本文選題：羧基化碳催化劑　切入點(diǎn)：釜式蒸汽處理　出處：《中國(guó)科學(xué)技術(shù)大學(xué)》2017年博士論文　論文類(lèi)型：學(xué)位論文

【摘要】：探索并應(yīng)用非金屬催化劑,作為對(duì)傳統(tǒng)金屬基工業(yè)催化劑的補(bǔ)充和替代選擇,具有廣闊的研究空間和市場(chǎng)前景,近年來(lái)已經(jīng)逐漸成為了學(xué)術(shù)界和工業(yè)界的共同熱點(diǎn)。在非金屬催化劑中,碳基固體酸催化劑具有酸性位種類(lèi)多樣、骨架具有豐富的被修飾可能性、可以調(diào)節(jié)表面親疏水性調(diào)控對(duì)底物分子的吸附、生物相容性好并且更容易綠色地回收與降解的獨(dú)特優(yōu)勢(shì)。碳材料表面的酸性位對(duì)負(fù)載金屬活性位也起到了非常關(guān)鍵的作用,對(duì)酸性位的研究也會(huì)對(duì)負(fù)載金屬催化劑的制備及研究金屬與載體間的相互作用提供指導(dǎo)。本論文以碳材料上的羧基基團(tuán)為目標(biāo)活性位,以酸催化反應(yīng)為核心應(yīng)用目標(biāo),分別從嘗試優(yōu)化引入羧基的合成方法,探索羧基化學(xué)環(huán)境對(duì)活性位構(gòu)效關(guān)系的影響,表征碳碎片化學(xué)結(jié)構(gòu)以推測(cè)碳材料表面化學(xué)性質(zhì)這三個(gè)角度,對(duì)羧基化碳材料(主要是碳納米管)在酸催化反應(yīng)中的應(yīng)用進(jìn)行了研究。得到的主要結(jié)論如下:(一)發(fā)明了一種以釜式硝酸蒸汽氧化裝置為核心的氣相氧化方法,不受沸點(diǎn)限制。通過(guò)提升氧化溫度,可以在更短的時(shí)間內(nèi)達(dá)到更強(qiáng)的氧化效果,并大幅降低了硝酸的用量。因?yàn)檠趸涛g產(chǎn)生的碳碎片在氣相中相對(duì)不容易脫離,能夠在一定程度上抑制持續(xù)刻蝕。當(dāng)氧化程度增加時(shí),單個(gè)羧基的平均催化活性也會(huì)隨之上升。羧基之間以及硝酸氧化過(guò)程中引入的硝基基團(tuán)可能通過(guò)吸電子誘導(dǎo)效應(yīng),增強(qiáng)了羧基的酸強(qiáng)度。(二)建立了一套完整的液相反應(yīng)動(dòng)力學(xué)分析程序,以氧化苯乙烯的酸催化開(kāi)環(huán)反應(yīng)為探針,通過(guò)動(dòng)力學(xué)研究測(cè)定了歸一化的初始反應(yīng)速率、反應(yīng)表觀活化能Ea、指前因子A、反應(yīng)級(jí)數(shù)等動(dòng)力學(xué)參數(shù)。利用指前因子A作為有效酸性位數(shù)量的替代描述因子,擬合出求取pKa值的工作曲線(xiàn),首次得到了碳材料上的羧基的平均擬合pKa值,實(shí)現(xiàn)了對(duì)不同碳材料羧基酸強(qiáng)度的定量比較。推測(cè)羧基化碳材料表面可能存在兩種硝基與羧基的相互作用,能夠不同程度地增強(qiáng)羧基酸強(qiáng)度,導(dǎo)致硝基基團(tuán)表現(xiàn)出不同的熱穩(wěn)定性。(三)首次非常清晰地確認(rèn)了碳材料上羧基、硝基、酸酐、內(nèi)酯的紅外特征峰歸屬,并且在原位加熱的條件下觀測(cè)到上述官能團(tuán)的熱分解,以及羧基向酸酐和內(nèi)酯的轉(zhuǎn)化。本論文在一定程度上推進(jìn)了對(duì)于碳基催化劑在酸催化反應(yīng)中應(yīng)用的理解,較為深入地研究了羧基酸強(qiáng)度與催化活性的構(gòu)效關(guān)系,初步摸索并證實(shí)出了一些對(duì)于優(yōu)化活性位化學(xué)環(huán)境具有指導(dǎo)意義的化學(xué)規(guī)律。
[Abstract]:To explore and apply non-metallic catalysts as a supplement and alternative to traditional metal-based industrial catalysts has broad research space and market prospects. In recent years, it has gradually become a common focus of academia and industry. Among non-metallic catalysts, carbon-based solid acid catalysts have a variety of acidic sites, and the skeleton has a rich possibility of modification. It can regulate the adsorption of substrate molecules by surface hydrophobicity, and has the unique advantages of good biocompatibility and easier green recovery and degradation. The acidic sites on the surface of carbon materials also play a very important role in loading metal active sites. The study of acidic sites will also provide guidance for the preparation of supported metal catalysts and the study of the interaction between metals and supports. In this thesis, carboxyl groups on carbon materials are regarded as the target active sites and acid catalytic reactions as the core application targets. In this paper, we try to optimize the synthesis method of introducing carboxyl groups, explore the influence of carboxyl chemical environment on the active structure-activity relationship, and characterize the chemical structure of carbon fragments in order to speculate the surface chemical properties of carbon materials. The application of carboxylated carbon materials (mainly carbon nanotubes) in acid catalytic reaction was studied. Not subject to boiling point. By raising the oxidation temperature, you can achieve a stronger oxidation effect in a shorter time, and greatly reduce the amount of nitric acid, because the carbon fragments produced by the oxidation etching are relatively difficult to detach in the gas phase. The average catalytic activity of a single carboxyl group increases with the increase of oxidation degree. Nitro groups introduced between carboxyl groups and during nitric acid oxidation may be induced by electron absorption. The acid strength of carboxyl group was enhanced. (2) A complete program for the kinetic analysis of liquid phase reaction was established. The initial reaction rate of normalized reaction was determined by kinetic study using the acid catalyzed ring-opening reaction of styrene oxide as the probe. The kinetic parameters such as apparent activation energy (EA), preexponential factor A, reaction order and so on. Using preexponential factor A as an alternative description factor of effective acid sites, the working curve of calculating pKa value is fitted. The average fitting pKa value of carboxyl groups on carbon materials is obtained for the first time, and the quantitative comparison of carboxylic acid strength of different carbon materials is realized. It is inferred that there may exist interaction between two nitro groups and carboxyl groups on the surface of carboxyl carbon materials. Can enhance the strength of carboxylic acid to varying degrees, leading to different thermal stability of nitro groups. (3) for the first time, the infrared characteristic peaks of carboxyl, nitro, anhydride and lactone on carbon materials are confirmed very clearly. The thermal decomposition of the above functional groups and the conversion of carboxyl groups to acid anhydride and lactone have been observed under in situ heating. To some extent, the understanding of the application of carbon-based catalysts in acid catalytic reactions has been advanced. The structure-activity relationship between carboxylic acid strength and catalytic activity was studied in depth, and some guiding chemical laws for optimizing the active site chemical environment were preliminarily explored and confirmed.
【學(xué)位授予單位】：中國(guó)科學(xué)技術(shù)大學(xué)
【學(xué)位級(jí)別】：博士
【學(xué)位授予年份】：2017
【分類(lèi)號(hào)】：O643.36

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