本文選題：富勒烯 + 自組裝　； 參考：《東華大學(xué)》2014年碩士論文

【摘要】：自富勒烯(C60)被發(fā)現(xiàn)近30年來,由于其獨(dú)特的分子結(jié)構(gòu)賦予其材料優(yōu)良的光電性能,持續(xù)得到了大量關(guān)注。另一方面,燃料電池曾被美國時(shí)代雜志評(píng)為21世紀(jì)對(duì)人類最有影響的十大高新技術(shù)之一近年來合成價(jià)格低廉且性能優(yōu)越的燃料電池催化劑亦為重要的熱點(diǎn)課題之一。富勒烯具有良好的自組裝能力,可以通過調(diào)控其自組裝得到大比表面積的復(fù)雜結(jié)構(gòu)形貌；由于催化劑的比表面積與其催化活性密切相關(guān),具有大比表面積富勒烯自組裝結(jié)構(gòu)在催化劑載體應(yīng)用方面應(yīng)具有潛在價(jià)值,但這方面的研究報(bào)道甚少。因此本論文主要從以下兩個(gè)方面開展了工作：合成功能化富勒烯衍生物并調(diào)控其自組裝以及探索富勒烯自組裝結(jié)構(gòu)在燃料電池催化劑材料中的應(yīng)用。 首先本論文設(shè)計(jì)合成了含有羧基、酯基和硝基等功能基團(tuán)的富勒烯衍生物(富勒烯本身比重高于75%),并系統(tǒng)研究了這些衍生物在不同實(shí)驗(yàn)條件下(如溶劑、基質(zhì)、氛圍和溫度等)的自組裝規(guī)律。結(jié)果表明：溶劑的性質(zhì)、功能基團(tuán)的位置等在一定程度影響其自組裝后的形貌；基質(zhì)并不是影響自組裝形貌的主要因素。對(duì)于所合成的功能化富勒烯衍生物,均可通過條件優(yōu)化來調(diào)控其自組裝行為,得到比表面積較大的復(fù)雜花球形貌結(jié)構(gòu)。通過XRD研究發(fā)現(xiàn),這些復(fù)雜花球形貌結(jié)構(gòu)中富勒烯通過π-π(C60/C60)堆積作用以之字形錯(cuò)位方式自組裝排列。同時(shí),本文還對(duì)功能化富勒烯衍生物的電化學(xué)性質(zhì)和光譜性質(zhì)進(jìn)行了研究；并通過理論計(jì)算研究了取代基位置與分子軌道能級(jí)之間的關(guān)系,在3種硝基苯基取代的富勒烯衍生物中,發(fā)現(xiàn)鄰位硝基的氧原子上的孤對(duì)電子與富勒烯籠π電子之間存在軌道相互作用力,可顯著提高其LUMO能級(jí)。 其次,將富勒烯衍生物自組裝結(jié)構(gòu)作為催化劑載體,探索了其在燃料電池中的應(yīng)用。將Pt或Pd利用電化學(xué)還原沉積在富勒烯自組裝結(jié)構(gòu)覆蓋的ITO電極上制得復(fù)合催化劑,通過催化甲醇氧化對(duì)其電催化性能進(jìn)行了評(píng)價(jià),初步結(jié)果表明富勒烯自組裝結(jié)構(gòu)的引入可使催化劑的催化活性顯著提高。同時(shí),用硼氫化鈉還原法制備了一類性能優(yōu)越的負(fù)載在羧基化多壁碳納米管上的空心型核殼結(jié)構(gòu)M@Pt-CNTs或M@Pd-CNTs新型催化劑(M為Co、Ni或CoNi合金)。
[Abstract]:Since the discovery of fullerene (C60) in recent 30 years, it has been paid more and more attention due to its unique molecular structure and its excellent optoelectronic properties. On the other hand, fuel cell has been regarded as one of the ten most influential high and new technologies in the 21st century by American time magazine. In recent years, low cost and superior performance fuel cell catalyst is also one of the important hot topics. Fullerene has good self-assembly ability and can obtain complex structure morphology of large specific surface area by regulating its self-assembly, because the specific surface area of the catalyst is closely related to its catalytic activity. Fullerene self-assembly structure with large specific surface area should have potential value in the application of catalyst carrier, but there are few reports in this field. Therefore, in this thesis, the following two aspects of work have been carried out: synthesis of functionalized fullerene derivatives and regulation of their self-assembly, and exploration of the application of fullerene self-assembly structure in fuel cell catalyst materials. In this paper, fullerene derivatives with carboxyl, ester and nitro groups were designed and synthesized (the specific gravity of fullerene is higher than 75%), and the effects of different experimental conditions (such as solvent, substrate, etc.) on these derivatives were systematically studied. The self-assembly law of atmosphere and temperature etc. The results show that the properties of the solvent and the position of the functional groups affect the morphology of the self-assembly to a certain extent, and the matrix is not the main factor affecting the morphology of the self-assembly. For the functionalized fullerene derivatives, the self-assembly behavior can be controlled by optimizing the conditions, and the morphology and structure of the complex floral spheres with large specific surface area can be obtained. It was found by XRD that fullerene was self-assembled by 蟺-蟺 C60 / C60 stacking in these complex orbicular structures in the form of zigzag dislocation. At the same time, the electrochemical and spectral properties of the functionalized fullerene derivatives are studied, and the relationship between the substituent positions and the molecular orbital energy levels is studied by theoretical calculation. Among the three kinds of nitrophenyl substituted fullerene derivatives, it is found that there exists orbital interaction between the lone pair electrons in the oxygen atom in the o-nitro-position and the 蟺 electrons in the fullerene cage, which can significantly improve the LUMO energy level of the fullerenes. Secondly, the self-assembly structure of fullerene derivatives was used as catalyst carrier to explore its application in fuel cells. A composite catalyst was prepared by electrochemical reduction deposition of Pt or PD on a fullerene self-assembled ITO electrode. The electrocatalytic performance of Pt or PD was evaluated by methanol oxidation. The preliminary results show that the addition of fullerene self-assembly structure can significantly improve the catalytic activity of the catalyst. At the same time, a class of hollow core-shell structure M@Pt-CNTs or M@Pd-CNTs catalysts with excellent properties supported on carboxylated multiwalled carbon nanotubes were prepared by sodium borohydride reduction method.
【學(xué)位授予單位】：東華大學(xué)
【學(xué)位級(jí)別】：碩士
【學(xué)位授予年份】：2014
【分類號(hào)】：O613.71;TM911.4

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相關(guān)期刊論文 前2條

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本文編號(hào)：1986985