plasma with Catalyst . 10.7 Summary . Acknowledgments . References . 11 Photochemical, Electrochemical, and Photoelectrochemical Reduction of Carbon Dioxide ( Emily Barton Cole and Andrew B. Bocarsly ). 11.1 Introduction . 11.2 Homogeneous Photochemical Reduction . 11.3 Electrochemical Reduction . 11.4 Semiconductor Systems for Reduction . 11.5 Concluding Remarks and Future Directions . References . 12 Recent Scientific and Technological Developments in Electrochemical Carboxylation Based on Carbon Dioxide ( Giuseppe Silvestri and Onofrio Scialdone ). 12.1 Introduction . 12.2 Electrocarboxylation . 12.3 The Electroreduction of Carbon Dioxide in Protic Media (Water and Alcohols) . Acknowledgments . References . 13 Indirect Utilization of Carbon Dioxide: Utilization of Terrestrial and Aquatic Biomass ( Michele Aresta and Angela Dibenedetto ). 13.1 Introduction . 13.2 The Natural Carbon Cycle . 13.3 The Utilization of Terrestrial Biomass . 13.4 The First-Generation Biofuels . 13.5 The New Generations of Biofuels . 13.6 Implementation of the Biorefinery Concept . 13.7 Concluding Remarks . References . 14 Fixation of Carbon Dioxide into Inorganic Carbonates: The Natural and Artificial Weathering of Silicates ( Ron Zevenhoven and Johan Fagerlund ). 14.1 Introduction: Inorganic Carbonate Uses and Natural Resources . 14.2 Natural Fixation of CO 2 in Carbonates . 14.3 Process Routes to Valuable Carbonate Products . 14.4 Mineral Carbonation for Carbon Capture and Storage (CCS) . 14.5 Other Carbonate Production Processes and Applications . Acknowledgments . References . Index .

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Preface . List of Contributors . 1 Carbon Dioxide: Utilization Options to Reduce its Accumulation in the Atmosphere ( Michele Aresta ). 1.1 Carbon Dioxide Emission . 1.2 The Accumulation of CO 2 in the Atmosphere, and the Effects that We Fear . 1.3 Technologies to Reduce CO 2 Accumulation in the Atmosphere . 1.4 The Utilization of CO 2 . 1.5 Conditions for Using CO 2 . 1.6 CO 2 : Sources and Prices . 1.7 The Potential for CO 2 Utilization, and the Content of This Book . 1.8 The Need for Research to Speed an Exploitation of the Utilization Option . References . 2 Utilization of Dense Carbon Dioxide as an Inert Solvent for Chemical Syntheses ( Alessandro Galia and Giuseppe Filardo ). 2.1 Introduction . 2.2 Dense Carbon Dioxide as Solvent Medium for Chemical Processes . 2.3 Enzymatic Catalysis in Dense Carbon Dioxide . 2.4 Other Reactions in Dense Carbon Dioxide . 2.5 Polymer Synthesis in Supercritical Carbon Dioxide . 2.6 Conclusions . Acknowledgments . References . 3 Autotrophic Carbon Fixation in Biology: Pathways, Rules, and Speculations ( Ivan A. Berg, Daniel Kockelkorn, W. Hugo Ramos-Vera, Rafael Say, Jan Zarzycki, and Georg Fuchs ). 3.1 Introduction . 3.2 The Mechanisms of CO 2 Fixation . 3.3 Rules to Explain the Diversity . 3.4 Evolutionary Aspects . 3.5 Chemical Aspects of CO 2 Fixation . Acknowledgments . References . 4 Carbon Dioxide Coordination Chemistry and Reactivity of Coordinated CO 2 ( Joelle Mascetti ). 4.1 Introduction . 4.2 Carbon Dioxide Bonding to Metals . 4.3 Synthesis and Structure of CO 2 Complexes . 4.4 Reactivity of CO 2 Complexes . 4.5 CO 2 Complexes as Reaction Intermediates in CO 2 Utilization Processes . 4.6 Conclusions . Acknowledgments . References . 5 Main Group Element- and Transition Metal-Promoted Carboxylation of Organic Substrates (Alkanes, Alkenes, Alkynes, Aromatics, and Others) ( Thomas Zevaco and Eckhard Dinjus ). 5.1 Introduction . 5.2 Formation of Aromatic Carboxylic Acids: The Kolbe-Schmitt Synthesis . 5.3 Reactive Organometallic Derivatives in the Synthesis of Carboxylic Acids . 5.4 Palladium (0)-Catalyzed Telomerization of Butadiene with CO 2 : Synthesis of delta-Lactone . References . 6 The Chemistry of N-CO 2 Bonds: Synthesis of Carbamic Acids and Their Derivatives, Isocyanates, and Ureas ( Eugenio Quaranta and Michele Aresta ). 6.1 Introduction . 6.2 Synthesis of Carbamic Acids and Alkylammonium Carbamates . 6.3 Synthesis of Carbamate Esters . 6.4 Synthesis of Isocyanates . 6.5 Synthesis of Ureas . 6.6 Conclusions . References . 7 Synthesis of Linear and Cyclic Carbonates ( Danielle Ballivet-Tkatchenko and Angela Dibenedetto ). 7.1 Introduction . 7.2 Acyclic Organic Carbonates . 7.3 Synthesis of Organic Cyclic Carbonates . 7.4 Transesterification Reactions . References . 8 Polymers from Carbon Dioxide: Polycarbonates, Polythiocarbonates, and Polyurethanes ( Donald J. Darensbourg, Jeremy R. Andreatta, and Adriana I. Moncada ). 8.1 Introduction . 8.2 Historical Perspective . 8.3 Metal Catalysts for the Copolymerization of Epoxides and CO 2 . 8.4 Metal Catalysts for the Copolymerization of Oxetanes and CO 2 . 8.5 Physical Methods for the Characterization of Copolymers Produced from Epoxides or Oxetane and Carbon Dioxide . 8.6 Copolymer Isolation and Catalyst Recycling . 8.7 Copolymerization of Carbon Disulfi de and Epoxides and Episulfides . 8.8 Copolymers from Aziridines and Carbon Dioxide . 8.9 Concluding Remarks . Acknowledgments . References . 9 In-Situ Study of Carbon Deposition during CO 2 Reforming of Methane for Synthesis Gas Production, Using the Tapered Element Oscillation Microbalance ( Wie Pan and Chunshan Song ). 9.1 Introduction . 9.2 Thermodynamic Analysis of Carbon Formation from CH 4 or CO . 9.3 Thermodynamic Analysis of Carbon Formation in CO 2 Reforming of Methane . 9.4 TEOM Measurement of Carbon Formation in CO 2 Reforming of Methane . 9.5 TPO Analysis of Carbon Formation in CO 2 Reforming . 9.6 TEM Analysis on Carbon Formed on Catalysts After CO 2 Reforming of Methane . 9.7 Kinetic Study of Carbon Formation on P CH4 and P CO in CO 2 Reforming . 9.8 H 2 O Effect on Carbon Formation in CO 2 Reforming . 9.9 Conclusions . Acknowledgments . References . Appendix A9.1 . 10 Utilization of Carbon Dioxide through Nonthermal Plasma Approaches ( Ji-Jun Zou and Chang-Jun Liu ). 10.1 Introduction . 10.2 Nonthermal Plasma Phenomena . 10.3 CO and/or H 2 Production from CO 2 . 10.4 Hydrocarbons Synthesis from CO 2 . 10.5 Oxygenates Synthesis from CO 2 . 10.6 Combination of Plasma with Catalyst . 10.7 Summary . Acknowledgments . References . 11 Photochemical, Electrochemical, and Photoelectrochemical Reduction of Carbon Dioxide ( Emily Barton Cole and Andrew B. Bocarsly ). 11.1 Introduction . 11.2 Homogeneous Photochemical Reduction . 11.3 Electrochemical Reduction . 11.4 Semiconductor Systems for Reduction . 11.5 Concluding Remarks and Future Directions . References . 12 Recent Scientific and Technological Developments in Electrochemical Carboxylation Based on Carbon Dioxide ( Giuseppe Silvestri and Onofrio Scialdone ). 12.1 Introduction . 12.2 Electrocarboxylation . 12.3 The Electroreduction of Carbon Dioxide in Protic Media (Water and Alcohols) . Acknowledgments . References . 13 Indirect Utilization of Carbon Dioxide: Utilization of Terrestrial and Aquatic Biomass ( Michele Aresta and Angela Dibenedetto ). 13.1 Introduction . 13.2 The Natural Carbon Cycle . 13.3 The Utilization of Terrestrial Biomass . 13.4 The First-Generation Biofuels . 13.5 The New Generations of Biofuels . 13.6 Implementation of the Biorefinery Concept . 13.7 Concluding Remarks . References . 14 Fixation of Carbon Dioxide into Inorganic Carbonates: The Natural and Artificial Weathering of Silicates ( Ron Zevenhoven and Johan Fagerlund ). 14.1 Introduction: Inorganic Carbonate Uses and Natural Resources . 14.2 Natural Fixation of CO 2 in Carbonates . 14.3 Process Routes to Valuable Carbonate Products . 14.4 Mineral Carbonation for Carbon Capture and Storage (CCS) . 14.5 Other Carbonate Production Processes and Applications . Acknowledgments . References . Index .

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Preface . List of Contributors . 1 Carbon Dioxide: Utilization Options to Reduce its Accumulation in the Atmosphere ( Michele Aresta ). 1.1 Carbon Dioxide Emission . 1.2 The Accumulation of CO 2 in the Atmosphere, and the Effects that We Fear . 1.3 Technologies to Reduce CO 2 Accumulation in the Atmosphere . 1.4 The Utilization of CO 2 . 1.5 Conditions for Using CO 2 . 1.6 CO 2 : Sources and Prices . 1.7 The Potential for CO 2 Utilization, and the Content of This Book . 1.8 The Need for Research to Speed an Exploitation of the Utilization Option . References . 2 Utilization of Dense Carbon Dioxide as an Inert Solvent for Chemical Syntheses ( Alessandro Galia and Giuseppe Filardo ). 2.1 Introduction . 2.2 Dense Carbon Dioxide as Solvent Medium for Chemical Processes . 2.3 Enzymatic Catalysis in Dense Carbon Dioxide . 2.4 Other Reactions in Dense Carbon Dioxide . 2.5 Polymer Synthesis in Supercritical Carbon Dioxide . 2.6 Conclusions . Acknowledgments . References . 3 Autotrophic Carbon Fixation in Biology: Pathways, Rules, and Speculations ( Ivan A. Berg, Daniel Kockelkorn, W. Hugo Ramos-Vera, Rafael Say, Jan Zarzycki, and Georg Fuchs ). 3.1 Introduction . 3.2 The Mechanisms of CO 2 Fixation . 3.3 Rules to Explain the Diversity . 3.4 Evolutionary Aspects . 3.5 Chemical Aspects of CO 2 Fixation . Acknowledgments . References . 4 Carbon Dioxide Coordination Chemistry and Reactivity of Coordinated CO 2 ( Joelle Mascetti ). 4.1 Introduction . 4.2 Carbon Dioxide Bonding to Metals . 4.3 Synthesis and Structure of CO 2 Complexes . 4.4 Reactivity of CO 2 Complexes . 4.5 CO 2 Complexes as Reaction Intermediates in CO 2 Utilization Processes . 4.6 Conclusions . Acknowledgments . References . 5 Main Group Element- and Transition Metal-Promoted Carboxylation of Organic Substrates (Alkanes, Alkenes, Alkynes, Aromatics, and Others) ( Thomas Zevaco and Eckhard Dinjus ). 5.1 Introduction . 5.2 Formation of Aromatic Carboxylic Acids: The Kolbe-Schmitt Synthesis . 5.3 Reactive Organometallic Derivatives in the Synthesis of Carboxylic Acids . 5.4 Palladium (0)-Catalyzed Telomerization of Butadiene with CO 2 : Synthesis of delta-Lactone . References . 6 The Chemistry of N-CO 2 Bonds: Synthesis of Carbamic Acids and Their Derivatives, Isocyanates, and Ureas ( Eugenio Quaranta and Michele Aresta ). 6.1 Introduction . 6.2 Synthesis of Carbamic Acids and Alkylammonium Carbamates . 6.3 Synthesis of Carbamate Esters . 6.4 Synthesis of Isocyanates . 6.5 Synthesis of Ureas . 6.6 Conclusions . References . 7 Synthesis of Linear and Cyclic Carbonates ( Danielle Ballivet-Tkatchenko and Angela Dibenedetto ). 7.1 Introduction . 7.2 Acyclic Organic Carbonates . 7.3 Synthesis of Organic Cyclic Carbonates . 7.4 Transesterification Reactions . References . 8 Polymers from Carbon Dioxide: Polycarbonates, Polythiocarbonates, and Polyurethanes ( Donald J. Darensbourg, Jeremy R. Andreatta, and Adriana I. Moncada ). 8.1 Introduction . 8.2 Historical Perspective . 8.3 Metal Catalysts for the Copolymerization of Epoxides and CO 2 . 8.4 Metal Catalysts for the Copolymerization of Oxetanes and CO 2 . 8.5 Physical Methods for the Characterization of Copolymers Produced from Epoxides or Oxetane and Carbon Dioxide . 8.6 Copolymer Isolation and Catalyst Recycling . 8.7 Copolymerization of Carbon Disulfi de and Epoxides and Episulfides . 8.8 Copolymers from Aziridines and Carbon Dioxide . 8.9 Concluding Remarks . Acknowledgments . References . 9 In-Situ Study of Carbon Deposition during CO 2 Reforming of Methane for Synthesis Gas Production, Using the Tapered Element Oscillation Microbalance ( Wie Pan and Chunshan Song ). 9.1 Introduction . 9.2 Thermodynamic Analysis of Carbon Formation from CH 4 or CO . 9.3 Thermodynamic Analysis of Carbon Formation in CO 2 Reforming of Methane . 9.4 TEOM Measurement of Carbon Formation in CO 2 Reforming of Methane . 9.5 TPO Analysis of Carbon Formation in CO 2 Reforming . 9.6 TEM Analysis on Carbon Formed on Catalysts After CO 2 Reforming of Methane . 9.7 Kinetic Study of Carbon Formation on P CH4 and P CO in CO 2 Reforming . 9.8 H 2 O Effect on Carbon Formation in CO 2 Reforming . 9.9 Conclusions . Acknowledgments . References . Appendix A9.1 . 10 Utilization of Carbon Dioxide through Nonthermal Plasma Approaches ( Ji-Jun Zou and Chang-Jun Liu ). 10.1 Introduction . 10.2 Nonthermal Plasma Phenomena . 10.3 CO and/or H 2 Production from CO 2 . 10.4 Hydrocarbons Synthesis from CO 2 . 10.5 Oxygenates Synthesis from CO 2 . 10.6 Combination of Plasma with Catalyst . 10.7 Summary . Acknowledgments . References . 11 Photochemical, Electrochemical, and Photoelectrochemical Reduction of Carbon Dioxide ( Emily Barton Cole and Andrew B. Bocarsly ). 11.1 Introduction . 11.2 Homogeneous Photochemical Reduction . 11.3 Electrochemical Reduction . 11.4 Semiconductor Systems for Reduction . 11.5 Concluding Remarks and Future Directions . References . 12 Recent Scientific and Technological Developments in Electrochemical Carboxylation Based on Carbon Dioxide ( Giuseppe Silvestri and Onofrio Scialdone ). 12.1 Introduction . 12.2 Electrocarboxylation . 12.3 The Electroreduction of Carbon Dioxide in Protic Media (Water and Alcohols) . Acknowledgments . References . 13 Indirect Utilization of Carbon Dioxide: Utilization of Terrestrial and Aquatic Biomass ( Michele Aresta and Angela Dibenedetto ). 13.1 Introduction . 13.2 The Natural Carbon Cycle . 13.3 The Utilization of Terrestrial Biomass . 13.4 The First-Generation Biofuels . 13.5 The New Generations of Biofuels . 13.6 Implementation of the Biorefinery Concept . 13.7 Concluding Remarks . References . 14 Fixation of Carbon Dioxide into Inorganic Carbonates: The Natural and Artificial Weathering of Silicates ( Ron Zevenhoven and Johan Fagerlund ). 14.1 Introduction: Inorganic Carbonate Uses and Natural Resources . 14.2 Natural Fixation of CO 2 in Carbonates . 14.3 Process Routes to Valuable Carbonate Products . 14.4 Mineral Carbonation for Carbon Capture and Storage (CCS) . 14.5 Other Carbonate Production Processes and Applications . Acknowledgments . References . Index .

Key concepts: Raw material, Carbon dioxide, Waste management, Environmental science, Environmental chemistry, Chemistry, Pulp and paper industry, Engineering

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