弱光上转换材料、构效关系与应用研究

发布时间：2018-02-07 15:43

本文关键词： 弱光上转换三线态-三线态湮灭微乳液光电流光降解　出处：《苏州科技学院》2015年硕士论文　论文类型：学位论文

【摘要】：基于三线态-三线态湮灭机制(triplet-triplet annihilation,TTA)的弱光上转换由于在太阳能电池、光催化、生物成像、光电器件以及三维光存储等领域具有潜在的应用价值而受到人们的广泛关注。弱光上转换材料的制备、结构与性能的关系以及上转换发光的探究是目前国内外重点研究课题之一。本论文研究的主要内容:1.材料设计与制备为了研究弱光上转换,基于文献知识,本文对卟啉和蒽衍生物展开分子设计,制备了一系列卟啉与蒽衍生物材料,分别是拥有较长的磷光寿命的:四苯基卟啉钯(PdTPP)和四苯基卟啉铂(PtTPP),以及具有很好的荧光性能的: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.金属配位对上转换的影响我们首先研究了双组分PdTPP/DTAMA和PtTPP/DTAMA的上转换现象,讨论了金属钯、铂配位对上转换效率的影响,发现钯配位的卟啉有利于弱光上转换。在DMF中,由钯配位的三线态敏化剂PdTPP呈现出较长的磷光寿命(15.4μs),较小的非磷光衰减速率常数(9.75×104 s-1)和较大的磷光量子产率(0.45%),这些动力学数据都有利提高三线态能量转移(TTT)效率。最终我们在低功率密度60mW?cm-2的激发下(532 nm),通过相对上转换效率公式,我们计算得出PdTPP/DTAMA的上转换效率(Φuc)高达19.12%,而PtTPP/DTAMA的是13.23%,所以,金属钯配位比铂配位的敏化剂更有利于提高上转换效率。最终,我们确定了钯配位的卟啉比较适合做上转换的敏化剂材料。3.发光剂结构对上转换的影响我们侧重研究了发光剂的荧光动力学对弱光上转换的影响。结果发现,发光剂的辐射衰减速率常数(kf)与非辐射衰减速率常数(knr)的比值控制着发光剂的荧光发射过程。实验测量结果与理论计算的对比揭示了TTT效率(FTTT)和荧光量子效率(Ff)在上转换效率(FUC)上有共同的贡献,而三线态-三线态湮灭(TTA)是可以忽略不计的。为了研究弱光上转换在光电化学方面的应用,我们找到了对蓝光非常敏感的ZnCdS光催化剂半导体,以此半导体为光阳极,通过用绿-转-蓝上转换荧光辐射负载在FTO导电玻璃上的ZnCdS,我们成功观察到了上转换蓝光响应的光电流。4.基于绿-转-蓝弱光上转换微乳液性能研究以PdTPP为敏化剂,DPA、DNACl为发光剂,制备了无毒环保、无需除氧脱气、空气稳定的上转换的微乳液,研究了上转换微乳液的相转变,首次发现了微乳液的相转变温度(PIT=38 OC)。之后我们侧重研究了微乳液中敏化剂磷光动力学对弱光上转换的影响。结果发现决定微乳液中上转换效率的是敏化剂的磷光寿命而不是磷光强度。5.绿-转-蓝上转换的应用研究我们首次研究了微乳液弱光上转换驱动罗丹明B(RhB)的光降解。结果发现绿-转-蓝上转换光的能量与ZnCdS价带和导带的能级差相符,通过上转换的光照射就能产生电荷分离。结果,绿-转-蓝上转换的光照射100min后,含有ZnCdS的罗丹明B溶液的光降解效率高达80%。据我们所知,目前的研究是弱光上转换驱动光降解的第一个实例,这为太阳光上转换驱动光降解奠定了基础。这项研究的意义在于:弱光上转换驱动的光降解可以实现太阳能对水的净化和环境政治。
[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.

【学位授予单位】：苏州科技学院
【学位级别】：硕士
【学位授予年份】：2015
【分类号】：TB34

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