本文關(guān)鍵詞： 卟啉 氧化石墨烯 金屬氧化物 非共價(jià)相互作用 界面電子轉(zhuǎn)移　出處：《上海應(yīng)用技術(shù)大學(xué)》2016年碩士論文　論文類型：學(xué)位論文

【摘要】：卟啉及其衍生物結(jié)構(gòu)特殊、易修飾、光電化學(xué)性能優(yōu)越,這使得卟啉類化合物在光學(xué)、傳感、染料敏化太陽能電池、分子識(shí)別和催化等領(lǐng)域有潛在的應(yīng)用前景。本論文基于卟啉分子結(jié)構(gòu)的特殊性、可調(diào)制性和優(yōu)異的物理化學(xué)性能,通過非共價(jià)相互作用快速構(gòu)筑多種結(jié)構(gòu)可控、性能可調(diào)的卟啉基功能組裝體,并進(jìn)一步研究各類組裝體的光電性能、光催化析氫活性、穩(wěn)定性及界面光生電子轉(zhuǎn)移,主要研究內(nèi)容如下：通過非共價(jià)相互作用組裝了三種氧化石墨烯(GO)/卟啉復(fù)合物,利用紫外光譜、熒光光譜、拉曼光譜和X射線衍射等手段表征了復(fù)合物中組分間的相互作用。利用透射電鏡觀察卟啉在GO表面的分布。研究了三種復(fù)合物的光電性能。研究發(fā)現(xiàn),卟啉環(huán)周邊的官能團(tuán)對卟啉分子與GO間的結(jié)合方式和性能有重要影響。其中,5,10,15,20-四(4-羥基苯基)卟啉(THPP)和GO間存在較強(qiáng)的氫鍵及π-π相互作用,使得THPP很容易與GO作用并緊密貼合在其表面,這進(jìn)一步增強(qiáng)了THPP與GO之間的相互作用。使GO/THPP復(fù)合物顯示出比另外兩種復(fù)合物更加優(yōu)異的光電性能。本研究工作為通過控制卟啉分子與氧化石墨烯的結(jié)合模式調(diào)控GO/卟啉復(fù)合物的物理化學(xué)性能提供了可能。以預(yù)先通過靜電相互作用鉚合到GO表面的金屬離子為界面連接劑,借助金屬離子與5,15-二苯基-10,20-二(4-吡啶基)卟啉(DPyP)間的配位作用將DPyP與GO復(fù)合,制備了一系列金屬離子橋連、DPyP柱撐的結(jié)構(gòu)新穎的GO/DPyP納米復(fù)合物。通過各種光譜、X射線衍射、氮?dú)馕摳角�和透射電鏡等手段對產(chǎn)物的結(jié)構(gòu)和形貌進(jìn)行表征。此外,研究了復(fù)合物的界面電子轉(zhuǎn)移、光電活性和光催化制氫活性。研究結(jié)果表明：金屬離子的引入可以調(diào)控GO/DPyP納米復(fù)合物的形貌及結(jié)構(gòu),并降低了GO與DPyP之間的界面電阻,提高了光生電子的轉(zhuǎn)移效率,進(jìn)而提高GO/DPyP納米復(fù)合物的光催化還原水制氫性能。本研究結(jié)果說明：在GO與卟啉界面引入金屬離子是一種優(yōu)化GO/卟啉納米復(fù)合物光生電子轉(zhuǎn)移路徑,提高其催化活性簡單而有效的方法。以周邊帶有四個(gè)羥基的四羥基苯基卟啉(THPP)與六面體的Cu20為主要反應(yīng)物,通過攪拌回流反應(yīng)制備得到了一種結(jié)構(gòu)新穎的THPP/Cu2O納米復(fù)合物。通過紫外光譜、熒光光譜等手段對比研究了THPP與Cu20的作用方式。通過電化學(xué)阻抗譜、光電性能和光催化析氫性能研究說明THPP環(huán)中心氮原子與Cu+配位,以及THPP周邊羥基與Cu20表面羥基間的相互作用對于提高Cu2O/THPP復(fù)合物的性能具有協(xié)同作用。本論文研究內(nèi)容的開展,為設(shè)計(jì)和開發(fā)制備方法簡單、結(jié)構(gòu)新穎、性能優(yōu)異的卟啉基組裝體提供新思路,也為解決太陽能轉(zhuǎn)化為氫能或電能過程中涉及的主要關(guān)鍵問題一光生電子轉(zhuǎn)移問題的研究提供理論指導(dǎo)。
[Abstract]:Porphyrins and their derivatives have special structure, easy modification and excellent photoelectrochemical properties, which make porphyrin compounds in the optical, sensing, dye sensitized solar cells. There are many potential applications in molecular recognition and catalysis. Based on the particularity of porphyrin molecular structure, modulability and excellent physical and chemical properties, various structures can be controlled rapidly by non-covalent interaction. Functional porphyrin-based assembly with adjustable properties and further study of the photoelectric properties, photocatalytic hydrogen evolution activity, stability and interface photoelectron transfer of all kinds of assemblies. The main research contents are as follows: three kinds of graphene oxide GOA / porphyrin complexes were assembled by noncovalent interaction. UV spectra and fluorescence spectra were used. Raman spectroscopy and X-ray diffraction were used to characterize the interaction between the components in the complex. The distribution of porphyrin on go surface was observed by transmission electron microscope. The photoelectric properties of the three complexes were studied. The functional groups around the porphyrin ring have an important influence on the binding mode and properties between porphyrin molecules and go. There is a strong hydrogen bond and 蟺-蟺 interaction between 20- tetra-4-hydroxyphenyl) porphyrin (THPP) and go, which makes it easy for THPP to interact with go and bind closely to its surface. This further enhances the interaction between THPP and go, and makes the GO/THPP complex exhibit better optoelectronic properties than the other two complexes. It is possible to regulate the physical and chemical properties of GO- / porphyrin complex by the binding mode of graphene. The metal ions which are riveted to go surface by electrostatic interaction in advance are used as interface binders. A series of metal ion bridges were prepared by the coordination of metal ions with 5 ~ (15) -diphenyl ~ (-10) -20 ~ (-20) -diazo _ 4-pyridyl) porphyrin (DPyP). The metal ions were synthesized by the combination of DPyP and go. Novel GO/DPyP nanocomposites with DPyP pillared structure. The structure and morphology of the products were characterized by various spectral X-ray diffraction, nitrogen adsorption and desorption curves and transmission electron microscopy. The interfacial electron transfer, photovoltaic activity and photocatalytic activity of GO/DPyP nanocomposites were studied. The results showed that the morphology and structure of GO/DPyP nanocomposites could be regulated by the introduction of metal ions. The interface resistance between go and DPyP is reduced and the transfer efficiency of photogenerated electrons is improved. Thus, the photocatalytic reduction of water for hydrogen production by GO/DPyP nanocomposites was improved. The introduction of metal ions into the interface between go and porphyrin is an optimization of photoelectron transfer path of GO- / porphyrin nanocomposites. It is a simple and effective method to improve its catalytic activity by using tetrahydroxyphenyl porphyrin (THPP) with four hydroxyl groups as the main reactant with hexahedron Cu20. A novel THPP/Cu2O nanocomposite was prepared by stirring reflux reaction. The interaction between THPP and Cu20 was studied by means of fluorescence spectroscopy. The coordination of nitrogen atom in the center of THPP ring with Cu was demonstrated by electrochemical impedance spectroscopy, photoelectric performance and photocatalytic hydrogen evolution. The interaction between the peripheral hydroxyl groups of THPP and the surface hydroxyl groups of Cu20 has synergistic effect on improving the properties of Cu2O/THPP complexes. It provides a new idea for the design and development of porphyrin-based assembly with simple preparation method, novel structure and excellent performance. It also provides theoretical guidance for the study of photoelectron transfer, which is the key problem involved in the conversion of solar energy to hydrogen or electric energy.
【學(xué)位授予單位】：上海應(yīng)用技術(shù)大學(xué)
【學(xué)位級(jí)別】：碩士
【學(xué)位授予年份】：2016
【分類號(hào)】：O626

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