本文關(guān)鍵詞： 弱光上轉(zhuǎn)換 三線態(tài)-三線態(tài)湮滅 微乳液 光電流 光降解　出處：《蘇州科技學(xué)院》2015年碩士論文　論文類型：學(xué)位論文

【摘要】：基于三線態(tài)-三線態(tài)湮滅機(jī)制(triplet-triplet annihilation,TTA)的弱光上轉(zhuǎn)換由于在太陽能電池、光催化、生物成像、光電器件以及三維光存儲(chǔ)等領(lǐng)域具有潛在的應(yīng)用價(jià)值而受到人們的廣泛關(guān)注。弱光上轉(zhuǎn)換材料的制備、結(jié)構(gòu)與性能的關(guān)系以及上轉(zhuǎn)換發(fā)光的探究是目前國(guó)內(nèi)外重點(diǎn)研究課題之一。本論文研究的主要內(nèi)容:1.材料設(shè)計(jì)與制備為了研究弱光上轉(zhuǎn)換,基于文獻(xiàn)知識(shí),本文對(duì)卟啉和蒽衍生物展開分子設(shè)計(jì),制備了一系列卟啉與蒽衍生物材料,分別是擁有較長(zhǎng)的磷光壽命的:四苯基卟啉鈀(PdTPP)和四苯基卟啉鉑(PtTPP),以及具有很好的熒光性能的:蒽(An),9,10-二苯基蒽(DPA),2-氯代-9,10-二萘基蒽(DNACl),2-氰基-9,10-二萘基蒽(DNACN),2-甲酯基-9,10-二甲苯基蒽(DTAMA)。2.金屬配位對(duì)上轉(zhuǎn)換的影響我們首先研究了雙組分PdTPP/DTAMA和PtTPP/DTAMA的上轉(zhuǎn)換現(xiàn)象,討論了金屬鈀、鉑配位對(duì)上轉(zhuǎn)換效率的影響,發(fā)現(xiàn)鈀配位的卟啉有利于弱光上轉(zhuǎn)換。在DMF中,由鈀配位的三線態(tài)敏化劑PdTPP呈現(xiàn)出較長(zhǎng)的磷光壽命(15.4μs),較小的非磷光衰減速率常數(shù)(9.75×104 s-1)和較大的磷光量子產(chǎn)率(0.45%),這些動(dòng)力學(xué)數(shù)據(jù)都有利提高三線態(tài)能量轉(zhuǎn)移(TTT)效率。最終我們?cè)诘凸β拭芏?0mW?cm-2的激發(fā)下(532 nm),通過相對(duì)上轉(zhuǎn)換效率公式,我們計(jì)算得出PdTPP/DTAMA的上轉(zhuǎn)換效率(Φuc)高達(dá)19.12%,而PtTPP/DTAMA的是13.23%,所以,金屬鈀配位比鉑配位的敏化劑更有利于提高上轉(zhuǎn)換效率。最終,我們確定了鈀配位的卟啉比較適合做上轉(zhuǎn)換的敏化劑材料。3.發(fā)光劑結(jié)構(gòu)對(duì)上轉(zhuǎn)換的影響我們側(cè)重研究了發(fā)光劑的熒光動(dòng)力學(xué)對(duì)弱光上轉(zhuǎn)換的影響。結(jié)果發(fā)現(xiàn),發(fā)光劑的輻射衰減速率常數(shù)(kf)與非輻射衰減速率常數(shù)(knr)的比值控制著發(fā)光劑的熒光發(fā)射過程。實(shí)驗(yàn)測(cè)量結(jié)果與理論計(jì)算的對(duì)比揭示了TTT效率(FTTT)和熒光量子效率(Ff)在上轉(zhuǎn)換效率(FUC)上有共同的貢獻(xiàn),而三線態(tài)-三線態(tài)湮滅(TTA)是可以忽略不計(jì)的。為了研究弱光上轉(zhuǎn)換在光電化學(xué)方面的應(yīng)用,我們找到了對(duì)藍(lán)光非常敏感的ZnCdS光催化劑半導(dǎo)體,以此半導(dǎo)體為光陽極,通過用綠-轉(zhuǎn)-藍(lán)上轉(zhuǎn)換熒光輻射負(fù)載在FTO導(dǎo)電玻璃上的ZnCdS,我們成功觀察到了上轉(zhuǎn)換藍(lán)光響應(yīng)的光電流。4.基于綠-轉(zhuǎn)-藍(lán)弱光上轉(zhuǎn)換微乳液性能研究以PdTPP為敏化劑,DPA、DNACl為發(fā)光劑,制備了無毒環(huán)保、無需除氧脫氣、空氣穩(wěn)定的上轉(zhuǎn)換的微乳液,研究了上轉(zhuǎn)換微乳液的相轉(zhuǎn)變,首次發(fā)現(xiàn)了微乳液的相轉(zhuǎn)變溫度(PIT=38 OC)。之后我們側(cè)重研究了微乳液中敏化劑磷光動(dòng)力學(xué)對(duì)弱光上轉(zhuǎn)換的影響。結(jié)果發(fā)現(xiàn)決定微乳液中上轉(zhuǎn)換效率的是敏化劑的磷光壽命而不是磷光強(qiáng)度。5.綠-轉(zhuǎn)-藍(lán)上轉(zhuǎn)換的應(yīng)用研究我們首次研究了微乳液弱光上轉(zhuǎn)換驅(qū)動(dòng)羅丹明B(RhB)的光降解。結(jié)果發(fā)現(xiàn)綠-轉(zhuǎn)-藍(lán)上轉(zhuǎn)換光的能量與ZnCdS價(jià)帶和導(dǎo)帶的能級(jí)差相符,通過上轉(zhuǎn)換的光照射就能產(chǎn)生電荷分離。結(jié)果,綠-轉(zhuǎn)-藍(lán)上轉(zhuǎn)換的光照射100min后,含有ZnCdS的羅丹明B溶液的光降解效率高達(dá)80%。據(jù)我們所知,目前的研究是弱光上轉(zhuǎn)換驅(qū)動(dòng)光降解的第一個(gè)實(shí)例,這為太陽光上轉(zhuǎn)換驅(qū)動(dòng)光降解奠定了基礎(chǔ)。這項(xiàng)研究的意義在于:弱光上轉(zhuǎn)換驅(qū)動(dòng)的光降解可以實(shí)現(xiàn)太陽能對(duì)水的凈化和環(huán)境政治。
[Abstract]:Three - three triplet triplet annihilation mechanism based on (triplet-triplet annihilation, TTA) of weak light conversion due to the solar cell, photocatalysis, biological imaging, photoelectric device and three-dimensional optical storage and other fields has potential application value and attention. Weak light conversion material preparation, structure and relationship the properties and upconversion luminescence of inquiry is one of the focus of the current research topic at home and abroad. The main contents of this paper: 1. material design and preparation in order to study the effect of weak light on conversion, based on the literature knowledge, this article launches the molecular design of porphyrin and anthracene derivatives, a series of porphyrin and anthracene derivatives were prepared, respectively. Is having a long phosphorescence lifetime: four phenyl porphyrin palladium (PdTPP) and four phenyl porphyrin platinum (PtTPP), and has good fluorescence properties of anthracene (An), 9,10- two (DPA, 2-) anthracene phenyl chloro -9,10- two naphthyl anthracene (DNACl) 2- -9,10- two naphthyl anthracene, cyano (DNACN), 2- methyl -9,10- DIMETHYLPHENYL anthracene (DTAMA).2. metal coordination effect on Upconversion we first study the two components of PdTPP/DTAMA and PtTPP/DTAMA on the conversion phenomenon, discussed the metal palladium, platinum coordination effect on the conversion efficiency. Found that palladium ligand porphyrin is conducive to the conversion of weak light. In DMF, the PdTPP three triplet sensitizer palladium ligand exhibits a long lifetime (15.4 s), non phosphorescence decay rate constant is smaller (9.75 x 104 s-1) and larger phosphorescence quantum yield (0.45%), these the kinetic data are beneficial to the improvement of the three triplet energy transfer (TTT) efficiency. Finally we at low power density 60mW? Under the excitation of cm-2 (532 nm), the relative efficiency of the formula, we calculated the conversion efficiency of PdTPP/DTAMA (UC) as high as 19.12%, while the PtTPP/DTAMA is 13.23%, so, metal Pd More than a sensitizer of platinum coordination to improve conversion efficiency. Finally, we determined the palladium ligand porphyrin sensitizer material more suitable for.3. upconversion luminescence agent structure influence on the conversion of our focus on the study of effect of fluorescence luminescence agent on the conversion of the weak light. The results showed that light agent radiation attenuation rate constant (KF) and non radiative decay rate constant (KNR) ratio controls the fluorescence emission luminescence agent process. Comparison of experimental results with theoretical calculation reveals the efficiency of TTT (FTTT) and fluorescence quantum efficiency (Ff) on the conversion efficiency (FUC) is the common contribution. Three - three triplet triplet annihilation (TTA) is negligible. In order to study the application of weak light on the photoelectric conversion in the field of chemistry, we found ZnCdS semiconductor photocatalyst is very sensitive to blue light, the semiconductor light through the anode. With the green - Blue upconversion fluorescence radiation load on FTO conductive glass ZnCdS, we successfully observed the photocurrent response of.4. upconversion blue green - Blue - weak light conversion of micro emulsion with PdTPP as sensitizer, DPA based on DNACl as light agent, preparation of non-toxic ring Paul, without oxygen degassing, microemulsion conversion air stability, phase transformation on the conversion of microemulsion, first discovered the phase transition temperature of microemulsion (PIT=38 OC). Then we focus on the study of microemulsion on the kinetics of phosphorescent sensitizer on the conversion of weak light effects. The results show that the decision the micro emulsion on conversion efficiency is sensitized phosphorescence lifetime instead of phosphorescence intensity.5. green - - Blue upconversion application we study the micro emulsion of weak light conversion driver Luo Danming B (RhB). The results showed that the degradation of light green to blue light energy conversion With the ZnCdS of the valence band and conduction band gap with the charge separation by light irradiation can convert. As a result, green turned light blue 100min conversion, light degradation efficiency of Luo Danming B solution with ZnCdS up to 80%. to our knowledge, the present study is the first example of weak light on transfer drive light degradation, the sun light conversion drive photodegradation of the foundation. The significance of this study is that: the photocatalytic degradation of weak light conversion can be achieved on the solar driven water purification and political environment.

【學(xué)位授予單位】：蘇州科技學(xué)院
【學(xué)位級(jí)別】：碩士
【學(xué)位授予年份】：2015
【分類號(hào)】：TB34

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