Table Of ContentTopics in Current Chemistry 348
Massimo Marcaccio
Francesco Paolucci Editors
Making and
Exploiting
Fullerenes,
Graphene, and
Carbon Nanotubes
348
Topics in Current Chemistry
EditorialBoard:
H.Bayley,Oxford,UK
K.N.Houk,LosAngeles,CA,USA
G.Hughes,CA,USA
C.A.Hunter,Sheffield,UK
K.Ishihara,Chikusa,Japan
M.J.Krische,Austin,TX,USA
J.-M.Lehn,StrasbourgCedex,France
R.Luque,Co´rdoba,Spain
M.Olivucci,Siena,Italy
J.S.Siegel,NankaiDistrict,China
J.Thiem,Hamburg,Germany
M.Venturi,Bologna,Italy
C.-H.Wong,Taipei,Taiwan
H.N.C.Wong,Shatin,HongKong
Aims and Scope
TheseriesTopicsinCurrentChemistry presentscriticalreviews ofthepresent and
futuretrendsinmodernchemicalresearch.Thescopeofcoverageincludesallareasof
chemical science including the interfaces with related disciplines such as biology,
medicineandmaterialsscience.
Thegoalofeachthematicvolumeistogivethenon-specialistreader,whetherat
theuniversityorinindustry,acomprehensiveoverviewofanareawherenewinsights
areemergingthatareofinteresttolargerscientificaudience.
Thuseachreviewwithinthevolumecriticallysurveysoneaspectofthattopicand
placesitwithinthecontextofthevolumeasawhole.Themostsignificantdevelop-
mentsofthelast5to10yearsshouldbepresented.Adescriptionofthelaboratory
procedures involved is often useful to the reader. The coverage should not be
exhaustiveindata,butshouldratherbeconceptual,concentratingonthemethodolog-
icalthinkingthatwill allowthenon-specialistreaderto understandtheinformation
presented.
Discussionofpossiblefutureresearchdirectionsintheareaiswelcome.
Reviewarticlesfortheindividualvolumesareinvitedbythevolumeeditors.
Readership:researchchemistsatuniversitiesorinindustry,graduatestudents.
Moreinformationaboutthisseriesat
http://www.springer.com/series/128
Massimo Marcaccio Francesco Paolucci
l
Editors
Making and Exploiting
Fullerenes, Graphene,
and Carbon Nanotubes
With contributions by
(cid:1) (cid:1) (cid:1) (cid:1)
P. Bachawala L. Ballerini M. Bonchio S. Bosi
(cid:1) (cid:1) (cid:1)
E. Cadelano S. Campidelli L. Colombo
(cid:1) (cid:1) (cid:1)
C. Degli Esposti Boschi F. D’Souza A. Filoramo
(cid:1) (cid:1) (cid:1) (cid:1)
P. Fornasiero G. Gavrel D.R. Jones B. Jousselme
(cid:1) (cid:1) (cid:1) (cid:1)
L. Kavan W. Kutner J. Mack A. Mateo-Alonso
(cid:1) (cid:1) (cid:1) (cid:1)
M. Melchionna A. Migliori V. Morandi L. Ortolani
F. Paolucci (cid:1) A. Pe´nicaud (cid:1) M. Prato (cid:1) P.S. Sharma
Editors
MassimoMarcaccio
FrancescoPaolucci
Dept.ofChemistryG.Ciamician
UniversityofBologna
Bologna
Italy
ISSN0340-1022 ISSN1436-5049(electronic)
ISBN978-3-642-55082-9 ISBN978-3-642-55083-6(eBook)
DOI10.1007/978-3-642-55083-6
SpringerHeidelbergNewYorkDordrechtLondon
LibraryofCongressControlNumber:2014947108
#Springer-VerlagBerlinHeidelberg2014
Thisworkissubjecttocopyright.AllrightsarereservedbythePublisher,whetherthewholeorpartof
the material is concerned, specifically the rights of translation, reprinting, reuse of illustrations,
recitation,broadcasting,reproductiononmicrofilmsorinanyotherphysicalway,andtransmissionor
informationstorageandretrieval,electronicadaptation,computersoftware,orbysimilarordissimilar
methodologynowknownorhereafterdeveloped.Exemptedfromthislegalreservationarebriefexcerpts
inconnectionwithreviewsorscholarlyanalysisormaterialsuppliedspecificallyforthepurposeofbeing
enteredandexecutedonacomputersystem,forexclusiveusebythepurchaserofthework.Duplication
ofthispublicationorpartsthereofispermittedonlyundertheprovisionsoftheCopyrightLawofthe
Publisher’s location, in its current version, and permission for use must always be obtained from
Springer.PermissionsforusemaybeobtainedthroughRightsLinkattheCopyrightClearanceCenter.
ViolationsareliabletoprosecutionundertherespectiveCopyrightLaw.
The use of general descriptive names, registered names, trademarks, service marks, etc. in this
publicationdoesnotimply,evenintheabsenceofaspecificstatement,thatsuchnamesareexempt
fromtherelevantprotectivelawsandregulationsandthereforefreeforgeneraluse.
While the advice and information in this book are believed to be true and accurate at the date of
publication,neithertheauthorsnortheeditorsnorthepublishercanacceptanylegalresponsibilityfor
anyerrorsoromissionsthatmaybemade.Thepublishermakesnowarranty,expressorimplied,with
respecttothematerialcontainedherein.
Printedonacid-freepaper
SpringerispartofSpringerScience+BusinessMedia(www.springer.com)
Preface
Carbon nanostructures, or nanocarbons (CNSs), i.e. the low-dimensional nanoma-
terialsthatcomprise0Dfullerenes,1Dnanotubesand2Dgraphene,haveemerged
over the last two decades in the field of new molecular materials for their unique
structuralandelectronicproperties,promptingahugeinterestworldwidebothfrom
the viewpointof fundamental research and for their application in molecular elec-
tronics,materialsscience,energystorageandconversion,biomedicine,sensingand
biosensing. The electronic properties of CNSs and their optical, spectroscopic and
electrochemical behaviour depend markedly on their characteristic nanometric
dimensions;theidentificationofspecificquantitiesrelativetoindividualnanostruc-
turesinthebulkphasehasprovedchallengingandhasrequiredextremeingenuity.
Making solutions (or suspensions) of CNSs where the nanostructures could retain
most of their pristine properties has been a prerequisite for either fundamental
investigation or for the development of any viable technological exploitation of
such properties. This was the case, for example, of the application of bandgap
fluorescence spectroscopy of aqueous, micelle-like suspensions of single-walled
carbon nanotubes (SWNTs) that has given access to the electronic energies of
individualsemiconductingSWNTsasafunctionofstructurediameterandhelicity.
Insuchacontext,thechapter“SolubilizationofFullerenes,CarbonNanotubesand
Graphene” by AlainPe´nicauddescribes thevarious ingeniousapproaches tosolve
the solubility issue and describes in particular how graphite, and modern nanocar-
bons, can be made soluble by reductive dissolution. A large part of the present
volumeconcernsthemergingofnanocarbonswithnanotechnologyandtheirimpact
on technical development in many areas. Fullerenes, carbon nanotubes, nanodia-
mond and graphene find, for instance, various applications in the development of
solarcells,includingdyesensitizedsolarcells.Thechapter“IncorporationofBalls,
TubesandBowlsinNanotechnology”byJamesMackdescribestherecentdevelop-
ment of the area of fullerene fragments, and corannulene in particular, and their
directapplicationstoorganiclightemittingdiode(OLED)technology,while,inthe
chapter“ExploitingNanocarbonsinDye-SensitizedSolarCells”byLadislavKavan,
the exploitation of nanocarbons in the development of novel dye sensitized solar
cellswithimprovedefficiency,durabilityandcostsisthoroughlyreviewed.
v
vi Preface
ThefunctionalizationofCNSshastheinvaluableadvantageofcombiningtheir
uniquepropertieswiththoseofotherclassesofmaterials.Supramolecularchemis-
try represents an elegant alternative approach for the construction of functional
systems by means of noncovalent bonding interactions. In the chapter “Supramo-
lecular Chemistry of Carbon Nanotubes” by Gildas Gavrel et al., the incredibly
varied world of supramolecular, non-covalent functionalization of carbon nano-
tubesandtheirapplicationsisexaminedandreviewed,andthesyntheticstrategies
devised for fabricating mechanically-linked molecular architectures are described
inthechapter“Fullerene-StopperedBistableRotaxanes”byAurelioMateo-Alonso,
which presents an overview of the different types of fullerene-stoppered bistable
rotaxanes,theirswitchingmechanismandtheirpotentialapplications.
Inthechapter“Catalysis-MaterialCrosstalkatTailoredNano-CarbonInterfaces”
by Michele Melchionna et al., carbon nanomaterials are described as supports for
molecular and nanostructured catalysts, where their outstanding electronic and
opticalproperties,highsurfaceareaandthermalandmechanicalstabilitycontribute
tocreateasynergisticeffectthatleadstoenhancedperformanceforawiderangeof
possibleapplications.Exploitationofnanocarbonsinbiologyandbiomedicalappli-
cations has been increasingly proposed and, in particular, the chapter “Carbon
Nanotubes in Tissue Engineering” by Susanna Bosi et al. explores applications of
CNTsfortissueengineeringpurposes,wherethetubesprovedtobeidealmaterials
forthegrowthandproliferationofmanykindoftissues.
Thelocalchemicalreactivity,themechanicalpropertiesandtheelectrontransfer
ingraphenemembraneshavebeenshowntobestronglyaffectedbythefold-induced
curvature; thus in the chapter “Folds and Buckles at the Nanoscale: Experimental
andTheoreticalInvestigationoftheBendingPropertiesofGrapheneMembranes”by
Vittorio Morandi, a novel methodologytoinvestigate the mechanicalpropertiesof
foldedandwrinkledgraphenecrystals,whichcombinetransmissionelectronmicros-
copymappingandtheoreticalmodelling,isdescribed.Grapheneandnanocarbonsin
general are intensively investigated as platforms for the development of sensing
devicesfortheselectiveandhighlysensitivedetectionofbiohazards.Theaimofthe
chapter “Graphene and Graphene Oxide Materials for Chemo- and Biosensing of
ChemicalandBiochemicalHazards”byPiyushSindhuSharmaetal.isthentobring
out important advances of graphene-based sensors, with particular attention to the
rapiddetectionandquantizationoftoxins,explosives,pesticidesandpathogens.
Becauseoftheseveralanddiversetechnologicalapplicationssofarproposed,and
of the many more expected in the near future, the present volume is addressed to
researchersfromseveraldifferentareas:chemistryandmaterialschemistry,nanotech-
nology,medicineandindustrialresearch.Wehopetheywillenjoythepresentations
andfindinspirationfortheirresearchactivityinthefascinatingfieldofnanocarbons.
Finally,we would liketo thank Prof. MargheritaVenturiwho, as amemberof
theEditorialBoardofTopicsinCurrentChemistry,promotedthepreparationofa
volumeonthissubject.
Bologna,Italy MassimoMarcaccio
November2013 FrancescoPaolucci
Contents
SolubilizationofFullerenes,CarbonNanotubes,andGraphene ........... 1
AlainPe´nicaud
IncorporationofBalls,Tubes,andBowlsinNanotechnology ............. 37
DerekR.Jones,PraveenBachawala,andJamesMack
ExploitingNanocarbonsinDye-SensitizedSolarCells ..................... 53
LadislavKavan
SupramolecularChemistryofCarbonNanotubes ......................... 95
GildasGavrel,BrunoJousselme,AriannaFiloramo,andSte´phaneCampidelli
Fullerene-StopperedBistableRotaxanes ................................... 127
AurelioMateo-Alonso
Catalysis-MaterialCrosstalkatTailoredNano-CarbonInterfaces ...... 139
MicheleMelchionna,MarcellaBonchio,FrancescoPaolucci,
MaurizioPrato,andPaoloFornasiero
CarbonNanotubesinTissueEngineering .................................. 181
SusannaBosi,LauraBallerini,andMaurizioPrato
FoldsandBucklesattheNanoscale:ExperimentalandTheoretical
InvestigationoftheBendingPropertiesofGrapheneMembranes ...... 205
VittorioMorandi,LucaOrtolani,AndreaMigliori,
CristianDegliEspostiBoschi,EmilianoCadelano,andLucianoColombo
GrapheneandGrapheneOxideMaterialsforChemo-andBiosensing
ofChemicalandBiochemicalHazards ..................................... 237
PiyushSindhuSharma,FrancisD’Souza,andWlodzimierzKutner
Index .......................................................................... 267
vii
TopCurrChem(2014)348:1–36
DOI:10.1007/128_2013_520
#Springer-VerlagBerlinHeidelberg2014
Publishedonline:20March2014
Solubilization of Fullerenes, Carbon
Nanotubes, and Graphene
AlainPe´nicaud
Abstract Processing of novel carbon forms, i.e. fullerenes, nanotubes and
graphene,insolutionisdescribed.C andhigherfullerenesappeartobetheonly
60
trulysolubleformsofpurecarbon.Waystodispersecarbonnanotubesandgraphene
arereviewed.Truesolutionsofcarbonnanotubesandgraphenecanbeobtainedby
reductive dissolution, leading to solution of polyelectrolyte nanocarbons of high
concentrations without damaging the nanocarbon. Finally it is shown that these
solutions allow to obtain high performing materials such as highly conducting
transparentelectrodes.
Keywords C (cid:1) Carbon (cid:1) Dissolution (cid:1) Entropy (cid:1) Fullerenes (cid:1) GIC (cid:1) Graphene (cid:1)
60
Graphenide (cid:1) Graphite (cid:1) Individualization (cid:1) Nanotube salts (cid:1) Nanotubes (cid:1)
Nanotubide(cid:1)Solutions
Contents
1 Introduction................................................................................. 2
1.1 SizeIsImportant...................................................................... 3
2 FromDiamondandGraphitetoNanocarbonsorNanocarbonSizeVsSolubility....... 4
2.1 SomeNomenclature.................................................................. 4
3 TheSpecialCaseofC .................................................................... 5
60
4 StrategiestoDisperseCarbonNanotubes.................................................. 9
4.1 DispersionsinOrganicSolvents..................................................... 10
4.2 AqueousSuspensions................................................................. 11
5 ReductiveDissolutionofNanotubes....................................................... 11
5.1 SynthesisofNanotubeSalts.......................................................... 12
5.2 Individualization...................................................................... 13
5.3 DissolutionMechanism............................................................... 15
5.4 MultiwalledNanotubes............................................................... 17
A.Pe´nicaud(*)
CNRS,CentredeRecherchePaulPascal(CRPP),Universite´deBordeaux,UPR8641,
Pessac33600,France
e-mail:penicaud@crpp-bordeaux.cnrs.fr
2 A.Pe´nicaud
5.5 ReducedNanotubesforFunctionalization........................................... 17
5.6 SortingNanotubes.................................................................... 19
5.7 ElectrochemicalSynthesis............................................................ 20
6 GraphenideSolutions....................................................................... 20
7 NanoconesDissolution..................................................................... 25
7.1 CarbonNanocones.................................................................... 25
8 OxidativeDissolutionofNanocarbons..................................................... 27
9 ApplicationsandMaterialsfromNanocarbideSolutions................................. 28
9.1 Cryogels............................................................................... 28
9.2 FieldEffectTransistors............................................................... 29
9.3 Catalysts............................................................................... 29
9.4 TransparentConductingFilms....................................................... 29
10 ConclusionandPerspectives............................................................... 30
References........................................................................................ 31
Abbreviations
AFM Atomicforcemicroscopy
CNT Carbonnanotube
CoMoCAT ProcessinwhichcarbonnanotubesaresynthesizedwithCo/Mo
catalysts
DMSO Dimethylsulfoxide
GIC Graphiteintercalationcompound
GO Grapheneoxide
HiPCO Highpressurecarbonmonoxideprocesstosynthesizecarbon
nanotubes
HOPG Highlyorderedpyrolyticgraphene
NMP N-Methylpyrrolidone
PAH Polyaromatichydrocarbon
RGO Reducedgrapheneoxide
SCE Standardcalomelelectrode
SEM Scanningelectronmicroscopy
SWCNT Single-wallcarbonnanotube
TEM Transmissionelectronspectroscopy
THF Tetrahydrofuran
1 Introduction
Excluding metallic elements, carbon is one of the few elements of the Periodic
Tablethathasledtomanyfundamentallyimportantmaterials.Unlikemetals,carbon
exhibitsavarietyofvalencetopology,dependingonitshybridizationsp,sp2,orsp3,
and even intermediate hybridization. This has led to an amazing variety of nature,
appearance, and properties within carbon materials. Let’s mention graphite and
diamond, the former opaque, slippery, and conducting, the latter transparent, hard,
andinsulating.Importantcarbonmaterialsarenotrestrictedtographiteanddiamond.
