本文選題：熒光開關(guān) + 多酸　； 參考：《吉林大學(xué)》2017年博士論文

【摘要】：多金屬氧酸鹽(簡稱:多酸)是一類無機-金屬氧簇,具有納米尺度。由于其組成豐富、結(jié)構(gòu)多樣、性質(zhì)可調(diào)等特點,使得其有高的水溶性、好的耐熱性、強的抗氧化性、好的可逆性、優(yōu)良的質(zhì)子和電子存儲能力、可逆靈活的氧化還原能力及對環(huán)境友好、無污染等獨有的優(yōu)勢,從而引起了廣大研究者的研究興趣。熒光開關(guān)是指在紫外燈照下,通過外界的刺激,熒光信號可逆的呈現(xiàn)與消失的過程。近些年來,熒光開關(guān)功能材料已在智能光窗、化學(xué)傳感、光學(xué)顯示、熒光成像、信息存儲等領(lǐng)域具有潛在的應(yīng)用,從而促進(jìn)了熒光開關(guān)材料研究的發(fā)展。熒光開關(guān)的實現(xiàn)要求功能材料中既包含發(fā)光組分又包含刺激變色組分。而多酸具有優(yōu)良的光致變色與電致變色的性能,含有稀土的多酸自身集發(fā)光組分稀土離子與變色組分多酸骨架于一體,因此可以將其組裝到復(fù)合功能材料中,從而實現(xiàn)熒光開關(guān)性能。多酸基熒光開關(guān)功能是通過著色態(tài)多酸與發(fā)光組分之間的熒光共振能量轉(zhuǎn)移來實現(xiàn)的。能量轉(zhuǎn)移的條件需滿足以下三點:1)能量給體(發(fā)光組分)與能量受體(變色組分)在一定距離范圍內(nèi);2)能量給體與能量受體以恰當(dāng)?shù)姆绞脚帕?3)能量給體的發(fā)射光譜與能量受體的吸收光譜有重疊部分。基于以上條件,通過分子設(shè)計,我們構(gòu)筑了一系列基于多酸的熒光開關(guān)材料。在本論文中,我們將多酸的電致變色性能與水溶性有機發(fā)光分子、稀土發(fā)光多酸的發(fā)光性能相結(jié)合,通過不同組裝技術(shù)構(gòu)筑了變色-發(fā)光薄膜材料,進(jìn)而實現(xiàn)了電化學(xué)調(diào)控下的紅光、綠光、橙光和白光的單色態(tài)熒光開關(guān)及白光到藍(lán)光的雙色態(tài)熒光開關(guān)。具體研究內(nèi)容如下:第一,我們選取可溶性的綠光分子8-羥基芘-1,3,6-三磺酸三鈉鹽(HOPTS)作為研究對象,通過電沉積與層層自組裝技術(shù)(LBL)結(jié)合的方法以及將綠光分子HOPTS負(fù)載到氧化石墨烯(GO)上生成雜合體GO@HOPTS后再與多酸組裝的方法,成功地制備了兩種類型的綠光復(fù)合薄膜材料。第一類型的綠光復(fù)合薄膜材料是通過簡易的電沉積方法在ITO導(dǎo)電玻璃基底上構(gòu)筑了一種新穎的綠光薄膜,然后,基于構(gòu)筑好的綠光薄膜,結(jié)合LBL技術(shù)成功構(gòu)筑了外包不同層數(shù)變色組分P5W30的綠光薄膜材料[(HOPTS)50/(PDDA/P5W30)n](n=10,film 1;n=27,film 2;n=57,film 3)。第二類型的綠光復(fù)合薄膜材料是基于正負(fù)電荷物質(zhì)間靜電相互作用的原理,我們把GO@HOPTS和變色組分多酸P5W30通過LBL技術(shù)在石英基底和ITO導(dǎo)電玻璃基底上制備了綠光薄膜材料{(PDDA/P5W30)5/[(PDDA/P5W30)5/PDDA/GO@HOPTS]15/(PDDA/P5W30)5}。通過循環(huán)伏安法表征了復(fù)合薄膜中P5W30的電化學(xué)活性、熒光光譜法表征了復(fù)合薄膜中HOPTS的發(fā)光性質(zhì)、原子力顯微鏡技術(shù)表征了復(fù)合薄膜的形貌、X-光電子能譜表征了復(fù)合薄膜的組成。此外,通過使用原位的紫外-可見光電化學(xué)體系、熒光光電化學(xué)體系研究了復(fù)合薄膜材料的電致變色性能與熒光開關(guān)行為。研究結(jié)果表明:上述兩類薄膜材料在電化學(xué)刺激下均顯示出綠光熒光開關(guān)性能,且具有很好的可逆性與穩(wěn)定性。進(jìn)一步比較發(fā)現(xiàn)電沉積與LBL技術(shù)結(jié)合的方法所制備的薄膜材料具有更寬的電壓范圍,因此這種方法為功能材料的組裝提供一種新的技術(shù)。第二,我們選取含有Sm~(3+)的橙光多酸Sm PW11作為研究對象。Sm PW11是一種集橙光組分Sm~(3+)與變色組分PW11于一體的分子二分體。首先,我們研究了在不同p H條件下Sm PW11的紫外可見吸收、電化學(xué)活性和熒光性質(zhì),確定了最佳p H條件,并在最佳p H溶液介質(zhì)中研究了Sm PW11的橙光開關(guān)性能。然后,我們通過選取兩種組分相同、結(jié)構(gòu)不同、電荷數(shù)不同的導(dǎo)電聚合物分子PDDA和PEI作為連接劑,在ITO導(dǎo)電玻璃基底上成功地制備了橙光薄膜材料[PDDA/P2W18]10/[PDDA/Sm PW11]60和[PEI/P2W18]10/[PEI/Sm PW11]60。通過紫外-可見光譜、熒光光譜、循環(huán)伏安法、計時電流法、X-射線光電子能譜和原子力顯微鏡技術(shù)對橙光薄膜材料進(jìn)行表征。最后,通過使用原位紫外-可見光電化學(xué)體系和熒光光電化學(xué)體系研究了橙光薄膜材料的橙光開關(guān)性能。研究結(jié)果表明:由于橙光發(fā)光組分稀土Sm~(3+)和電還原變色組分PW11之間的分子內(nèi)能量轉(zhuǎn)移,在電化學(xué)調(diào)控下,橙光復(fù)合薄膜材料不僅顯示了橙光的性能,還體現(xiàn)了穩(wěn)定可逆的橙色熒光開關(guān)行為。此外,與PDDA相比,PEI被認(rèn)為是構(gòu)筑多酸基復(fù)合薄膜材料的最佳分子連接劑。第三,我們選取含有Dy~(3+)的發(fā)白光多酸Dy PW11作為研究對象。首先,我們在不同p H條件下考察了Dy PW11的紫外-可見吸收光譜、熒光光譜和循環(huán)伏安,從而確定了Dy PW11的穩(wěn)定p H范圍及最佳的實驗條件,并在最佳實驗條件下研究了Dy PW11的白光開關(guān)性能。然后,通過合理的分子設(shè)計,我們成功地制備了三個發(fā)白光的薄膜(PEI/Dy PW11)41、{(PEI/P8W48)1/(PEI/Dy PW11)5}9和{(PEI/P8W48)3/(PEI/Dy PW11)5}9,并通過原位的光電化學(xué)體系研究了它們在-0.7V與0.7 V電位之間的熒光開關(guān)行為。研究結(jié)果表明:一方面,三個薄膜均顯示了很好的可逆性與穩(wěn)定性;另一方面,薄膜(PEI/Dy PW11)41實現(xiàn)了不完全的白光淬滅、薄膜{(PEI/P8W48)1/(PEI/Dy PW11)5}9實現(xiàn)了可逆的白-藍(lán)光雙色態(tài)熒光開關(guān)、薄膜{(PEI/P8W48)3/(PEI/Dy PW11)5}9實現(xiàn)了完全的白光熒光開關(guān)。因此,我們的研究工作不僅制備了純無機的白光薄膜材料,而且提供了一種潛在的選擇性淬滅特定顏色熒光的方法。第四,在第一部分研究工作的基礎(chǔ)上,我們選取了純無機的含有Tb~(3+)的發(fā)綠光多酸Tb Ge W作為研究對象。首先,我們在不同p H條件下研究了Tb Ge W的紫外-可見吸收、電化學(xué)活性和熒光性質(zhì),并找到了Tb Ge W穩(wěn)定的p H范圍及最佳實驗條件,并研究了溶液中綠光熒光開關(guān)行為。然后,我們使用質(zhì)子化的PEI聚電解質(zhì)作為分子連接劑,通過層層組裝技術(shù)成功地構(gòu)筑了發(fā)綠光的薄膜材料(PEI/Tb Ge W)42,在較高負(fù)電位-0.9 V時其熒光淬滅度僅達(dá)到24.6%。為了能夠提升此薄膜材料的熒光淬滅度,通過分子設(shè)計,我們在上述薄膜材料中引入了變色組分P2W18,進(jìn)而制備出P2W18和Tb Ge W具有不同比例的綠光薄膜材料(PEI/P2W18/PEI/Tb Ge W)42和{(PEI/P2W18)3/PEI/Tb Ge W}42,它們在外加-0.7 V電位時,其熒光淬滅度分別達(dá)到了56.9%和94.7%。研究結(jié)果表明:通過綠光組分稀土Tb~(3+)和電致變色組分Ge W之間的分子內(nèi)能量轉(zhuǎn)移以及與P2W18之間的分子間能量轉(zhuǎn)移,我們實現(xiàn)了純無機發(fā)綠光多酸Tb Ge W基礎(chǔ)上薄膜材料的綠光熒光開關(guān)。第五,我們選取含有Eu~(3+)的發(fā)紅光多酸簇Eu PW11作為研究對象。首先,我們在溶液中詳細(xì)考察了Eu PW11的紫外-可見吸收、電化學(xué)活性和熒光性質(zhì)與溶液p H的關(guān)系,最終確定了Eu PW11穩(wěn)定的p H范圍及最佳實驗條件,并研究了溶液中紅光熒光開關(guān)行為。然后,通過層層組裝技術(shù)制備了發(fā)紅光的薄膜材料(PEI/Eu PW11)39,其在外加-0.7 V電位時熒光淬滅度僅為69%。為了能夠徹底地實現(xiàn)紅光薄膜材料的熒光開關(guān),我們在上述薄膜材料中引入了變色組分P5W30,進(jìn)而組裝了發(fā)紅光的薄膜材料(PEI/P5W30/PEI/Eu PW11)39,其在外加-0.7 V電位時熒光淬滅度達(dá)到了94%。這項研究結(jié)果證明通過合理地引入電致變色多酸組分即可實現(xiàn)對紅光熒光的完全淬滅。總之,以熒光開關(guān)為導(dǎo)向,以多酸為構(gòu)筑基元,基于分子內(nèi)與分子間能量轉(zhuǎn)移的基本原理,我們分別制備了一系列不同顏色發(fā)光的薄膜材料,而且實現(xiàn)了紅光、綠光、橙光和白光的單色態(tài)熒光開關(guān)及白-藍(lán)光轉(zhuǎn)換的雙色態(tài)熒光開關(guān)。此外,發(fā)展了一種構(gòu)筑薄膜材料的新方法,即電聚合和層層組裝結(jié)合的方法。因此,此論文研究工作不僅促進(jìn)了多酸在熒光開關(guān)材料方面研究的進(jìn)展,而且在發(fā)展純無機熒光開關(guān)材料的研究方面提供了有益的借鑒。
[Abstract]:Polyoxometalates (polyoxometalates) are a class of inorganic metal oxygen clusters, which have nano scale. Due to their rich composition, diverse structure and adjustable properties, they have high solubility in water, good heat resistance, strong antioxidation, good reversibility, excellent proton and electronic storage capacity, reversible and flexible redox ability and environment. In recent years, fluorescent switch functional materials have been used in intelligent light windows, chemical sensing, optical display, optical display, fluorescence imaging, information storage and so on. The field has potential applications, which promotes the development of the study of fluorescent switching materials. The realization of the fluorescent switch requires that the functional materials include both the luminescent components and the discoloration components. The polyacid has excellent photochromism and electrochromic properties, and the rare earth's polyacid self set luminescence component and the discoloration component contain the rare earth. The acid skeleton is integrated so that it can be assembled into the composite functional material to achieve the performance of the fluorescent switch. The function of the polyacid based fluorescent switch is realized by the fluorescence resonance energy transfer between the colored polyacid and the luminescent component. The energy transfer conditions need to meet the following three points: 1) energy donor (luminescent component) and energy receptor ( Discoloration components) within a certain range; 2) the energy donor and energy receptors are arranged in a proper way; 3) the emission spectrum of the energy donor is overlapped with the absorption spectrum of the energy receptor. Based on the above conditions, we have constructed a series of polyacid based fluorescent switching materials by molecular design. In this paper, we will be polyacid. The electrochromic properties are combined with water-soluble organic luminescent molecules and the luminescent properties of rare earth luminescent polyacids. The color change luminescent film materials are constructed by different assembly techniques, and the red light, green light, orange and white light fluorescence switches under the electrochemical regulation and the double color fluorescence switch from white to blue light under the electrochemical control are realized. The contents are as follows: first, we select the soluble green light molecule 8- hydroxy pyrene -1,3,6- three sulfonic acid three sodium salt (HOPTS) as the research object, through the method of combining electrodeposition with layer layer self-assembly technology (LBL) and the method of generating complex GO@HOPTS by loading the green light molecule HOPTS to the graphene oxide (GO) and then assembling the polyacid with the polyacid. Two types of green light composite film materials are prepared. The first type of green light composite film is a novel green light thin film on the ITO conductive glass substrate by simple electrodeposition. Then, based on the constructed green light thin film and LBL technology, the green light thin film with different layers of discoloration components P5W30 is constructed successfully. The membrane material [(HOPTS) 50/ (PDDA/P5W30) n] (n=10, film 1; n=27, film 2; n=57, film 3). The second type green light composite film material is based on the principle of electrostatic interaction between positive and negative charge materials. DDA/P5W30) 5/[(PDDA/P5W30) 5/PDDA/GO@HOPTS]15/ (PDDA/P5W30) 5}. characterized the electrochemical activity of P5W30 in the composite film by cyclic voltammetry. The luminescence properties of HOPTS in the composite film were characterized by fluorescence spectroscopy. The morphology of the composite films was characterized by atomic force microscopy. The composition of the composite films was characterized by the X- photoelectron spectroscopy. Furthermore, the composition of the composite films was characterized by the atomic force microscopy. By using in situ UV visible photochemical system, the electrochromic properties and fluorescence switch behavior of the composite film materials are studied by the fluorescence photoelectrochemical system. The results show that the above two kinds of thin film materials show the performance of the green light switch under the electrochemical stimulation, and have good reversibility and stability. It is found that the thin film materials prepared by the combination of electrodeposition and LBL technology have a wider range of voltage. Therefore, this method provides a new technique for the assembly of functional materials. Second, we select the orange polyacid Sm PW11 containing Sm~ (3+) as the study object,.Sm PW11, an orange component Sm~ (3+) and a color component PW11. First, we studied the UV visible absorption, electrochemical activity and fluorescence properties of Sm PW11 under different P H conditions, determined the optimum P H condition, and studied the orange switch performance of Sm PW11 in the best p H solution medium. Then, we chose the same two components, the structure is different, the charge number is different. The conductive polymer molecules PDDA and PEI are used as connecting agents to prepare orange light thin film materials [PDDA/P2W18]10/[PDDA/Sm PW11]60 and [PEI/P2W18]10/[PEI/Sm PW11]60. on ITO conductive glass substrates by UV visible spectra, fluorescence spectra, cyclic voltammetry, chronoamperometric method, X- ray photoelectron spectroscopy and atomic force microscopy. Orange light thin film materials are characterized. Finally, the orange light switching properties of orange light thin film materials are studied by using in situ UV visible photoelectrochemistry and fluorescent photoelectrochemical system. The results show that the intramolecular energy transfer between the rare earth Sm~ (3+) and the electrochromic component PW11 of the orange light luminescence is controlled by electrochemistry The orange light composite film not only shows the properties of orange light, but also reflects the stable and reversible orange fluorescent switch behavior. In addition, compared with PDDA, PEI is considered as the best molecular linking agent for constructing polyacid based composite film materials. Third, we select the white light polyacid Dy PW11 containing Dy~ (3+) as the research object. First, we are not Under the condition of P H, the UV visible absorption spectra, fluorescence spectra and cyclic voltammetry of Dy PW11 were investigated, and the stable P H range of Dy PW11 and the best experimental conditions were determined. The white light switching performance of Dy PW11 was studied under the best experimental conditions. Then, we successfully prepared three thin white light thin films by rational molecular design. The film (PEI/Dy PW11) 41, {(PEI/P8W48) 1/ (PEI/Dy PW11) 5}9 and {(PEI/P8W48) 3/ (PEI/Dy PW11) 5}9 are studied by in situ photochemical systems. 41) 41 realized incomplete white light quenching, the film {(PEI/Dy PW11) 5}9 realized reversible white blue double color fluorescence switch, and the film {(PEI/P8W48) 3/ (PEI/Dy PW11) 5}9 realized complete white light fluorescence switch. Therefore, our research work not only prepared pure inorganic white light thin film material, but also provided a potential of potential. The method of selectively quenching specific color fluorescence. Fourth, on the basis of the first part of the study, we selected pure inorganic Tb~ (3+) Tb Ge W as the research object. First, we studied the UV visible absorption, electrochemical activity and fluorescence properties of Tb Ge W under different P H conditions, and found the Tb Ge. W stable P H range and the best experimental conditions, and study the behavior of green light fluorescence switch in the solution. Then, we use the protonated PEI polyelectrolyte as a molecular connector, successfully constructed the green light thin film material (PEI/Tb Ge W) 42 through the layer assembly technology, and the fluorescence quenching degree is only to 24.6%. at the higher negative potential -0.9 V, and the fluorescence quenching degree is only to 24.6%.. In order to improve the fluorescence quenching degree of this film material, by molecular design, we introduced the discoloration component P2W18 in the above film materials, and then prepared the green light film materials (PEI/P2W18/PEI/Tb Ge W) 42 and {(PEI/P2W18) 3/ PEI/Tb Ge as P2W18 and Tb Ge W. The 56.9% and 94.7%. results show that the green light switch between the green light component rare earth Tb~ (3+) and the electrochromic component Ge W between the molecular energy transfer and the intermolecular energy transfer between P2W18, and the pure inorganic green polyacid Tb Ge W based on the green fluorescent switch. Fifth, we choose to contain The red light polyacid cluster Eu PW11 of Eu~ (3+) is used as the research object. First, we investigated the ultraviolet visible absorption of Eu PW11 in the solution, the relationship between the electrochemical activity and the fluorescence property and the solution P H. Finally, the P H range and the optimum experimental conditions for the Eu PW11 stabilized, and the behavior of the red fluorescence switch in the solution were studied. Then, through the study, the behavior of the red light fluorescence switch in the solution was studied. The red thin film material (PEI/Eu PW11) 39 was prepared by layer assembly technology. The fluorescence quenching degree of the film was only 69%. at the -0.7 V potential in order to complete the fluorescence switch of the red film material thoroughly. We introduced the discoloration component P5W30 in the film materials above, and then assembled the red thin film material (PEI/P5W30/PEI/Eu PW11). 39, the fluorescence quenching degree of the -0.7 V potential was reached to 94%.. The result of the study proved that the red light fluorescence could be completely quenched by the rational introduction of electrochromic polyacid components. In a word, we made the basic principle of the fluorescence switch as the guidance, the polyacid as the building element and the intramolecular and intermolecular energy transfer based on the basic principle. A series of thin film materials with different colors are prepared, and the monochromatic fluorescence switches of red, green, orange and white light and white blue light switching are used. In addition, a new method of building thin film materials is developed, that is, the method of electropolymerization and layer assembly and bonding. Therefore, this research work not only promotes the research work of this paper. The research progress of Polyoxometalates in fluorescent switch materials has provided a useful reference for the development of pure inorganic fluorescent switch materials.
【學(xué)位授予單位】：吉林大學(xué)
【學(xué)位級別】：博士
【學(xué)位授予年份】：2017
【分類號】：O657.3

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2 孫朝霞;;全國光學(xué)功能薄膜材料標(biāo)準(zhǔn)化技術(shù)委員會2012年度標(biāo)準(zhǔn)化工作會議暨行標(biāo)審查會在濟南圓滿舉行[J];信息記錄材料;2013年01期

3 ;美國成功發(fā)明出可變色薄膜材料[J];河南化工;2013年07期

4 劉江龍,鄒至榮;激光化學(xué)氣相沉積薄膜材料技術(shù)的研究進(jìn)展[J];材料導(dǎo)報;1991年10期

5 ;薄膜材料科學(xué)與技術(shù)──青年科學(xué)家論壇第44次活動[J];學(xué)會;2001年04期

6 王懷文,亢一瀾,富東慧;應(yīng)用數(shù)字散斑相關(guān)技術(shù)進(jìn)行薄膜材料斷裂問題研究[J];煙臺大學(xué)學(xué)報(自然科學(xué)與工程版);2001年02期

7 夏德宏,吳永紅,李樹柯;薄膜材料的熱輻射穿透深度研究[J];熱科學(xué)與技術(shù);2003年03期

8 胡江川,王萬錄,馬平,陳松林;幾種紫外薄膜材料的閾值場強分析[J];重慶大學(xué)學(xué)報(自然科學(xué)版);2005年08期

9 史芳;賴欣;崔春華;何見超;畢劍;高道江;;功能薄膜材料的環(huán)境協(xié)調(diào)性制備技術(shù)研究進(jìn)展[J];科學(xué)技術(shù)與工程;2006年09期

10 龍斌;;韓國開發(fā)出使薄膜材料領(lǐng)域研究成果最大化的高速研究技法[J];功能材料信息;2007年01期

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1 張斌;施立群;承煥生;王建中;李嘉慶;張杰雄;;核分析技術(shù)在薄膜材料中的應(yīng)用[A];第十四屆全國核物理大會暨第十屆會員代表大會論文集[C];2010年

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3 劉書田;許衛(wèi)凱;董炎章;;左手薄膜材料的設(shè)計優(yōu)化[A];第十五屆全國復(fù)合材料學(xué)術(shù)會議論文集（上冊）[C];2008年

4 蔡s，

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