基于光響應(yīng)偶氮苯表面活性劑修飾石墨烯及其復(fù)合材料的制備研究
發(fā)布時(shí)間：2018-07-27 13:45
【摘要】：石墨烯作為二維SP2網(wǎng)絡(luò)結(jié)構(gòu)的碳材料,以其獨(dú)特的物理化學(xué)性質(zhì)被廣泛關(guān)注。其優(yōu)秀的導(dǎo)電、機(jī)械強(qiáng)度、電荷傳輸?shù)刃阅苁故┎牧蠌V泛應(yīng)用于光電設(shè)備。目前石墨烯功能化的主要方法是物理和化學(xué)方法改性,各種各樣的有機(jī)或無(wú)機(jī)化合物添加到石墨烯表面。其中,大量研究工作集中在石墨烯復(fù)合材料組分之間的自組裝、協(xié)同作用以及界面效應(yīng)等。近些年,光響應(yīng)石墨烯材料成為石墨烯材料發(fā)展的熱點(diǎn)之一。一些重要的修飾方法(π-堆積和化學(xué)共價(jià)鍵作用)制備光響應(yīng)石墨烯復(fù)合材料相繼報(bào)道。由于其獨(dú)特的光響應(yīng)特性,該類材料在光電和能量?jī)?chǔ)備等應(yīng)用領(lǐng)域有潛在的應(yīng)用價(jià)值。雖然這些光響應(yīng)石墨烯復(fù)合材料已經(jīng)報(bào)道,光響應(yīng)分子結(jié)構(gòu)變化引起石墨烯空間構(gòu)象、微結(jié)構(gòu)、光電子能量轉(zhuǎn)變等科學(xué)問(wèn)題仍然是重大挑戰(zhàn)。因此,重點(diǎn)研究這些科學(xué)問(wèn)題以及新的改性技術(shù)十分必要和關(guān)鍵。本論文通過(guò)小分子偶氮苯表面活性劑修飾石墨烯,制備出新型的光響應(yīng)偶氮苯-石墨烯復(fù)合材料。同時(shí)進(jìn)一步以該類偶氮苯表面活性劑作為穩(wěn)定劑,制備出光響應(yīng)偶氮苯-石墨烯-金納米粒子復(fù)合材料。為光響應(yīng)石墨烯材料的發(fā)展提供了一種嶄新的改性技術(shù)。具體研究?jī)?nèi)容為:(1)偶氮苯表面活性劑采用有機(jī)合成和分子設(shè)計(jì)制備出光響應(yīng)偶氮苯陽(yáng)離子表面活性劑。對(duì)其化學(xué)結(jié)構(gòu)和光致異構(gòu)變化進(jìn)行了表征。研究結(jié)果表明,偶氮苯表面活性劑在波長(zhǎng)為350nm紫外光和455 nm的可見光誘導(dǎo)下具有光響應(yīng)特性,其紫外可見吸收光譜(UV-Vis)能夠可逆轉(zhuǎn)變。此外,再次對(duì)偶氮苯表面活性劑進(jìn)行分子結(jié)構(gòu)設(shè)計(jì),制備出雙子型Gemini偶氮苯表變活性劑,為光響應(yīng)石墨烯-金屬納米復(fù)合材料的制備提供穩(wěn)定劑。(2)偶氮苯-石墨烯復(fù)合材料基于陽(yáng)離子偶氮苯表面活性劑的電荷屬性,通過(guò)離子鍵作用將陽(yáng)離子偶氮苯表面活性劑(Azo C7NO)修飾到帶負(fù)電荷的氧化石墨烯表面,制備出光響應(yīng)偶氮苯-石墨烯復(fù)合材料(Azo-GO)。Zeta電位測(cè)試結(jié)果表明,該偶氮苯表面活性劑的引入改變了氧化石墨烯的表面電位,其表面電荷由負(fù)電位快速變?yōu)檎娢�。熒光光譜表明,該偶氮苯-石墨烯復(fù)合材料具有熒光性,證明Azo C7NO主要以離子鍵作用在氧化石墨烯上,而非常見的π-堆積(熒光猝滅),從而為光響應(yīng)偶氮苯表面活性劑對(duì)石墨烯的修飾提供了理論支持。X射線衍射(XRD)、掃描電鏡(SEM)、原子力顯微鏡(AFM)研究結(jié)果表明,本偶氮苯-石墨烯復(fù)合材料具有獨(dú)特的自組裝特性,主要由于靜電作用使氧化石墨烯中的負(fù)電荷(羧基基團(tuán))抵消,使其羧基之間的靜電排斥作用消失。此外,紅外光譜(FTIR)、X射線光電子能譜(XPS)、熱重(TGA)表明,復(fù)合材料中偶氮苯基團(tuán)的接枝率為每71個(gè)石墨烯碳原子修飾一個(gè)偶氮苯分子,具有較高的接枝率。(3)偶氮苯-石墨烯復(fù)合材料光響應(yīng)基于偶氮苯基團(tuán)的光響應(yīng)屬性,對(duì)偶氮苯-石墨烯復(fù)合材料的光響應(yīng)特性進(jìn)行了研究。紫外可見吸收光譜(UV-Vis)表明,該偶氮苯-石墨烯復(fù)合材料具有光化學(xué)特性。X射線衍射(XRD)、原子力顯微鏡(AFM)以及拉曼光譜(Raman)表明,紫外光和藍(lán)光誘導(dǎo)能夠引起偶氮苯表面活性劑順-反可逆異構(gòu)以及親疏水性的可逆轉(zhuǎn)變,從而光控制該復(fù)合材料的自組裝特性發(fā)生可逆變化。此外,電化學(xué)循環(huán)伏安(CV)研究結(jié)果表明,該復(fù)合材料的電化學(xué)性質(zhì)同樣能夠被光可逆控制。在已經(jīng)報(bào)道的偶氮苯-石墨烯復(fù)合材料中,通過(guò)π-堆積和共價(jià)鍵作用制備的復(fù)合材料,其光響應(yīng)性質(zhì)的變化主要是由于偶氮苯分子內(nèi)部的空間異構(gòu)變化。而本論文制備的偶氮苯-石墨烯復(fù)合材料的光響應(yīng)性質(zhì)的變化,主要由偶氮苯表面活性劑特有的光誘導(dǎo)分子極性和親疏水的變化引起復(fù)合材料的自組裝的轉(zhuǎn)變來(lái)決定。該光控自組裝現(xiàn)象是一種嶄新的自裝現(xiàn)象,對(duì)其進(jìn)一步研究有可能為自組裝理論提供介觀范圍內(nèi)的研究實(shí)例和理論模型,促進(jìn)自組裝理論的發(fā)展。(4)光響應(yīng)偶氮苯-石墨烯-金納米粒子復(fù)合材料為進(jìn)一步發(fā)展偶氮苯表面活性劑在石墨烯納米復(fù)合材料的應(yīng)用,從分子結(jié)構(gòu)設(shè)計(jì)出發(fā),制備出雙子Gemini偶氮苯表面活性劑(Azo C10N2O2)。該類偶氮苯表面活性劑以偶氮苯為連接基團(tuán)具有兩個(gè)陽(yáng)離子基團(tuán)。因此,以Azo C10N2O2作為穩(wěn)定劑通過(guò)靜電作用來(lái)定位金屬納米粒子到石墨烯表面。同時(shí),利用化學(xué)還原法一鍋法制備出一種新型的光響應(yīng)偶氮苯-石墨烯-金納米粒子復(fù)合材料(Azo-RGO-GNP)。利用X射線衍射(XRD)、X射線光電子能譜(XPS)、熱重(TGA)、透射電鏡(TEM)和紫外可見吸收光譜(UV-Vis)對(duì)復(fù)合材料的結(jié)構(gòu)和性質(zhì)進(jìn)行研究。研究結(jié)果表明,以Azo C10N2O2作為穩(wěn)定劑可以使金納米粒子均勻的分布在石墨烯表面,實(shí)現(xiàn)了準(zhǔn)確定位。穩(wěn)定劑中的偶氮苯基團(tuán)使該復(fù)合材料具有光化學(xué)性質(zhì)。通過(guò)該技術(shù),首次合成光響應(yīng)偶氮苯-石墨烯-金納米粒子復(fù)合材料。此外,電化學(xué)循環(huán)伏安(CV)研究表明,該復(fù)合材料的導(dǎo)電性能同樣可以通過(guò)光來(lái)控制。因此,該偶氮苯-石墨烯-金納米粒子復(fù)合材料在光敏傳感器以及電化學(xué)領(lǐng)域具有潛在的應(yīng)用價(jià)值。
[Abstract]:Graphene, as a carbon material of two-dimensional SP2 network structure, is widely concerned with its unique physical and chemical properties. Its excellent conductivity, mechanical strength, charge transmission and other properties make graphene materials widely used in optoelectronic devices. The main methods of graphene functionalization are physical and chemical modification, a variety of organic or inorganic methods. Compounds are added to the surface of graphene. A large number of research work is focused on the self-assembly, synergism and interfacial effects of graphene composite components. In recent years, photoresponse graphene materials have become one of the hotspots of the development of graphene materials. Some important modified methods (PI accumulation and chemical covalent bond action) have been used to produce light response. Graphene composites have been reported successively. Due to their unique optical response characteristics, these materials have potential applications in the applications of photoelectric and energy reserves. Although these photoresponse graphene composites have been reported, the changes in the molecular structure of the photoresponse cause the space conformation, microstructures, photoelectron energy transformation and other science of graphene. The problem is still a major challenge. Therefore, it is necessary and key to focus on these scientific problems and the new modified technology. This paper has prepared a new type of photoresponse azobenzene graphene composite by modifying the graphene by the small molecular azobenzene surfactant, and further uses the azobenzene surfactant as a stabilizer. The photoresponse of azobenzene graphene gold nanoparticle composites provides a new modification technology for the development of photoresponse graphene materials. The specific contents are as follows: (1) azobenzene surfactants are prepared by organic synthesis and molecular design for the preparation of photoresponse azobenzene cationic surfactant. The results show that the azobenzene surfactant has the light response characteristics under the visible light of 350nm UV light and 455 nm, and the UV visible absorption spectrum (UV-Vis) can be reversible. In addition, the molecular structure of the double azobenzene surfactant is designed, and the double sub type Gemini couple is prepared. The azobenzene surface variable active agent provides a stabilizer for the preparation of photoresponse graphene metal nanocomposites. (2) the azobenzene graphene composite is based on the charge property of the cationic azobenzene surfactant, and modifies the cationic azobenzene surface active agent (Azo C7NO) to the surface of the negatively charged graphene oxide surface through the ion bond action. The results of.Zeta potential test of azobenzene graphene composite material (Azo-GO) showed that the surface potential of the azobenzene surfactant changed the surface potential of the graphene oxide, and the surface charge changed from negative potential to positive potential rapidly. The fluorescence spectrum showed that the azobenzene carbide composite was of a fluorescent property, which proved that Azo C7NO was the main factor. .X ray diffraction (XRD), scanning electron microscopy (SEM), and atomic force microscopy (AFM) have been applied to the modification of graphene by the ionic bond on graphene oxide, which is a very visible pion accumulation (fluorescence quenching). The results of the atomic force microscopy (AFM) study show that the azobenzene graphene composite has a unique self composition. In addition, the infrared spectrum (FTIR), X ray photoelectron spectroscopy (XPS) and thermogravimetric (TGA) show that the grafting rate of azo phenyl group in the composites is modified for a azobenzene per 71 carbon atoms in the composite. Molecular, with high grafting rate. (3) photoresponse of azobenzene graphene composite is based on the optical response properties of azobenzene group, and the photoresponse characteristics of azobenzene graphene composite have been studied. The UV visible absorption spectroscopy (UV-Vis) shows that the azobenzene graphene composite has photochemical properties.X ray diffraction (XRD). Atomic force microscopy (AFM) and Raman spectroscopy (Raman) show that UV and blue light induction can cause the reversible and reversible isomerization of azobenzene surfactants and the reversible change of hydrophobicity, thus the self assembly of the composite is reversible. The results of the electrochemical cyclic voltammetry (CV) study show that the composite material is the composite. The electrochemical properties of the material can also be controlled by the light reversible control. In the reported azobenzene graphene composite, the properties of the composites prepared by the pion accumulation and covalent bond are mainly due to the spatial isomerization of azobenzene molecules. The azobenzene graphene composite prepared in this paper is prepared in this paper. The changes in the photoresponse properties are determined mainly by the change of the photoinduced polarity and hydrophobicity of azobenzene surfactants, which can lead to the self assembly of the composites. The light controlled self assembly is a new self-assembly phenomenon. The further study of it may provide a mesoscopic study of the self-assembly theory. Examples and theoretical models promote the development of self-assembly theory. (4) the application of azobenzene graphene gold nanoparticles composite material to further develop azobenzene surface active agent in the application of graphene nanocomposites. Based on the molecular structure design, a Gemini Gemini azobenzene surfactant (Azo C10N2O2) is prepared. The surface of this kind of azobenzene surface is prepared. The active agent has two cationic groups with azobenzene as the connecting group. Therefore, Azo C10N2O2 is used as a stabilizer to locate the metal nanoparticles to the surface of graphene by electrostatic action. At the same time, a new type of photoresponse of azobenzene graphene gold nanoparticle composite (Azo-RGO-GNP) is prepared by chemical reduction method. X ray diffraction (XRD), X ray photoelectron spectroscopy (XPS), thermogravimetric (TGA), transmission electron microscopy (TEM) and ultraviolet visible absorption spectroscopy (UV-Vis) are used to study the structure and properties of the composites. The results show that the gold nanoparticles can be evenly distributed on the surface of graphene with Azo C10N2O2 as a stabilizer, and a stable positioning agent is realized. The azobenzene group in the composite made the composite photochemical. By this technique, the first synthesis of azobenzene graphene gold nanoparticle composites was made for the first time. In addition, the electrochemical cyclic voltammetry (CV) study showed that the conductive properties of the composite could also be controlled by light. Therefore, the azobenzene graphene gold nanoparticle was obtained. Composite materials have potential applications in photosensitive sensors and electrochemistry.
【學(xué)位授予單位】：湖南大學(xué)
【學(xué)位級(jí)別】：博士
【學(xué)位授予年份】：2016
【分類號(hào)】：TQ127.11;TB33
本文編號(hào)：2148018
[Abstract]:Graphene, as a carbon material of two-dimensional SP2 network structure, is widely concerned with its unique physical and chemical properties. Its excellent conductivity, mechanical strength, charge transmission and other properties make graphene materials widely used in optoelectronic devices. The main methods of graphene functionalization are physical and chemical modification, a variety of organic or inorganic methods. Compounds are added to the surface of graphene. A large number of research work is focused on the self-assembly, synergism and interfacial effects of graphene composite components. In recent years, photoresponse graphene materials have become one of the hotspots of the development of graphene materials. Some important modified methods (PI accumulation and chemical covalent bond action) have been used to produce light response. Graphene composites have been reported successively. Due to their unique optical response characteristics, these materials have potential applications in the applications of photoelectric and energy reserves. Although these photoresponse graphene composites have been reported, the changes in the molecular structure of the photoresponse cause the space conformation, microstructures, photoelectron energy transformation and other science of graphene. The problem is still a major challenge. Therefore, it is necessary and key to focus on these scientific problems and the new modified technology. This paper has prepared a new type of photoresponse azobenzene graphene composite by modifying the graphene by the small molecular azobenzene surfactant, and further uses the azobenzene surfactant as a stabilizer. The photoresponse of azobenzene graphene gold nanoparticle composites provides a new modification technology for the development of photoresponse graphene materials. The specific contents are as follows: (1) azobenzene surfactants are prepared by organic synthesis and molecular design for the preparation of photoresponse azobenzene cationic surfactant. The results show that the azobenzene surfactant has the light response characteristics under the visible light of 350nm UV light and 455 nm, and the UV visible absorption spectrum (UV-Vis) can be reversible. In addition, the molecular structure of the double azobenzene surfactant is designed, and the double sub type Gemini couple is prepared. The azobenzene surface variable active agent provides a stabilizer for the preparation of photoresponse graphene metal nanocomposites. (2) the azobenzene graphene composite is based on the charge property of the cationic azobenzene surfactant, and modifies the cationic azobenzene surface active agent (Azo C7NO) to the surface of the negatively charged graphene oxide surface through the ion bond action. The results of.Zeta potential test of azobenzene graphene composite material (Azo-GO) showed that the surface potential of the azobenzene surfactant changed the surface potential of the graphene oxide, and the surface charge changed from negative potential to positive potential rapidly. The fluorescence spectrum showed that the azobenzene carbide composite was of a fluorescent property, which proved that Azo C7NO was the main factor. .X ray diffraction (XRD), scanning electron microscopy (SEM), and atomic force microscopy (AFM) have been applied to the modification of graphene by the ionic bond on graphene oxide, which is a very visible pion accumulation (fluorescence quenching). The results of the atomic force microscopy (AFM) study show that the azobenzene graphene composite has a unique self composition. In addition, the infrared spectrum (FTIR), X ray photoelectron spectroscopy (XPS) and thermogravimetric (TGA) show that the grafting rate of azo phenyl group in the composites is modified for a azobenzene per 71 carbon atoms in the composite. Molecular, with high grafting rate. (3) photoresponse of azobenzene graphene composite is based on the optical response properties of azobenzene group, and the photoresponse characteristics of azobenzene graphene composite have been studied. The UV visible absorption spectroscopy (UV-Vis) shows that the azobenzene graphene composite has photochemical properties.X ray diffraction (XRD). Atomic force microscopy (AFM) and Raman spectroscopy (Raman) show that UV and blue light induction can cause the reversible and reversible isomerization of azobenzene surfactants and the reversible change of hydrophobicity, thus the self assembly of the composite is reversible. The results of the electrochemical cyclic voltammetry (CV) study show that the composite material is the composite. The electrochemical properties of the material can also be controlled by the light reversible control. In the reported azobenzene graphene composite, the properties of the composites prepared by the pion accumulation and covalent bond are mainly due to the spatial isomerization of azobenzene molecules. The azobenzene graphene composite prepared in this paper is prepared in this paper. The changes in the photoresponse properties are determined mainly by the change of the photoinduced polarity and hydrophobicity of azobenzene surfactants, which can lead to the self assembly of the composites. The light controlled self assembly is a new self-assembly phenomenon. The further study of it may provide a mesoscopic study of the self-assembly theory. Examples and theoretical models promote the development of self-assembly theory. (4) the application of azobenzene graphene gold nanoparticles composite material to further develop azobenzene surface active agent in the application of graphene nanocomposites. Based on the molecular structure design, a Gemini Gemini azobenzene surfactant (Azo C10N2O2) is prepared. The surface of this kind of azobenzene surface is prepared. The active agent has two cationic groups with azobenzene as the connecting group. Therefore, Azo C10N2O2 is used as a stabilizer to locate the metal nanoparticles to the surface of graphene by electrostatic action. At the same time, a new type of photoresponse of azobenzene graphene gold nanoparticle composite (Azo-RGO-GNP) is prepared by chemical reduction method. X ray diffraction (XRD), X ray photoelectron spectroscopy (XPS), thermogravimetric (TGA), transmission electron microscopy (TEM) and ultraviolet visible absorption spectroscopy (UV-Vis) are used to study the structure and properties of the composites. The results show that the gold nanoparticles can be evenly distributed on the surface of graphene with Azo C10N2O2 as a stabilizer, and a stable positioning agent is realized. The azobenzene group in the composite made the composite photochemical. By this technique, the first synthesis of azobenzene graphene gold nanoparticle composites was made for the first time. In addition, the electrochemical cyclic voltammetry (CV) study showed that the conductive properties of the composite could also be controlled by light. Therefore, the azobenzene graphene gold nanoparticle was obtained. Composite materials have potential applications in photosensitive sensors and electrochemistry.
【學(xué)位授予單位】：湖南大學(xué)
【學(xué)位級(jí)別】：博士
【學(xué)位授予年份】：2016
【分類號(hào)】：TQ127.11;TB33
【參考文獻(xiàn)】
相關(guān)碩士學(xué)位論文 前1條
1 史會(huì)敏;石墨烯的制備及其性質(zhì)研究[D];鄭州大學(xué);2010年
，本文編號(hào)：2148018
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