本文選題：多金屬氧酸鹽 + 卟啉�。� 參考：《東北師范大學(xué)》2017年碩士論文

【摘要】：能源危機(jī)使環(huán)境污染越來(lái)越嚴(yán)峻,人類亟需尋求安全、清潔的可再生能源。在各類可再生能源中,光伏發(fā)電效能最長(zhǎng)遠(yuǎn)。其中染料敏化太陽(yáng)能電池(DSSC)因?yàn)榈统杀�、高效率、制造工藝�?jiǎn)單等優(yōu)點(diǎn)而備受關(guān)注。染料敏化劑作為DSSC的光吸收劑,其性能的優(yōu)劣直接影響電池的光電轉(zhuǎn)換效率和光吸收效率。多金屬氧酸鹽,簡(jiǎn)稱多酸(POM),是一類金屬氧簇類化合物。它不僅結(jié)構(gòu)穩(wěn)定,而且還具有優(yōu)異的光電性質(zhì),較強(qiáng)的吸電子能力,可以與有機(jī)基團(tuán)結(jié)合形成具有良好光吸收性質(zhì)的有機(jī)-無(wú)機(jī)雜化物,在DSSC中具備潛在的應(yīng)用價(jià)值。本論文中,我們?cè)O(shè)計(jì)了多種多酸基有機(jī)-無(wú)機(jī)雜化物,采用密度泛函理論(DFT)和含時(shí)DFT(TDDFT)方法系統(tǒng)地研究了電子結(jié)構(gòu)、吸收光譜和電荷轉(zhuǎn)移特征,目的是探究其在DSSC中的應(yīng)用。主要內(nèi)容包括以下三部分:1.基于卟啉衍生物(體系1),設(shè)計(jì)了Lindqvist、Keggin、Anderson型多酸基有機(jī)-無(wú)機(jī)雜化衍生物(體系2-4)。采用DFT和TDDFT方法研究了體系1-4的電子結(jié)構(gòu)、吸收光譜和電荷轉(zhuǎn)移特征,篩選高效p-型染料。結(jié)果表明,Lindqvist和Keggin型多酸影響衍生物的最低空軌道能級(jí)和分布,而Anderson型多酸對(duì)衍生物的前線分子軌道沒(méi)有貢獻(xiàn)。Lindqvist型多酸卟啉衍生物(體系2)的吸收光譜在可見(jiàn)光區(qū)表現(xiàn)出強(qiáng)而寬的吸收,與體系1相比紅移大約100 nm,有望成為性能良好的染料敏化劑。2.基于優(yōu)異的染料敏化劑—苯乙炔基鋅卟啉,設(shè)計(jì)了一系列鋅卟啉多酸雜化物作為p-型染料敏化太陽(yáng)能電池的敏化劑。為了揭示π橋?qū)γ艋瘎┬阅艿挠绊?采用DFT和TDDFT方法研究它們的吸收光譜和電荷轉(zhuǎn)移特征。與體系1相比,體系2-5具有更長(zhǎng)的π橋和更高的離域性,吸收光譜紅移且拓寬�；陔姾赊D(zhuǎn)移量、電荷轉(zhuǎn)移距離和空間電荷分離程度的電荷轉(zhuǎn)移分析,結(jié)果表明,體系3達(dá)到了最大程度的電荷轉(zhuǎn)移量和電荷分離度。此外,體系3的吸收光譜與太陽(yáng)光譜重疊程度最大,有望成為良好性能的p-型染料敏化劑。3.為研究多酸對(duì)染料性能的影響,將Lindqvist型多酸引入實(shí)驗(yàn)合成的有機(jī)染料中,設(shè)計(jì)了一系列D-A-π-A型雜化物�；贒FT和TDDFT方法,系統(tǒng)研究了體系的電子結(jié)構(gòu)、吸收光譜和電荷轉(zhuǎn)移特征。與合成的染料對(duì)比發(fā)現(xiàn),設(shè)計(jì)的染料分子光譜響應(yīng)范圍更大,其電荷轉(zhuǎn)移方向均為給體向多酸和-COOH,證明染料與二氧化鈦之間存在較強(qiáng)的電子耦合。電荷轉(zhuǎn)移參數(shù)的分析表明,引入多酸后使染料的電荷轉(zhuǎn)移能力增強(qiáng)。綜合考慮光譜和電荷轉(zhuǎn)移特征,WS-51-POM與太陽(yáng)光譜的重疊面積最大,具有強(qiáng)的電荷轉(zhuǎn)移能力,是潛在的優(yōu)質(zhì)染料敏化劑。
[Abstract]:Environmental pollution is becoming more and more serious due to the energy crisis, and human beings urgently need to seek safe and clean renewable energy. Among all kinds of renewable energy, photovoltaic power generation efficiency is the longest. Dye-sensitized solar cells (DSSCs) have attracted much attention because of their advantages of low cost, high efficiency and simple manufacturing process. As the optical absorbent of DSSC, the performance of dye sensitizer has a direct impact on the photovoltaic conversion efficiency and optical absorption efficiency of the battery. Polyoxometalate (POM) is a kind of metal oxygen cluster compound. It not only has stable structure, but also has excellent optoelectronic properties and strong electron absorption ability. It can be combined with organic groups to form organic-inorganic hybrids with good light absorption properties. It has potential application value in DSSC. In this paper, we have designed a variety of polyacid organic-inorganic hybrids. The electronic structure, absorption spectra and charge-transfer characteristics have been systematically studied by using density functional theory (DFT) and time-dependent DFT-TDDFTFT (time-dependent DFT-TDDFTFT). The purpose of this study is to explore their application in DSSC. The main content includes the following three parts: 1. Based on porphyrin derivatives (system 1), Lindqvistr Kegginn Anderson type organic-inorganic hybrid derivatives (system 2-4) were designed. The electronic structure, absorption spectrum and charge-transfer characteristics of 1-4 system were studied by DFT and TDDFT methods. The results show that Lindqvist and Keggin type polyacids affect the lowest empty orbital energy levels and distributions of derivatives. The absorption spectra of Anderson type porphyrin derivatives (system 2) showed strong and wide absorption in the visible region. Compared with system 1, the red shift is about 100 nm, which is expected to be a good dye sensitizer. 2. Based on the excellent dye sensitizer phenylethynyl zinc porphyrin a series of zinc porphyrin polyacid hybrids were designed as sensitizers for p- type dye sensitized solar cells. In order to reveal the effect of 蟺 -bridge on the properties of sensitizers, the absorption spectra and charge-transfer characteristics of the sensitizers were studied by DFT and TDDFT. Compared with system 1, system 2-5 has longer 蟺 -bridge and higher delocalization, and the absorption spectrum is red-shifted and broadened. The results of charge transfer analysis based on charge transfer quantity, charge transfer distance and the degree of space charge separation show that the system 3 achieves the maximum charge transfer quantity and charge separation degree. In addition, the absorption spectrum of system 3 has the greatest overlap with the solar spectrum, which is expected to be a good p- type dye sensitizer. 3. In order to study the effect of polyacid on the properties of dyes, Lindqvist polyacid was introduced into the organic dyes synthesized experimentally, and a series of D-A- 蟺 -A hybrids were designed. Based on the DFT and TDDFT methods, the electronic structure, absorption spectrum and charge transfer characteristics of the system were systematically studied. Compared with the synthesized dyes, it is found that the designed dyes have a larger spectral response range, and their charge transfer directions are donor polyacid and -COOH, which indicates that there is a strong electronic coupling between the dyes and TIO _ 2. The analysis of charge transfer parameters showed that the charge transfer ability of dyes was enhanced by the introduction of polyacids. Considering the spectral and charge-transfer characteristics, WS-51-POM has the largest overlapping area with the solar spectrum and has a strong charge transfer ability. It is a potential high quality dye sensitizer.
【學(xué)位授予單位】：東北師范大學(xué)
【學(xué)位級(jí)別】：碩士
【學(xué)位授予年份】：2017
【分類號(hào)】：O641.4;TM914.4

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相關(guān)期刊論文 前1條

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本文編號(hào)：2033855