螺旋状碳纳米管

:20085,:20086*(No.20606020)(973)(No.2006CB932702)**e-mail:[e-mail]螺旋状碳纳米管*黄佳琦张强魏飞**(清华大学化工系绿色反应工程与工艺北京市重点实验室北京100084)螺旋状碳纳米管(coiledcarbonnanotubes,CCNTs)是一种弯曲环绕,形成螺线状结构的碳纳米管其螺旋形态特有的手性螺旋状,以及非线性力学响应等性质,使其在微纳器件复合材料等领域具有应用前景,逐渐成为人们关注的热点方向本文从制备形成机理结构调变以及应用几个方面详细阐述了CCNTs的研究进展螺旋碳纳米管制备生长机理应用:O613171;TB383:A:1005-281X(2009)04-0637-07CoiledCarbonNanotubesHuangJiaqiZhangQiangWeiFei**(BeijingKeyLaboratoryofGreenReactionEngineeringandTechnology,DepartmentofChemicalEngineering,TsinghuaUniversity,Beijing100084,China)AbstractCoiledcarbonnanotubes(CCNTs)areCNTswithspiralstructure.TheCCNTspossessuniquepropertiesofhelix,chiralityandnonlinearmechanicalbehavior.Itattractsgreatinterestsinthesynthesis,growthmechanismsandapplicationdevelopments.TheCCNTsiscommonlysynthesizedbycatalys-tsupportedchemicalvapordeposition(CVD)andfloatingcatalystCVD.TheselectiveproductionofCCNTshasbeenachieved.BasedontheanalysisoftheformationmechanismofCCNTs,theprospectsonstructuremodulationofCCNTsareinvestigated.Thechallengesinthisfieldincludedelicatecontrolofparametersinstructure,thesynthesisofCCNTsinring,doublehelixandtheselectiveproductionofCCNTswithchirality.Duetotheuniqueproperties,someCCNTshavepotentialapplicationsinnano-electromechanicaldevices,compositereinforcements,etc.TheapplicationsbasedonsingleCCNT,CCNTsarrayandmacroscopicquantityofCCNTsarebrieflyoutlinedaswell.Keywordscoiledcarbonnanotubes;synthesis;growthmechanisms;applicationsContents1Introduction2CCNTssynthesis211Chemicalvapordepositionwithsupportedcatalyst212Chemicalvapordepositionwithfloatingcatalyst3Formationmechanismandstructuremodulations311FormationmechanismofCCNTs312StructuremodulationsofCCNTs4ApplicationsofCCNTs411ApplicationbasedonsingleCCNT412ApplicationbasedonCCNTsarray413ApplicationbasedonmacroscopicquantityofCCNTs5Conclusions1(carbonnanotubes,CNTs)21420094化学进展PROGRESSINCHEMISTRYVol.21No.4Apr.,20091991IijimaCNTs[1]CNTs,CNTs;,(coiledcarbonnanotubes,CCNTs)1993,DunlapIhara[2,3]1994,Zhang[4](transmissionelectronmicroscopy,TEM),CCNTs,CCNTsCCNTs,,CCNTs,CCNTsCCNTsCCNTs,,,CCNTsCNTs,,,CCNTsCCNTs,CCNTsCCNTs2CCNTs,3[5,6],,,(chemicalvapordeposition,CVD),,,CVD,,CCNTs211,,,,100nm,[7,8],Zhang[4]CCNTsCoSiO2,CCNTs[9]Ni,PCl3,ArPH2,[10]Co,,,CCNTsCCNTs,,,Pan[11]ITO(indiumtinoxide)CCNTs(1a)CCNTs[12],CCNTs,1(a)ITOCCNTs[11];(b)CCNTs[14]Fig.1(a)CCNTsobtainedviasupportingcatalystprocessonITOglasssubstrate[11];(b)CCNTsofdifferentcoildiametersandpitchesbycontrollingtheatmosphere[14],CCNTsBai[13],CCNTsZhong[14]#638#化学进展21,CNTs,,CCNTs,CCNTs1bTEMCCNTs1CCNTs,,CVD500)800e,CCNTs,CCNTs1CCNTsTable1SynthesisofCCNTsthroughsupportingcatalystprocessescarbonsourcecatalystatmospheretemperature(e)substraterefacetylenePCl3NiArPH2500)800graphiteplate9acetyleneCo)720silicagel10acetyleneFefilmsHe700indiumtinoxide12ethyleneFeH2700Al2O3powder11acetyleneFeCoNiN2PArPH2650porousaluminumoxide13methaneFeN2550alignedCNTarrays14212,,,,CCNTs2(a)CCNTs;(b)CCNT[17]Fig.2(a)CCNTsarraysviafloatingcatalystprocess;(b)TEMimageofasingleCCNT[17],CCNTsHou[15],,CCNTs(2)Bajpai[16]CCNTs,-CCNTsWang[17],,CCNTsCCNTs,,2CCNTs,,,,CCNTsCCNTs2CCNTsTable2SynthesisofCCNTsthroughfloatingcatalystprocessescarbonsourcecatalystprecursoratmospheretemperature(e)substraterefpyridineortolueneFe(CO)5H21050)1150siliconwafers15pyridineFe(CO)5ArPH2900)1100quartzsubstrates16xyleneandacetyleneferroceneandindiumisopropoxideAr700quartzsubstrates17ethanolcupricacetateAr850quartz183CCNTs311CCNTsCCNTs,3,1994,Amelinckx[19]:,,,,3,[20,21],[22],,,,,100nm,Motojima[20,23],,#639#4[21],,,FePIn[17,24],FePSn[17,25],FePNi[26],,,,P[9,27]S[15,16,28]Na[29]N[14,30],,3CCNTs,($t)(VmVM)[19]Fig.3TheformationofCCNTscausedbydifferentactivitiesonsinglecatalystparticle.Differentgrowthvelocities(VmandVM)indifferentsitecausethecurveintimeinterval$t[19],CGao[12]:-CCNTs;--;--CCNTsHou[15]-,,C2C24,C2,C2(),C2,,,,,,,,[31]4-C2[15]Fig.4SchemeoftheformationofC5-C7ringsbytheinsertionofaC2cluster[15],,,CCNTs312CCNTs1994,CCNTs,CCNTs,,CCNTs[15];,CCNTs[16,17]CCNTs,,CCNTs3,,CCNTs015)70nm,1145)250nm,313)470nm3CCNTsTable3ThemorphologiesofCCNTsviadifferentprocessesCNTsdiameter(nm)coi-lpitch(nm)coi-ldiameter(nm)remarkref156070125080220doublehelix90151145313single-walled321010050doublehelixmainlyCCNTs1370250470somedoublehelix1460250120mainlyCCNTs1515100501065400550CCNTsarray161570503370100200somedoublehelix34156035353012050CCNTsarray17#640#化学进展21,CCNTs,,,,,CCNTsDNA[9,13],Tang[36]Fe,,5/V0CCNTs,CCNTBlank[37],CCNTs,(111)FeCCNTs,CCNTs,CCNTs,CNTs[38],[39];[40)42],5[36]Fig.5LeftandrighthandedCCNTsattachedtoonecatalystnanoparticle[36]4CCNTsCCNTs,CCNT;CCNTsCCNTs,,;,CCNTs,CNTsCCNTs411CCNT,[43],,,[44]CCNT,Volodin[45]CCNTCCNT,CCNT,CCNT100)400MHz,,CCNT,CCNT,10-18g,412CCNTs,Daraio[46]CCNTs,CCNTsColuci[47],,,CCNTs,CCNTs,413CCNTsCCNTsCNT,,Qian[48]CNTsPCNTs,CCNTs,,,#641#4,CNTsLu[49,50](SWCNT)(MWCNT)CCNTs(4)CCNTs,SWCNT,,CCNTs,,CCNTs60%,18%SWCNT(32%),CCNTs,,,CCNTs4CNTsP[51]Table4PerformancecomparisonofdifferentCNTsPepoxycomposites[51]sampleTg(e)$H(JPg)flexuralstrength(MPa)microhardness(HV)pureepoxy541477128274131018SWCNTP