25--染料敏化太陽(yáng)能電池關(guān)鍵材料的設(shè)計(jì) 郭文躍 中國(guó)石油大學(xué)

1、項(xiàng)目類(lèi)別重點(diǎn)項(xiàng)目山東省自然科學(xué)基金資助項(xiàng)目結(jié)題報(bào)告項(xiàng)目負(fù)責(zé)人（簽字）:郭文躍項(xiàng)目編號(hào):ZR2011EMZ002項(xiàng)目名稱(chēng):染料敏化太陽(yáng)能電池關(guān)鍵材料的設(shè)計(jì)所在單位:中國(guó)石油大學(xué)（華東）研究工作完成時(shí)間:2014年10月山東省自然科學(xué)基金委員會(huì)辦公室二O四年制一、開(kāi)展的主要研究工作(概述在項(xiàng)目執(zhí)行期內(nèi)，完成的主要工作內(nèi)容及進(jìn)度情況。不超過(guò)1000字。)在項(xiàng)目執(zhí)行期間，主要開(kāi)展了6方面工作：非貴金屬Fe(II)配位染料敏化劑分子的設(shè)計(jì)和理論研究、非貴金屬Cu(I)基染料敏化劑的設(shè)計(jì)和理論研究、Zn基卟啉染料敏化劑的設(shè)計(jì)和理論研究、三苯胺基純有機(jī)染料敏化劑的設(shè)計(jì)和理論研究、染料敏化劑在半導(dǎo)體TiO2表

2、面的吸附性質(zhì)研究、激發(fā)態(tài)染料敏化劑分子在常用I-/I3-電解液中電子傳輸性質(zhì)的理論研究。具體的研究?jī)?nèi)容及進(jìn)度情況如下：(1) 設(shè)計(jì)了一系列的Fe中心離子配合體染料敏化劑分子，優(yōu)化了敏化劑分子在液相中的結(jié)構(gòu)，計(jì)算了結(jié)構(gòu)參數(shù)；分析了敏化劑分子軌道組成以及軌道能級(jí)；模擬了液相中紫外/可見(jiàn)光(UV/VIS)吸收光譜、吸收強(qiáng)度以及電子激發(fā)轉(zhuǎn)移路徑。計(jì)算和分析工作已經(jīng)完成，相關(guān)文章已經(jīng)發(fā)表。(2) 設(shè)計(jì)了一系列的Cu中心離子配合體染料敏化劑分子，優(yōu)化了敏化劑分子在液相中的結(jié)構(gòu)，計(jì)算了機(jī)構(gòu)參數(shù)；分析了敏化劑分子軌道組成以及軌道能級(jí)；模擬了液相中紫外/可見(jiàn)光(UV/VIS)吸收光譜、吸收強(qiáng)度以及電子激發(fā)轉(zhuǎn)移路

3、徑。計(jì)算和分析工作已經(jīng)完成，相關(guān)文章已經(jīng)被接收。(3) 設(shè)計(jì)了一系列的Zn中心離子配合體染料敏化劑分子，優(yōu)化了敏化劑分子在液相中的結(jié)構(gòu)，計(jì)算了結(jié)構(gòu)參數(shù)；分析了敏化劑分子軌道組成以及軌道能級(jí)；模擬了液相中紫外/可見(jiàn)光(UV/VIS)吸收光譜、吸收強(qiáng)度以及電子激發(fā)轉(zhuǎn)移路徑。計(jì)算和分析工作已經(jīng)完成，相關(guān)文章已經(jīng)被接收。(4) 設(shè)計(jì)了一系列三苯胺純有機(jī)染料敏化劑分子，優(yōu)化了敏化劑分子在氣相與液相中的結(jié)構(gòu)，計(jì)算了機(jī)構(gòu)參數(shù)；分析了敏化劑分子軌道組成以及軌道能級(jí)；模擬了氣相與液相中紫外/可見(jiàn)光(UV/VIS)吸收光譜、吸收強(qiáng)度以及電子激發(fā)轉(zhuǎn)移路徑。計(jì)算和分析工作已經(jīng)完成，相關(guān)文章已經(jīng)發(fā)表。(5) 計(jì)算了羧酸

4、根的模型分子HCOOH(甲酸)和C6H5COOH(苯甲酸)在銳鈦礦相TiO2(101)面各吸附構(gòu)型的吸附能和結(jié)合方式，總結(jié)了其吸附規(guī)律；對(duì)鏈接-COOH基團(tuán)的有機(jī)染料進(jìn)行了理論計(jì)算研究，分析了受光激發(fā)電子注入半導(dǎo)體的方式和注入時(shí)間，從微觀理論上分析了影響電子注入時(shí)間的因素。(6) 對(duì)敏化劑分子及電解質(zhì)溶液分子的結(jié)構(gòu)、單點(diǎn)能和頻率進(jìn)行了計(jì)算，模擬了激發(fā)態(tài)染料敏化劑分子在常用I-/I3-電解液中電子傳輸過(guò)程，分析了電解質(zhì)與敏化劑分子的相互作用；研究了在常用I-/I3-電解液中添加添加劑(含有Li+、Na+、K+等離子)對(duì)激發(fā)態(tài)染料分子充電性能的影響。二、取得的主要成績(jī)(比照研究工作計(jì)劃，簡(jiǎn)述所做的

5、代表性工作及取得的標(biāo)志性成果、應(yīng)用情況，不超過(guò)1500字。)取得的主要成績(jī)：按照研究計(jì)劃，本項(xiàng)目共在國(guó)外學(xué)術(shù)期刊上發(fā)表SCI文章15篇；申請(qǐng)發(fā)明專(zhuān)利2項(xiàng)；將該類(lèi)項(xiàng)目進(jìn)行了升級(jí)，申請(qǐng)了國(guó)家自然科學(xué)基金；共培養(yǎng)博士研究生3人，碩士研究生4名，俱已畢業(yè)并獲得了學(xué)位。具體的代表性工作及取得的標(biāo)志性成果、應(yīng)用情況如下。代表性工作：(1) 按照研究計(jì)劃，我們?cè)O(shè)計(jì)了一系列的非貴金屬中心離子(包括Cu、Fe、Zn等)配合體染料敏化劑分子和基于三苯胺等純有機(jī)分子材料的新型染料敏化劑分子，優(yōu)化了敏化劑分子在氣相與液相中的結(jié)構(gòu)；分析金屬中心離子同配體的成鍵、穩(wěn)定性以及結(jié)合能情況；分析敏化劑分子軌道組成以及軌道能級(jí)；

6、模擬氣相與液相中紫外/可見(jiàn)光(UV/VIS)吸收光譜、吸收強(qiáng)度以及此過(guò)程中電子激發(fā)轉(zhuǎn)移路徑；修改共軛配體以拓展光譜吸收范圍，并提高光吸收率、光穩(wěn)定性以及熱穩(wěn)定性。(2) 研究了染料敏化劑分子在TiO2、ZnO等半導(dǎo)體表面的吸附位與結(jié)合方式，比較不同被吸附基團(tuán)的吸附位置，分析吸附能差異；研究敏化劑吸附對(duì)半導(dǎo)體自身性能的影響；研究電子由受激發(fā)的染料敏化劑分子至半導(dǎo)體表面電子轉(zhuǎn)移路徑；研究半導(dǎo)體捕獲自由電子過(guò)程以及輸運(yùn)方式。(3) 模擬了激發(fā)態(tài)染料敏化劑分子在常用I-/I3-電解液中電子傳輸過(guò)程；研究在常用I-/I3-電解液中添加添加劑(含有Li+、Na+、K+等離子)對(duì)激發(fā)態(tài)染料分子充電性能的影響

7、。取得的標(biāo)志性成果、應(yīng)用情況：(1) Fe金屬中心類(lèi)敏化劑的成果已經(jīng)發(fā)表于JournalofOrganometallicChemistry。X.Q.Lu,K-S.Chau,S.X.Wei,乙G.Deng,N.Ding,L.M.Zhao,C.-M.L.Wu,W.Y.Guo.*J.Organomet.Chem.,2013,74142,168-175.(2) Cu金屬中心類(lèi)敏化劑的成果已經(jīng)接收于ScienceofAdvancedMaterialsoS.X.Wei,X.F.Shi,X.Q.Lu,*Y.Shao,D.L.Jin,乙G.Deng,乙G.Zhao,K.Li,W.Y.Guo.Sci.Adv.M

8、ater.,2014,DOI:10.1166/sam.2014.2052.Zn中心離子配合體染料敏化劑分子的成果已經(jīng)接收于ScienceofAdvancedMaterials。X.F.Shi,X.Q.Lu,*YShao,S.X.Wei,Q.Zhu,D.L.Jin,乙G.Deng,W.Y.Guo.*Sci.Adv.Mater.,2014,DOI:10.1166/sam.2014.2007.(4) 以三苯胺為基礎(chǔ)的純有機(jī)分子敏化劑的成果已經(jīng)發(fā)表于InternationalJournalofPhotoenergy。S.X.Wei,X.Q.Lu,*X.F.Shi,乙G.Deng,Y.Shao,L.M.

9、Zhao,W.Y.Guo,*C.-M.L.Wu,Int.J.Photoenergy,2014,art.no.280196.(5) Cu金屬中心類(lèi)敏化劑的成果已經(jīng)申請(qǐng)發(fā)明專(zhuān)利一項(xiàng)“一種設(shè)計(jì)與篩選銅基聯(lián)吡啶染料敏化劑的方法”，目前已經(jīng)公開(kāi)，專(zhuān)利號(hào)為201410205648.2。(6) 申請(qǐng)發(fā)明專(zhuān)利“二硫富瓦烯基染料敏化劑的分子設(shè)計(jì)方法”，目前已經(jīng)公開(kāi)，專(zhuān)利號(hào)為201410205490.9。(7) 將該基金進(jìn)行了升級(jí)，在2014年申請(qǐng)了國(guó)家自然科學(xué)基金“新型非貴金屬染料敏化劑的理論設(shè)計(jì)與篩選”項(xiàng)目編號(hào)為21303266。標(biāo)志性科研成果（列舉能夠體現(xiàn)本項(xiàng)目研究工作與水平的標(biāo)志性成果1-2項(xiàng)，并另附標(biāo)志

10、性成果影印件；所列論文、專(zhuān)著等須已公開(kāi)發(fā)表且標(biāo)注本基金項(xiàng)目資助）。標(biāo)志性成果清單序號(hào)成果名稱(chēng)完成人類(lèi)型完成時(shí)間項(xiàng)目負(fù)責(zé)人署名次序1Cu(I)-basedsensitizersfeaturing6,6-dimethyl-4,4-dicarboxylate-2,2-bipyridinewithfunctionalized2,9-dimethyl-l,10-phenanthrolineligands:Astructural,electronicandspectralinvestigation.魏淑賢論文20149/92TheoreticalInvestigationonNovelPorphyrinD

11、yeswithFunctionalizedBridgeandDonorGroupsforDye-SensitizedSolarCells.史曉凡論文20148/8類(lèi)型是指：論文、專(zhuān)著、發(fā)明專(zhuān)利等附:比IAE孔IGANseiEHTin亡PUBLESHER.SCopyngMO-Ml*by丹nrm古訊!創(chuàng)血PuMshcn-削聞hisFrnudintTitUnkudSaaialAfruraARTOLESciwn-otAaV3.ncadiUaranaVW.EkpH1-7.2014hwwwQipbt.tcinlZiaffOCu(l卜BasedSensitizersFeaturing6?6-Dimethyl

12、-4,4-Dicarboxylate-2r2r-BipyridinewithFunctionalized2,9-Dimethyl-ljlO-PhenanthrolineLigands:AStructural,ElectronicandSpectralInvestigationShuxianWeiPXiaofanShkXiacqingLu*;YangDongliarigJin,ZhigangDengrZigngZhao,KeLi,andWenyueGuo*GoWegeofScience.CfweMi囲竝yofR?Jrud,eumi咖日aS*w?tong2665S0,PeopledReptrfti

13、fcafChinaABSTRACTAseriesofheterolepticCu(1)-basedcomplexesfeaturing6占-dimethyl-4,4!-dicarboxylate-22-bipyridine(dmd-cbpy)withftjnctonaliz目d2,9-dimelii/l-1,10-phenanthiroline(dmp)ligandsareinvestigatedb甲densityfunctionallheory(OFT)andtime-dep&rKfenlDFT(TD-DFT),Moleculargeo-metry,electronicstruclurePa

14、ndaibsorp-liorispectralpropertyarepredictedindiehloromethsrte(CH7Cla)solution,Ourresurtsshowthatirbcreasingir-ccimjugilionandheiefdaromalicgroupstoancillarydnvpligandwoulddecreaseHOMO-LUMOgap,broatf-enspectralcoverrange,boostabsorpttonifTtensity,enhancelighl-harveslingeffici&rcy(LHEJiandthusimprovet

15、iieabsorptionspectralproperties.Structuraloptiinizationondmpligandhascomparableinfluenceontheelectronicstructure,speclralproperty,andLHEofCu(l)-basedcomplexesfeaturingdnnpandbpyligandsmlativeiothosefeaturingdoublebpyligands.ThisworkhighlightstFislhelerolepticCu(l)七asedsensitizerswilhmoreefficientfun

16、ctionalizedgroupswouldprovideappliestkiFiprospectinDSSCs.KEYWORDS:LINTRODUCTIONDe-sertsicizedsolarcells(DSSCs)basedcnmeci-pofDusnanocrystallincfilmsarcproniisingphotowlcajcdeiceswithex&ellenlcosVperfbrrrtariceraEioforthecomingkw-carboiiienergyckmaiiKtzThe5onsili?iisaftchonedtoainLe-bandgarpsemicondu

17、ctcrdeclrode,s4uidsictKdtLsgethjerwilJiCEMinLtrtltclrudje,u.ndthegapi&AiledbyckclrolytcconlamingredoscouptcK/WhentheisumHUzHTahstffbslighL.CheptuuCD-extikdek-c-Ironispujnpedfrom生IwcrgroundHsiteInahihjcrcscilcdstfitcandtothecondiKtionbfindofscmkondiK-ii匚Ajtd0Rthem,DSSCwithpolypridylRli|U卜hasedsensidz

18、enhaveachievedacony-dcrablchighefficiencysindirvnuTk.iibLeplmflQ-.eletlrWhuEiwrebfiiHlkrncv-ateuldbtuddTvwd.Ejnuilb.hiiqf*upt.cdluL4.il.wyy;iHJupt:.tdu.aiAsccpwd：XXXxKXXXK5(ligands,withhcxylthiophcrKf3jkIinseLlingasulfuratomtelweeiihexylaindihioptieiK(CIW)1Q,inefeasesthejnifLarexhcicUu口tocJJitienLup

19、LuH8.7xItTM-1tm-1iiE5500nitii.FurtherextendingcbecofijingationleniglhoftheanciUuryliEndwithuLkyLbLChiuphtnegruups(CYC-lil)17iLndhtyllhiobilhkiphcTit血伽口砧(CC-Bll|ilHbcur-slslheDSSCspeidannain.eeLouhnghefficiencyupLo113%.Jrlnwevcr,ilisslillshugechullenctocaptuircioJjr廿口ergjandOMivcritoeletlncaty口/叮呂iih

20、uniJEUilLyavailablematerialsinsteadofheexpensive也vidscarcemalerialofRuindyesensitizens.Recemly;Cu(I)-coordLnatdcomplexesexhibiitffas-ibkphotophysiealandpftenocheitiicproperties恥MnsitizeraJ1*11suchasstrongmCiil-tu-landuhiirgcLnLDf&r(MLCT)iibrpUu口mthevisibleruiige,relaflivelylimg-livtdcxciltdsluflelif

21、etime,andapulentreducldiiil(ofihtIhcmniillyquLlibniLtdMLCT也ale嚴(yán)Also,lheCtf(l)-cuuTiJinated-悴LmhudralgcoE撫iryJat:iliLuLsLoiisNcmhJt:dixirsilyofheLerolcpIiLccniOgULralionsbymeansoftheproperchoiceofanci-ImyIjgamdls-2*-371MtireimpLirtLinlCuaukkusuEUiin-ablcndtnvironmcncaJ-friciidyrawmaterialwiithrcspccl

22、loRu.DSSCswilhbipyridylCu(I)-basedsensitizershaveSa.Adv.仙日r.2tJ?4rVaf.6,Naxx1947-2935.20ITO?etaJO.IaSE/sam-EOH.aJSSCu(i卜BasedSensitizersFeaturingdmacbpywithFunctionalaedar。UganOs.AStructural曰ectronicandSpectralInvesugaiioniVWAaf.1乙剛-5.9142-2.S4-5.&W3-2.40-5.8704-2.86-5.8575-2.SM-5.7166-2.妙-5.761(CuL

23、LT-2-2.%5-5.80iCuLLj*-7-2.721-5.513N3-2.$0-5.44CYCBII-5.260.218IOOO0.21U1.2130.2911.2370.32613370.50917490.53017860.3331XW00.6201.4190.1261.0001).1ll曲.,222.2.2.S.2.07.73旳.(M.79.54.46totheseattheB3LYP；DZVPlevel,including(hespectralcoverrangelntcmilydislribulion.andpeakposilicms.Except

24、ionally,forcomplexes5and6.theabsorptionintensitiesin450.0-600.0nmobtainedatlheB3LYP/DZVPlevelarcrelativelyweakerthanthoseattheLANL2DZlevel.Asforthealterationtrendofspectraalongwiththestructuralupliinizalion,1-6isfoundtobesimilaruCuLLT2-CuLLf-7/7Thatis.Cu(I卜basedcomplexesfeaturingbpyanddmpligandsshow

25、similarspectrapropertieswiththosefeaturingdoublebpyligandsMongwilhlhesimilarslructuraloptimization.3.4.StructuralOptimizationandSpectralPropertyLight*harvestingefficiency(LHE).asagoodindicatoroftheincidentphoton-to-clcctronconversionefficiency(IPCE),characterizesthecapabilityofsensitizersinharvestin

26、glight.ToobtaingoodphotocurrentresponsesensitizersshouldownLHEU5high4possible.TheL11EcanbeapproximatelyexpressedastheFollowingequation:5BLHE=l-10-x=l-10whereA(f)istheabsorption(oscillatorstrength)oflhedyeassociatedtothelowestverticalexcitationenergy(EA).TheHOMOandLUMOenergies,HOMO-LUMOgaps,lowestver

27、ticalexcitationenergies(4)andoscillatorMrcnglhs(/)ofallthedesignedcomplexes.(CuLLJ*-2and|CuLLT-7,N3andCYC-B11arelistedinTabkIII.Forthespectracoverrange.5and6coverlhelongestwasclcngthregionwhile1coverstheshortestregion.Thistrendisconsistentwith(hevariationinthelowestverticalexciuitionenergyofcomplexe

28、s.AsshowninTableIII.complexesSand6ownthesmallestlowestverticalexcitationenergyof2.38eVwhilecomplex1hasthelargest2.47eV.Thatis.increasingtheconjugationandthehet-eroaromatkgroupsloancillarydmpligandcaneflkicntlybroadenabsorptionbands.Inordertoestimatetheharvestinglightcapabilityquantitatively,weinvest

29、igate(herelativeLHE(RLHE=LllE4/LHE|.n=).asshowninTabk111.TheRLHEof2-6arccalculatedtorangefrom1.213of2to1.786of6withtheorderof65432.isgoodagreementwilh(hetrendofoscillatorMn?ngth/Thisresultindicatesthattheiniruduclionoflheir-conjugalionandthehctcroaromaticgroupsonancillarydmpligandenhances(he

30、harvestinglightcapabilityComparatively,lhecakuhtcdRLHEof(CuLL-2-(CuLL-7andN3fCYCB11is1.419and1.341.respectively,whichissmallerthan1.786of1-6.asshowninTableIII.Therefore,takingthecoverrange,theabsorptionstrength,andimprovementtrendinfoaccount,Cu(l)-bascdscnsiliz-ersfeaturingdmpandbpyligandsmaycapture

31、lightasefficientlyasthosekaluringdoublebpyligandsalongwith(hestructuraloptimization.TaNvIII.gHOMOaixlLUMOcne咚心.MOMO-LUMO鬧戶.kiwcMvcnicalcxcMMionenergies(4).omhIImotstrcnihs.andrclothvLHEIRLHE)forCU(IHxisdcomplexescakulatedinCH:CI:sotauoa?CcmpigJLUMOHOMOHOMO-LUMOAfRLHE.V*C5：“AllcncrHireinV;comwi-6nbuw

32、edaiAcDZVB&3】G(d)fcsdinOi.CX敘uM川;CLU|2*CuLL廣7&dncdalAcDZ*Pif3-2IGdllodinaxlwiiifilcwlulkn;RMIJ)Ji*CBUYWSDDlevetRvuMEuix!uitibeB5LYP/3-2ICXd)le*el4CONCLUSIONSIn(hepresentwork,ascriesofheterolepancilliirydmpliganddecreases11OMO-LUMOgap.broadensbandcoverrangeboostsabsorptionintensilyivd-yhifblheabsorpt

33、ionspectraenhanceslighl-hancstingefficiency,andthusimprovestheabsorptionspectralpropcnics.Comparedwithsensitizersfeaturingdoublebpyligands.Cu(I)bavnice(BS2O13CLO31).PetroChinaInnovationFoundation(2013D-5006-0406).andtheFundamentalResearchFundsforlheCentralUnivcrxilics(13CXO5O2OA.1SCXO2O25A.and13CXO5

34、OO4A).ReferencesandNotes1.BOganandM.Gnixcl.Naiu/e353,737(1991).XM.Gral/el.Natuir421.586120031.3. L.M.GoocjIvc%.V.rjh!20U6AmennSgnHcPuHMeAdr艸ggjPrintedinthaUrtiadSUtMerfAmadoaTheoreticalInvestigationonNovelPorphyrinDyeswithFunctionalizedBridgeandDonorGroupsforDye-SensitizedSolarCellsXiaofanShi,Xiaoqi

35、ngLu,YangShao,ShuxianWei,QingZhu,DongliangJin,ZhigangDeng,andWenyueGuoCollegeofScience.ChinaUniversityofPetroleum.Qingdao.Shandong266580.PR.ChinaABSTRACTAseriesofporphyrindyeswithfunctionalizedbridgeanddonorgroupsareinvestigatedasorganicdyesindye-sensitizedsolarcells(DSSCs)usingthedensityfunctionalt

36、heory(DFT)andtime-dependentDFTapproach.Moleculargeomotries.Glectronicstructures,opticalabsorptionspectra.andlight-harvestingefficiencyareanalyzedintetrahydrofuransolution.Ourresultsshowthatbithiophenyl,biphenyl,andnaphthylgroupsonbridgedecreasetheHOMO-LUMOgapsandleadtoobviousredshiftofspectrawithstr

37、ongerintensitiesatthekngwavelengthregion.Dithiafulvenyl,carbazolylandnaphthylgroupsondonorsubunitresultinsimilarHOMO-LUMOgapstothedyeYD2-O-C&butpromotetheabsorptionintensitysignificantly.Thedesignedporphynndyesshowbetterlight-harvestingefficiencyandcoveragerangealongwiththestructuraloptimizationsonb

38、ridgeanddonorgroups.ThistheorGticalinvestigationwouldfacilitatethscreeningofthefunctionalizedbridgeanddonorgroupsforefficientporphyrindyesinDSSCsKEYWORDS:Dye-SensitizedSolarCells,PorphyrinDyes,ElectronicStructures,OpticalProperties.Light-HarvestingEfficiency.ART_CLE1INTRODUCTIONDye-sensitizedsolarce

39、lls(DSSCs).duetotheirabundantrawmaterials,simplefabricationprocessandlow-costpnxluctioncomparedwilh(rudiliona!siliam-basedphotovoltaicdevices,havegainedtherapiddevelopmentasnovelrenewableenergyresources.1-5IntheDSSCdevice,dyeusuallyadvrbionamewpurvusM?iniconduclortnxic.andplaysacorerolemgeneratingan

40、dtransfemngckclrvnswhencxcikdbylightDiversityofdyeshavebeeninvestigatedtoimprovetheDSSCsperformanceduringthepasttwodecades.6-12Amongthem.Rufll)-bascddyesarethemostcommonlyusedTiO2dyeatpresent,whichhavereachedanovemllphulon-lo-clcclrunenergyconversionefficiencyover12%basedonbipvndylRu(ll)-baseddyeswi

41、thcarboxylicacidgroups.13However,theelementRuisrare,expensiveandharmfultoenvironment,limitingRu-baseddyesiobewidelyusedinindustryComparatively,organicdyesarouseextenMVx:attcnlioninrecentyearsbecauseoftheirlowcost,highnu)arextinctioncocflficicnUgoodflexibilityinmoleculartailoringandcnvironmcnicompati

42、bility.14AuthorsioutiomcorrespcodcixcshouldbeEintnh:luxqupcxduxv.*fiRcvciwd:xaXakxxxkiAbundanceoforganicdyes,suchastriphcnylaminc.15pcr)lcnc.16coumarin.17indolinc.,ssquarainc/9porphrin.20haveexhibitedpromisingphotophysicalandphotocbcmi-calpropertiesaspotentialdyesforncxt-gcncrationDSSCs.P

43、cxphyrin-buMxldyes,inspiringfromnaturalphotosynthesis.haveexhibitedprominentconversionefficiencyover12.3%inDSSCs.211(takesadvantageofitsstableplaneconfigurationaswellasfourmesoandeightftpositionswhichlacililate(opromotemoreefficientfunctionalizedgroups.SinceCu-poiphyrinfirstappearedwithanefficiencyo

44、f2.6%in1993?vastamountsofattemptshave(henfocusedonthemoreefficientZn-porphyrindyesinrecentyearsPorphyrindyesderivedbysubstitul-ing-positionwithdificrcnianchoringgroupsexhibitedincreasingefficiencyfrom4.8%in2OO4*7to7.1%in2007”byGratae!andco-workcn.Moreover,ahigherefficiencyof7.5%wasobtainedbyKimandco

45、-workers,comparableco7.7%efficiencywithN3underthesamecondition.-*Replacingmesopositionswithadiarykiminodonorgrouponporphyrin,thedyeYD2boostedtheefficiencyrecord(o10.9Q511untilahigherrj=12.3%wasobtainedbyYD2yC8co-scnsitizcdwiththedyeY123.ThedyeYD2-O-C8hasthetypicaldonor-ir-bridgc-acccptor(DttA)struct

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