基于增加长波吸收的卟啉类敏化染料的设计及光电性能分析-design and photoelectric properties analysis of porphyrin sensitized dyes based on increasing long wave absorption.docxVIP

体的光电转化效率。用对甲基二吡咯烷和对甲氧羰基苯甲醛为原料，采用[2+2]法合成卟啉化合物P1和P2，将这两种卟啉分别还原、氧化再与金属膦盐进行Wittig反应得到了四种双卟啉分子DP1-4(其中DP1和DP3中位含一酯基，DP2和DP4中位含一醛基)。将含酯基的双卟啉分子DP1和DP3分别水解得到两个含羧基的双卟啉染料分子DPD1和DPD2，并通过1H-NMR和质谱对其结构进行了表征。然后，将两种双卟啉染料分子DPD1-2与其相应的两种单体染料分子MPD1-2进行了光学性能、电化学性能以及光电转换性能的对比研究。通过对荧光光谱的分析发现，在双卟啉分子内存在着由锌卟啉向自由碱卟啉的能量/电子转移。该结果表明，在双卟啉体系中的锌卟啉向TiO2进行电子转移过程是以自由碱卟啉为“中转站”并通过两步电子转移完成的。这在一定程度上减少了电子回传，提高了电子注入效率。并且交流阻抗谱表明，由于双卟啉分子结构较大，降低了光生电子与电解质中I3-的结合，所以暗态电阻增加，暗电流降低。通过对比四种染料分子的光伏性能得出，DPD2的转化效率比其两种单体染料MPD1和MPD2的效率都高，然而DPD1由于溶解度较差，在光阳极上的吸附不好，导致其光电转换效率偏低。关键词：DSSCChlorin氟硼二吡咯共敏化双卟啉膜紫外ABSTRACTInthispaper,threestrategieshavebeenemployedtoimprovethelongwavelengthabsorptionofporphyrin-basedsensitizersystemsinDSSC,i.e.reductionoftheporphyrintodihydroporphyrin,co-sensitizedsystembetweenChlorin-typesensitizersandBODIPYsensitizers,andconstructionofbis-porphyrinsystem.Chlorin-typeframeworkwithlongwavelengthabsorptionhasbeenpreparedbythe1,3-dipolarcycloadditionbetweenA3B-porphyrinP0andnitrileoxides(2,6-dichlorophenylnitrileoxideand2,4,6-trimethylphenylnitrileoxide).ThenafterthemetallizationofthemonoadductsbyZn2+andthefollowinghydrolysisofCOOMegroup,Chorin-typesensitizersChD1a-4awith2,6-dichlorophenylgroupandChD1b-4bwith2,4,6-trimethylphenylgroupwereobtainedandcharacterizedby1H-NMR,MS,UV-Vis,fluorescence,cyclicvoltammetry,I-VandIPCEspectra,aswellastheTD-DFTcalculation.Byanalysisoftheaboveresults,itwasfoundthatthephotovoltaicperformanceincreasedwithgrowingabsorptionintensityofQbandonTiO2film.ThisresultindicatedthecontributionofintrinsicenhancedabsorptionpropertiesofchlorinsinQ-bandregionsontheimprovementoftheoverallphotovoltaicperformanceinDSSCs.Ontheotherhand,theircapabilityofsolarenergyconversionalsoexhibitedcloserelationshipwithstericstructuresofthesensitizers.ForChD1a-4a,thelowersterichindrancegroupwouldaggregateinthesolutionwhenthedichlorophenylgrouplocateat10-positionofChlorinframework.Thustheorientationofsterichindrancegrouptothe5-or15-position(theanchorgroupisat20-position)gavehighersolarenergy-to-electri