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Carbon Dioxide as Chemical Feedstock

Michele Aresta (Editor)
ISBN: 978-3-527-62992-3
414 pages
January 2010
Carbon Dioxide as Chemical Feedstock (3527629920) cover image
Filling the need for an up-to-date handbook, this ready reference closely investigates the use of CO2 for ureas, enzymes, carbamates, and isocyanates, as well as its use as a solvent, in electrochemistry, biomass utilization and much more.
Edited by an internationally renowned and experienced researcher, this is a comprehensive source for every synthetic chemist in academia and industry.
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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 CO2 in the Atmosphere, and the Effects that We Fear.

1.3 Technologies to Reduce CO2 Accumulation in the Atmosphere.

1.4 The Utilization of CO2.

1.5 Conditions for Using CO2.

1.6 CO2: Sources and Prices.

1.7 The Potential for CO2 Utilization, and the Content of This Book.

1.8 The Need for Research to Speed an Exploitation of the Utilization Option.


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.



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 CO2 Fixation.

3.3 Rules to Explain the Diversity.

3.4 Evolutionary Aspects.

3.5 Chemical Aspects of CO2 Fixation.



4 Carbon Dioxide Coordination Chemistry and Reactivity of Coordinated CO2 (Joëlle Mascetti).

4.1 Introduction.

4.2 Carbon Dioxide Bonding to Metals.

4.3 Synthesis and Structure of CO2 Complexes.

4.4 Reactivity of CO2 Complexes.

4.5 CO2 Complexes as Reaction Intermediates in CO2 Utilization Processes.

4.6 Conclusions.



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 CO2: Synthesis of δ-Lactone.


6 The Chemistry of N–CO2 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.


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.


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 CO2.

8.4 Metal Catalysts for the Copolymerization of Oxetanes and CO2.

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.



9 In-Situ Study of Carbon Deposition during CO2 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 CH4 or CO.

9.3 Thermodynamic Analysis of Carbon Formation in CO2 Reforming of Methane.

9.4 TEOM Measurement of Carbon Formation in CO2 Reforming of Methane.

9.5 TPO Analysis of Carbon Formation in CO2 Reforming.

9.6 TEM Analysis on Carbon Formed on Catalysts After CO2 Reforming of Methane.

9.7 Kinetic Study of Carbon Formation on PCH4 and PCO in CO2 Reforming.

9.8 H2O Effect on Carbon Formation in CO2 Reforming.

9.9 Conclusions.



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 H2 Production from CO2.

10.4 Hydrocarbons Synthesis from CO2.

10.5 Oxygenates Synthesis from CO2.

10.6 Combination of Plasma with Catalyst.

10.7 Summary.



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.


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).



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.


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 CO2 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.




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Michele Aresta is full Professor of Inorganic Chemistry at the University of Bari and Honorary Professor of the Tianjin University. He is President of the Inorganic Chemistry Division of Italian Chemical Society and Director of the "Interuniversity Consortium on Chemical Reactivity and Catalysis". His areas of research are carbon dioxide utilisation in synthetic chemistry, catalysis, coordination and metallorganic chemistry. Professor Aresta is author of more than 200 papers and editor of four books. He has received several awards, like the Award of the Italian Chemical Society and the Prize of the Société Francaise de Chimie for Inorganic Chemistry.
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