Nanocarbon-Inorganic Hybrids: Next Generation Composites for Sustainable Energy Applications

537 Pages·2014·12.562 MB·English

by  Dominik Eder, Robert Schlögl (eds.)

Eder,Schlögl(Eds.)
Nanocarbon-InorganicHybrids
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RobertSchlögl(Editor-in-Chief)
ISSN1869-8778
Nanocarbon-
Inorganic
Hybrids
|
Next GenerationComposites for Sustainable
Energy Applications
Edited by
Dominik Eder and Robert Schlögl
Editors
Prof.DominikEder
WestfälischeWilhelmsUniversity
DepartmentofPhysicalChemistry
Correnstr.28/30
48149Münster
Germany
Prof.RobertSchlögl
FritzHaberInstituteoftheMaxPlanckSociety
DepartmentofInorganicChemistry
Faradayweg4–6
14195Berlin
Germany
ISBN978-3-11-026971-0
e-ISBN978-3-11-026986-4
Set-ISBN978-3-11-026987-1
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Preface
Today’sworldisfacingmajorchallengesthatdirectlyafectourmodernlife.Thede-
mandforenergyisexpectedtodoublebytheyear2050.Asaconsequenceofincreased
energyutilizationtheneedisgrowingtoprotectourenvironmentfromtheadverseef-
fectsofpollutionandthedestructionofnaturalhabitats.Toensuresufficientsupply
ofcleanwaterandair andtonourishthegrowingpopulationwithoutconlictsand
povertyareadditionalglobalchallenges.Inthisarena,thetransformationofthefos-
silenergysystemintoasustainable operation and thetechnical increase ofenergy
efficiencyarekeyobjectivesofchemicalscienceswiththeirabilitytocreatenovelfu-
els,materialsandprocessesofmoleculartransformations.Usingtheenergyofsun-
lighttosplitwaterintohydrogenasacleanenergysourceandstoringenergyinbatter-
iesandsupercapacitorsaretwopopularexamplesofenergyscience.Bothchallenges
criticallyinvolvetheavailabilityofnovelcarbonmaterials.Carbonisthemostversa-
tilechemicalelementfordesigningmoleculesandmaterials.Itenablesustoaddress
awiderangeoffunctionalcharacteristicsbyvaryingtheassemblyofonlyonetypeof
atomsinteractingwitheachotherinessentiallyonlytwobindingmodes,i.e.sp2/sp3
hybridization.
Theunlimitednumberofcombinationsofthetwobasicbondingmotivesallows
therealizationofmolecularandsupra-molecularpropertieslimitedonlybyourimagi-
nation.Hetero-atomicadditionstothecarbonbackbonegiveadditionalchemicaland
structuraldiversitythatneedsexploitationininterface-controlledmaterialscienceap-
plications.Theinterplaybetweencombiningbuildingblocksofcarbonanddecorat-
ingtheproductswithhetero-elementsformsthebasisofaknowledge-basedcarbon
materialscience.Acriticalstrategyofmaterialdesignistocombinecarbonwithother
materialswithdivergingproperties intospatialarrangementsthatcreatesynergistic
functions.Such materials,known as composites, were developed for carbon-based
systemswiththematuration of polymer science and are implemented todayin nu-
merousproductsrangingfrommaterialsforpackaging,dentalandmedicaluse,en-
ergyproductionandstorage,tostructuralmaterialsforlightweightapplications.
Nanocarboncompositesaremultiphasematerials,inwhichananostructuredfiller
(i.e.particles,whiskers,fibers,nanotubesorlamellae)isdispersedinanorganic(i.e.
polymer) or inorganic (i.e. carbon, ceramic or metal) matrix. In the last few years,
carbon in the form of nanotubes (CNTs) in addition to nanostructured fibers or as
graphenehasattractedwideinterestasafillerfornanocomposites.Typicalapplica-
tionprofilesareahighelectricalconductivityintransparentconductingpolymersora
remarkablefracturetoughnessreinforcingceramicssuchashydroxyapatiteforbone
replacement.Nanocomposites have a considerable impact onlarge-scale industrial
applicationsoflightweightstructuralmaterialsinaerospaceande-mobility,ofelec-
tricallyconductingplasticsforelectronicapplicationsoraspackagingmaterialswith
reducedgaspermeabilityforfoodstufandair-sensitivegoods.
vi | Preface
Nanocarbonhybridsareanewclassofcompositematerialsinwhichthecarbon
nanostructures are compounded with thin layers of metals, semiconductors, inor-
ganic glasses or ceramics. Thecarbon component gives ready access for gasesand
luidstoalargefractionoftheinnersurfaceareaoftheinorganiccompound.Inad-
dition,alargeinterfacebetweentwomaterialswithdiferentbulkproperties allows
forthedesignofmaterialswithinterface-dominatedproperties.Theirspecialappeal
arisesfromchargeandenergytransferthroughthisinterface,givingrisetotransport
properties diferent from the linear combination of the respective bulk properties.
Althoughstillatanearlystageofresearch,suchhybridmaterialshavedemonstrated
potential in applications concerning energy conversion and environmental protec-
tion.Theseincludeimprovedsensitivitiesinbio/chemicalsensors,increasedenergy
densitiesinbatteriesandlargercapacitiesinsupercapacitors,highercurrentsinfield
emission devices, more efficient charge separation and thus superior activities in
photocatalystsandimprovedefficienciesinphotovoltaics.
Thisbookisdedicatedexclusivelytothefamilyofnanocarbonhybridscoveringa
multidisciplinaryresearchfieldthatcombinesmaterialschemistryandphysicswith
nanotechnologyandappliedenergysciences.Itprovidesbothintroductorymaterial
onfundamentalprinciples aswellasreviewsofthecurrentresearch.Therefore,this
bookshouldbehelpfulforMasterandPhDstudentswishingtobecomefamiliarwith
amodernfieldofknowledge-drivenmaterialscienceaswellasforseniorresearchers
andindustrialstafscientistswhoexplorethefrontiersofknowledge.
Thefirst part ofthis bookintroducestheconcept ofnanocarbons asbuilding
blocks.Itestablishesascientificfoundationfortheirsubsequentuseinhybridsand
composites.Chapter1providesaconciseintroductionintotheworldofcarbonnano-
tubes(CNTs),explainingtheiruniquestructuralcharacteristics,synthesisroutesand
keycharacterizationtechniques.Itsummarizestheprofileofexceptionalpropertiesof
CNT.Chapter2concentratesonthesynthesisandcharacterizationofgraphene-based
materials,includingsingle-layerand few-layergraphene as wellas graphene oxide
anditschemically/thermallyreducedcounterpart.Thechapterfurtherdemonstrates
that the dispersion of nanocarbons remains a key challenge for their implementa-
tionintohybrids.Chapters3and4arededicatedtothepost-synthesis processingof
nanocarbons. In particular, Chapter3 focuses on the chemical functionalization of
CNTs,providingexamplesforawholerangeofcovalentandnoncovalentfunctional-
izationroutes.Chapter4ofersacomprehensivereviewondopingandfillingofCNTs
andtheefectofdefectsonthehybridizationofCNTswithpolymers.
Thesecondpart ofthisbook,comprisingChapters5to10,isdedicated tothe
synthesisofnanocarbonhybridsandcomposites.Chapter5beginsbyidentifyingthe
generalsynthesisroutestowardsnanocarbonhybrids,whichcanbecategorizedinto
exsitu(i.e.“buildingblock”)andinsituapproaches,andcomparingtheiradvantages
anddisadvantagesonthebasisofsomeofthemostintriguingrecentresults.Ingen-
eral,theexsiturouteisatwo-stepprocessinwhichtheinorganiccompoundissynthe-
sizedfirst,takingadvantageoftheexistingwealthofknowledgeinsynthesizingnano-
Preface | vii
materials(i.e.structure-property relationship). Inasecondstep,theinorganic com-
poundislinkedtothenanocarbonsurfaceviacovalent,noncovalentorelectrostatic
interactions.Intheinsituapproachtheinorganicorpolymericcompoundisgrownon
the(modified)nanocarbonsurfacefrommolecularprecursorsvia(electro)chemical,
vapor-based or physical deposition techniques, exploiting the stabilizing efects of
nanocarbonastemplatesandaslocalheatsinks.
The examples discussed in Chapter 5 cover a wide range of synthetic aspects,
yet concentrate on hybrids involving CNTs,while Chapter6 summarizes recent de-
velopmentsonthehybridizationofgraphene-basedmaterials.Chapter7ontheother
handintroducessustainablecarbonmaterialsmadefromhydrothermalcarbonization
(HTC)aspromisingcandidatesforhybridmaterials.Chapter8thencombinesnanocar-
bonswithpolymersanddocumentsthatengineeringtheinterfacesisachallengethat
isequallyimportantinthesynthesisofnanocarbonhybridsandofcarboncomposites.
ThebooksectionisconcludedbyChapters9and10,whicharededicatedtospeciic
examplesofhybrids.Chapter9describes hybridswhosecomponentsareallcarbon
based,suchasCNTshybridizedwithgraphene,whileChapter10discussestheincor-
porationofgrapheneoxideintometal-organicframeworkstructures(MOFs).
The third part of thebookhighlightsthe potentialofnanocarbon hybrids for
variousimportantapplications,particularly concerningenvironmentalandsustain-
ableenergyapplications.Theseincludeelectrodematerialsinbatteriesandelectro-
chemicalcapacitors (Chapters11and12), sensorsand emittersinfieldemission de-
vices (Chapter13), electrocatalysts in fuelcells (Chapter14), supports for heteroge-
neouscatalysts(Chapter15),next-generation photocatalysts(Chapter16),aswellas
activecompoundsinelectrochromicandphotovoltaicapplications(Chapters17and
18).Allthesechaptersdiscussthebenefitsofnanocarbonhybridsintherespectiveap-
plication,identifymajorchallengesandcriticallyreviewthepresentstateofresearch
withthemostintriguing recentdevelopments.Finally,Chapter19elaboratesonthe
importanceofdefectsandedgeatomsingraphene-basedhybridmaterials.
Thisbookillustratesthatnanocarbonhybridmaterialsareanexcitingnewclassof
multi-purposecompositeswithgreatpotentialtobecomethenext-generationenergy
materials.Thesynergisticefectsinnanocarbon hybridsaremanifoldanditisclear
thatadetailedfundamentalunderstandingoftheiroriginswillbeessentialtoexploit
theoptionsgivenbycombiningclassesofmaterialswithdivergingproperties.
We foremostexpress ourdeepest thankstoourcolleagueswhospent consider-
abletimeandefortinwritingthechaptersinthisbook.Wehopethatthisbookwill
beusefultothoseinterestedinthesubjectofnanocarbonhybridsfrommanydifer-
entperspectivesandthatitwillestablishasoundfoundationforfutureresearch.We
furtherwouldliketothankJuliaLauterbachandKarinSoraofDeGruyterPublishers
fortheirtirelesssupportandguidance.Itisaparticularpleasuretoacknowledgethe
studentsoftheMünstergroupfortheirinvaluablehelpinproof-reading.
June2014 DominikEderandRobertSchlögl
Contents
Preface|v
Contributingauthors|xvii
PartI: Nanocarbonbuildingblocks
PaulGebhardtandDominikEder
1 Ashortintroductiononcarbonnanotubes|3
1.1 Introduction|3
1.2 Structuralaspects|4
1.2.1 Chirality|4
1.2.2 Defects|5
1.2.3 Doping|6
1.3 PropertiesofCNTs|7
1.3.1 Mechanicalproperties|7
1.3.2 Electronicproperties|8
1.3.3 Thermalproperties|9
1.4 Characterization|10
1.5 Synthesis|11
1.5.1 Laserablation|12
1.5.2 Arcdischarge|12
1.5.3 Moltensaltroute/electrolyticprocess|13
1.5.4 Chemicalvapordeposition(CVD)|13
1.6 Post-synthesistreatments|14
1.6.1 Purification|14
1.6.2 SeparationofmetallicandsemiconductingCNTs|15
1.6.3 Functionalization |16
1.6.4 Assembly|18
1.7 Summary|18
KeithPaton
2 Synthesis,characterisationandpropertiesofgraphene|25
2.1 Introduction|25
2.2 Properties|25
2.3 Synthesis|26
2.3.1 Micromechanicalcleavage|26
2.3.2 Liquidphaseexfoliation|27
2.3.3 Precipitationfrommetals/CVD|30
2.3.4 EpitaxialgrowthfromSiC|31
2.4 Characterization|32
x | Contents
MicheleMelchionnaandMaurizioPrato
3 Functionalizationofcarbonnanotubes|43
3.1 Introduction|43
3.2 Functionalization.Why?|44
3.3 Typesoffunctionalization|46
3.3.1 Covalentfunctionalization|46
3.3.2 Noncovalentfunctionalization|54
3.4 Functionalizationwithmetals|61
3.5 Summary|65
S.M.Vega-Diaz,F.TristánLópez,A.Morelos-Gómez,R.Cruz-Silva,andM.Terrones
4 Theimportanceofdefectsanddopantswithincarbonnanomaterialsduring
thefabricationofpolymercomposites|71
4.1 Introduction|71
4.1.1 Carbonnanostructuresandtheirproperties |72
4.1.2 Dopedcarbonnanostructures|74
4.1.3 Defectsincarbonnanostructures|76
4.1.4 Functionalizationofcarbonnanostructuresfornanocomposites|79
4.2 Incorporationofnanocarbonsintopolymercomposites
andhybrids|83
4.2.1 Typesofpolymercomposites|83
4.2.2 Synthesisapproaches|86
4.3 Properties|89
4.3.1 Mechanicalproperties|89
4.3.2 Thermalproperties|93
4.3.3 Electricalproperties|95
4.3.4 Opticalproperties|97
4.3.5 Biocompatibility|98
4.3.6 Biodegradation|99
4.3.7 Permeability|102
4.4 Summary|104
PartII: Synthesisandcharacterisationofhybrids
CameronJ.ShearerandDominikEder
5 Synthesisstrategiesofnanocarbonhybrids|125
5.1 Introduction|125
5.2 Exsituapproaches|127
5.2.1 Covalentinteractions|127
5.2.2 Noncovalentinteractions|129
5.3 Insituapproaches|134
5.3.1 Insitupolymerization|135