导电高分子精选PPT.ppt
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1、导电高分子第1页,此课件共85页哦Introduction第2页,此课件共85页哦Polymerswerethoughtofaselectrialinsulatorsuntilthediscoverythatiodine-dopedpolyacetylene(聚乙炔)exhibitedelectricalconductivitymanyordersofmagnitudehigherthanneutralpolyacetylene.ThisdiscoverywaspublishedbyShirakawa,H.,Louis,E.,MacDiarmid,A.,Heeger,A.,(1977).Asa
2、resultofthispioneeringwork,theyreceivedthe2000NobelPrizeinChemistry.Introduction第3页,此课件共85页哦Nobel Prize in Chemistry 2000“For the discovery and development of conductive polymers”G.MacDiarmid H.Shirakawa J.Heeger第4页,此课件共85页哦黑格(黑格(Alan J.Alan J.Heeger,1936Heeger,1936 )美国美国加利福尼亚大学加利福尼亚大学的的著名物理学家,著名物理学
3、家,20002000年年1010月月1010日,因日,因对导电聚合物的发现对导电聚合物的发现和发展而获得诺贝尔和发展而获得诺贝尔化学奖。化学奖。Introduction第5页,此课件共85页哦麦克迪尔米德麦克迪尔米德(Alan G.Alan G.MacDiarmidMacDiarmid,19371937 )美国美国宾夕法尼亚大宾夕法尼亚大学的学的著名化学家,著名化学家,20002000年年1010月月1010日,日,因对导电聚合物的因对导电聚合物的发现和发展而获得发现和发展而获得诺贝尔化学奖。诺贝尔化学奖。Introduction第6页,此课件共85页哦白川英树白川英树(Hideki(Hide
4、ki ShirakawaShirakawa,19361936 )日本筑波大学的著日本筑波大学的著名化学家,名化学家,20002000年年1010月月1010日,因对导日,因对导电聚合物的发现和电聚合物的发现和发展而获得诺贝尔发展而获得诺贝尔化学奖。化学奖。Introduction第7页,此课件共85页哦ConductivityIntroduction第8页,此课件共85页哦Thediscoveryofconductivepolymersisuniqueinitsaccomplishmentasapossiblesubstitute(替代物替代物)formetallicconductorsand
5、semiconductors.Scientistsfrommanydisciplinesarenowcombiningexpertise(专门技术)tostudyorganicsolidsthatexhibitremarkableconductingproperties.Alargenumberoforganiccompounds,whicheffectivelytransportchargeareroughlydividedintothreegroupsi.e.chargetransfercomplexes/ionradical(基基)salts,organometallicspeciesa
6、ndconjugatedorganicpolymers.Introduction第9页,此课件共85页哦Electronicallyconductingpolymersdifferfromallthefamiliarinorganiccrystallinesemiconductorsintwoimportantfeaturesthatpolymersaremolecularinnatureandlacklongrangeorder.Akeyrequirementforapolymertobecomeintrinsically(本征本征)electricallyconductingisthatt
7、hereshouldbeanoverlapofmolecularorbitalstoallowtheformationofdelocalized(离域离域)molecularwavefunction.Besidesthis,molecularorbitalsmustbepartiallyfilledsothatthereisafreemovementofelectronsthroughoutthelattice.Introduction第10页,此课件共85页哦Conductingpolymerscontain-electronbackboneresponsiblefor(是的原因)their
8、unusualelectronicpropertiessuchaselectricalconductivity,lowenergyopticaltransitions,lowionizationpotentialandhighelectronaffinity.Thisextended(延长延长)-conjugatedsystemoftheconductingpolymershavesingleanddoublebondsalternatingalongthepolymerchain.Thehighervaluesoftheelectricalconductivityobtainedinsuch
9、organicpolymershaveledtothenamesyntheticmetals.Introduction第11页,此课件共85页哦IntroductionThedevelopmentofpolymerswithconductivitiesequaltosemiconductorsandmetalshavebeenpresentedinTable1andtheircorrespondingstructuresareshowninFig.1.第12页,此课件共85页哦Introductionisothianaphthene:异硫茚;异硫茚;azulene:甘菊蓝;甘菊蓝;furan:
10、呋喃呋喃第13页,此课件共85页哦IntroductionPoly-acetylenePolypyrrolePolythiophenePolyanilinePoly-p-phenylenePoly-phenylenevinylenePoly-p-phenylenesulphidePoly-iso-thianaphthene第14页,此课件共85页哦Historical background of electronically conducting polymers第15页,此课件共85页哦Historical background of electronically conducting po
11、lymersResearchonconductingpolymersintensified(增强)soonafterthediscoveryofpoly(sulphurnitride)(SN)xin1975whichbecomessuperconductingatlowtemperatures(Greeneetal.,1975).Although,conductingpolymercomplexesintheformoftetracyano(四氰基)andtetraoxalato-platinates(四草酸铂酸盐),theKrogmansaltschargetransfercomplexes
12、hadbeenknownearlier,thesignificanceliesintherediscoveryofPAin1977(initiallydiscoveredbyShirakawaetal.,1977usingaZieglerNattatypepolymerizationcatalyst)byMacDiarmidandHeeger,UniversityofPennsylvania(宾夕法尼亚).重视第16页,此课件共85页哦TheywereabletoenhancetheelectricalconductivityofPA(109Scm1)byseveralordersi.e.10
13、5Scm1bysimpledopingwithoxidizingagentse.g.I2,AsF5,NOPF6(p-doping)orreducingagents(n-doping)e.g.sodiumnapthalide(萘钠).Thishasgeneratedrenewedinterestofthescientificcommunitytowardsthestudyanddiscoveryofnewconductingpolymericsystems.Historical background of electronically conducting polymers第17页,此课件共85
14、页哦Poly-paraphenylene(对苯基)wassynthesizedbyIvoryetal.(1979).Itformshighlyconductingchargetransfercomplexeswithbothnandptypedopants.DopingwithAsF5increasesitsconductivitytoitsvaluesfrom105to500Scm1.TheoreticalmodelsandelectronspinresonancemeasurementsindicatethatthechargetransportinPPPisapolaron(极化子)/b
15、ipolaron.PPS(聚苯硫醚)wasthefirstnon-rigid,butnotfullycarbonbackbonelinkedconductingpolymer.Itsdiscoverywasparticularlyexciting,sinceitspropertyofsolutionprocessabilityopenedthedoorforpotentiallyobtainingcommerciallyviableconductingplastics(Raboltetal.,1980).Historical background of electronically condu
16、cting polymers第18页,此课件共85页哦Amongstpolyheterocyclines(聚杂环聚杂环),polypyrrole(PPY)hasbeeninvestigatedthemost.TheelectrochemicaloxidationofpyrroleinaqueousH2SO4canbecarriedoutonplatinumelectrode.TheproductisaconductingpolymerknownasPyrroleBlackKanazawaetal.(1979)producedcoherentfilmsofPPYwithaconductivity
17、of100Scm1andexhibitedexcellentairstability.Butthemainhindrance(障碍)ofitsprocessabilityisinitsinsolubilityinanyorganicsolvents.Historical background of electronically conducting polymers第19页,此课件共85页哦PTH(聚噻吩)showsremarkablestabilityofbothoxidized(p-doped)conductingformanditsneutral(undoped)insulatingfo
18、rminbothairandwater.Itshowshighdopinglevelupto50%whichmaybeattributedtoitspartiallycrystallinenaturethathasbeenconfirmedbyX-rayphotoelectronspectroscopystudies.Manyotherconductingpolymerssuchaspolyfuran(聚呋喃聚呋喃),polyindole(聚吲哚聚吲哚),polycarbazole(聚咔唑聚咔唑),polyanilineetc.havealsobeensynthesized.Structure
19、sofsometypicalconductingpolymershavebeenshowninFig.1.Historical background of electronically conducting polymers第20页,此课件共85页哦Synthesis of conducting polymers第21页,此课件共85页哦Thereisnosingularmethodforsynthesisingpolymersthatcanbetransformedintoconductivepolymers,theincorporationofextended(延长延长)-electron
20、conjugation(共轭共轭)isofforemostimportance.Conductivepolymersexceptionomeric(离子交联的)polymersmaybesynthesisedusingstandardmethodsofpolymerisationincludingconventionalaswellasspecificrouteswhichincludeWitting(维狄希),Horner(霍纳)andGrignard(格林尼亚)reactions,polycondensationprocessesandmetalcatalysedpolymerisatio
21、ntechniques.Oxidativecoupling(偶合)withoxidisingLewisacidcatalystsgenerallyleadstopolymerswitharomaticorheterocyclicbuildingblocks(构件构件).Synthesis of conducting polymers第22页,此课件共85页哦Conductivepolymersmaybesynthesisedbyanyoneofthefollowingtechniques:1.Chemicalpolymerisation2.Electrochemicalpolymerisati
22、on3.Photochemicalpolymerisation4.Metathesis(复分解)polymerisation5.Concentratedemulsion(浓乳液浓乳液)polymerisation6.Inclusion(夹杂)polymerisation7.Solid-statepolymerisation8.Plasma(等离子体)polymerisation9.Pyrolysis(高温分解)10.Solubleprecursor(前体)polymerpreparationSynthesis of conducting polymers第23页,此课件共85页哦Amongal
23、ltheabovecategories,chemicalpolymerisationisthemostusefulmethodforpreparinglargeamountsofconductivepolymers,sinceitisperformedwithoutelectrodes.Chemicalpolymerisation(oxidativecoupling)isfollowedbytheoxidationofmonomerstoacation(阳离子)radicalandtheircouplingtoformdicationsandtherepetition(重复)ofthispro
24、cessgeneratesapolymer.Alltheclassesofconjugatedpolymersmaybesynthesisedbythistechnique.Synthesis of conducting polymers第24页,此课件共85页哦Electrochemicalpolymerisationisnormallycarriedoutinasingle-ordual-compartment(隔间隔间)cellbyadoptingastandardthree-electrodeconfigurationinasupportingelectrolyte,bothdisso
25、lvedinanappropriate(适当的适当的)solvent.Electrochemicalpolymerisationcanbecarriedoutpotentiometricallybyusingasuitablepowersupply(potentiogalvanostat).Synthesis of conducting polymers第25页,此课件共85页哦Generally,potentiostaticconditionsarerecommendedtoobtainthinfilms,whilegalvanostaticconditionsarerecommendedt
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