Table Of ContentMichele Aresta · Angela Dibenedetto
Eugenio Quaranta
Reaction
Mechanisms in
Carbon Dioxide
Conversion
Reaction Mechanisms in Carbon Dioxide
Conversion
ThiSisaFMBlankPage
Michele Aresta (cid:129) Angela Dibenedetto (cid:129)
Eugenio Quaranta
Reaction Mechanisms in
Carbon Dioxide Conversion
MicheleAresta AngelaDibenedetto
ChemicalandBiomolecular DepartmentofChemistryandCIRCC
EngineeringDepartment UniversityofBari
NUS Bari,Italy
Singapore,Singapore
CIRCC
Pisa,Italy
EugenioQuaranta
DepartmentofChemistryandCIRCC
UniversityofBari
Bari,Italy
ISBN978-3-662-46830-2 ISBN978-3-662-46831-9 (eBook)
DOI10.1007/978-3-662-46831-9
LibraryofCongressControlNumber:2015950373
SpringerHeidelbergNewYorkDordrechtLondon
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Lella, Gianluca, Brunella, Manuela, Mattia,
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Gianluca, Rosangela
Milena, Chiara
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Preface
Carbon dioxide (CO ) is today at the centre of attention of the scientific and
2
technological world because of its potential role in climate change, which is
supposed to be, directly or indirectly, caused by the growing level of CO in the
2
atmosphere. Policy-makers work out solutions ranging over a large number of
options, including carbon capture and disposal or sequestration (CCS) or carbon
captureandutilization(CCU).
TheconversionofCO intoadded-valueproducts(chemicals,materials,fuels)is
2
today one of the most widespread research themes, and the scientific literature
presents a large number of reviews, papers and books that disclose the CO
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chemistry or, in general, utilization. Industry is also much involved, as witnessed
bytheevergrowingnumberofindustrialpatentsandnewprocesses.
Despite the large number of volumes published, an organized collection of
information about the mechanisms concerning the many reactions in which CO
2
isinvolveddoesnotexist.However,thisbookhasbeendesignedwiththeprecise
idea of filling the gap and collecting the knowledge we have of the reaction
mechanism of CO conversion when it is used either as a building block for the
2
productionofchemicalsandmaterials,orasacarbonsourceforC1andCnenergy-
richmolecules.
Thisbookcovers40yearsofresearcheffortsinunderstandingthereactivityof
CO .ItsaimisnottopresentanexhaustivelistofallreactionsinwhichCO canbe
2 2
involved, even if it shows quite a large number of them, but to analyze the
thermodynamicsandkineticsofitsconversion.
The book is organized in ten chapters, each devoted to a particular subject.
Referencespointthereadertomorespecificissuesormoregeneralapplications.
Chapter1 presents the CO molecule and gives fundamental information for
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understanding the chemistry of the heterocumulene. It also discusses the excited
states of CO and its radical anion and radical cation. Such species are often
2
encountered in other chapters. The spectroscopic techniques (infrared, ultraviolet,
nuclearmagneticresonance)usedforcollectinginformationaboutthestateofthe
vii
viii Preface
CO moiety in the products are introduced here, and applied in the following
2
chapters.
Chapter2 discusses the co-ordination of CO to metal centres in various tem-
2
perature conditions and the effects of such interaction on the heterocumulene
structure. It addresses the question of whether preliminary co-ordination of CO
2
toametalcentreisanessentialprerequisiteforCO conversion.
2
In Chap.3 the interaction of CO with selected electron-rich moieties such as:
2
H–, OH(cid:1), NR (cid:1), R C(cid:1), RO(cid:1) and NRR0R00 is presented. This chapter discusses
2 3
reactions not mediated by a metal centre, which are discussed extensively in the
followingchapter.
Chapter4isdedicatedtotheanalysisoftheinteractionofCO withE–Xbonds,
2
whereE–X¼M–H,M–R,M–OH,M–OR,M–O ,M–M,C–C,C–O,N–H,N–C,N–
2
PandSi–H.Theanalysisofsuchelementarystepsisabridgetothemoregeneral
aspectofreactivityofCO .Suchreactionsillustratetheroleofmetalsininitiating
2
the reactions and give the fundamentals for understanding the use of CO in
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syntheticchemistryundercatalyticconditions.
Chapter5coversthetopicofCO interactionwithmultipleC–Cbonds(alkenes,
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alkynes,cumulenesandconjugateddienes)relevanttocarboxylationreactionswith
formation of new C–C bonds and to the synthesis of fine chemicals or
intermediates.
Chapter6isdedicatedtothesynthesisoforganiccarbonates,linearandcyclic,
molecular compounds and polymeric materials, and of polyurethanes. Organic
carbonates (monomeric) find a wide use in various sectors of the chemical and
energy industries. Polymers, which can be considered as chemical sinks of CO
2,
find a continuously growing application in architecture and are used for making
CDs, sanitary tools and laboratory glassware, among others.Polyurethanes play a
keyroleasinsulatorsandpackagingmaterials.
Chapter7 introduces the high-temperature processes of CO conversion: Dry
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Reforming of Methane (DRM) and the relevant general use of CO as oxidant or
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dehydrogenating (DH) agent. The conversion of CO into methanol is discussed
2
here as it has similarities to the other processes. Such applications deal with the
conversionoflargevolumesofCO intofuelsorenergy-richmolecules.
2
Chapter8 deals with the 1e(cid:1)(cid:1)2e(cid:1) transfer to CO in electrochemical, photo-
2
chemical, photo-electrochemical processes, a topic of great importance for the
conversion of CO into energy-rich molecules. This chapter is relevant to the use
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ofperennialenergysources,suchassolar,wind,geothermal,hydro-energy,inthe
conversion of large volumes of CO . The use of solar energy brings about the
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man-made photosynthesis (direct and indirect) which is the future technology for
theconversionoflargevolumesofCO intochemicalsandfuels.
2
Chapter9 makes the analysis of bioprocesses (enzyme catalysed reactions) in
which CO is converted. Carboxylation processes and reduction of CO to other
2 2
C1-molecules such as HCOOH, H CO, CH OH and CH are discussed here. A
2 3 4
comparisontochemicalprocessesdiscussedinpreviouschaptersisstraightforward.
Chapter10 presents quite a new subject: the properties of hydrate-CO . This
2
topicisafrontierresearchareaandhasgreatpotentialintherecoveryofmethane
Preface ix
from hydrates. Only a limited amount of information exists in the scientific and
technicalliterature,buttheinterestforfutureapplicationsisveryhigh.
Initsentirety,thisbookpresentstheessentialknowledgeoftheCO conversion
2
reaction mechanisms. We believe that it will be of great help to those who are
newcomersinthefascinatingfieldofcarbon-cycling(CO conversion)mimicking
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Natureandbeforallreadersaguidetodiscoveringaspectsoftherecenthistoryof
CO chemistry, atopicofgreatinterest todayfor its potential impact on avoiding
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CO emissionsandreducingfossilcarbonextraction.
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Theauthorswish tothankProf. SibudjingKawi andDr.YasothaKathiraserof
the Department of Chemical and Biomolecular Engineering of the National Uni-
versity of Singapore, Singapore, for their great help, having co-authored Chap.7,
and Prof. Praven Linga, Dr. Junjie Zheng and Ponnivalavan Babu of the same
Departmentforhavingco-authoredChap.10.
ThanksareduetoDr.AntonellaAngelini,DepartmentofChemistry-University
ofBari,Bari-IT,andDr.DanieleCornacchia,CIRCC-IT,fortheirassistance.
Michele Aresta is grateful to NUS, Chemical and Biomolecular Engineering
Department,fortheirverykindhospitalityduringthewritingofpartsofthisbook
andtoIC2Rforsomesupport.
Singapore-SG,June2015 MicheleAresta
Bari-IT,June2015 AngelaDibenedetto
EugenioQuaranta
