本文選題：催化氧化　切入點：選擇性氧化　出處：《南京航空航天大學》2017年碩士論文

【摘要】：近年來,隨著材料技術(shù)的不斷進步,一系列氮摻雜材料由于具備制備簡單、性能優(yōu)越等優(yōu)點,成功進入到有機化學家的視線中,特別是負載了過渡金屬的氮摻雜材料被廣泛的運用在有機合成中。本文制備了一種Co-N-C材料,并將其運用在液相氧化上,結(jié)果表明,該催化劑在芳烴側(cè)鏈的選擇性氧化以及烯烴烯丙位的選擇性氧化方面擁有突出的催化性能。首先,我們采用球磨的方法將前驅(qū)體三聚氰胺和六水合硝酸鈷反應,制備了相應的Co-N-C材料。其次,對所制備的材料進行了SEM,BET,HRTEM,XRD,XPS和FTIR等表征,結(jié)果顯示前驅(qū)體三聚氰胺和鈷離子結(jié)合形成Co-N-C材料,該材料具有片層微孔結(jié)構(gòu),同時三聚氰胺可能自身發(fā)生聚合生成類似于g-C_3N_4的CN材料。最后,探索了Co-N-C催化劑在液相氧化方面的催化性能。結(jié)果表明,該催化劑在芳烴側(cè)鏈的選擇性氧化以及烯烴烯丙位的選擇性氧化方面的性能突出。整個氧化過程的條件溫和,僅僅需要千分之五的Co-N-C催化劑,氧化劑則為綠色氧源--氧氣,在此條件下,可以十分高效的選擇性氧化乙基苯,得到目標產(chǎn)物苯乙酮(92.8%的底物轉(zhuǎn)化率以及95.5%的目標產(chǎn)物選擇性),把該反應進行放大到200g級別的反應也獲得了成功,得到了接近70%的單程收率,除此之外,我們將反應的催化劑進行了循環(huán)性能的測試,測試的結(jié)果十分優(yōu)異,同一催化劑在循環(huán)5次之后,其氧化性能并沒有出現(xiàn)下降,仍然保持高效。綜上,本文通過新穎、廉價、簡單的方法制得Co-N-C材料,綠色、高效的實現(xiàn)了芳烴側(cè)鏈的選擇性氧化以及烯烴烯丙位的選擇性氧化,并具有良好的底物適應性和官能團容忍性。
[Abstract]:In recent years, with the development of material technology, a series of nitrogen-doped materials have successfully entered the view of organic chemists because of their advantages of simple preparation and superior performance. Especially, nitrogen-doped materials loaded with transition metals have been widely used in organic synthesis. In this paper, a kind of Co-N-C material was prepared and used in liquid phase oxidation. The catalyst has outstanding catalytic properties in selective oxidation of aromatics side chains and selective oxidation of olefin allylic sites. Firstly, the precursor melamine was reacted with cobalt nitrate hexahydrate by ball milling. The corresponding Co-N-C materials were prepared. Secondly, the prepared materials were characterized by SEMBETTEMTEMTEMT-XRDX and FTIR. The results showed that the precursor melamine combined with cobalt ions to form Co-N-C material, which had a lamellar microporous structure. At the same time, melamine may polymerize itself to produce CN material similar to g-C_3N_4. Finally, the catalytic performance of Co-N-C catalyst in liquid phase oxidation is explored. The catalyst has excellent performance in selective oxidation of aromatics side chain and selective oxidation of olefin allylic sites. The conditions of the whole oxidation process are mild, only 5/1000 Co-N-C catalyst is needed, and the oxidant is green oxygen source-oxygen. Under these conditions, ethyl benzene can be oxidized very efficiently, the target product acetophenone is 92.8% of the substrate conversion and the target product is 95.5% selective. The reaction is also successfully amplified to 200g level. Nearly 70% of the single pass yield was obtained. In addition, the cyclic performance of the catalyst was tested, and the results were excellent. After 5 cycles, the oxidation performance of the same catalyst did not decrease. In this paper, Co-N-C materials are prepared by novel, cheap and simple methods. Green, efficient and selective oxidation of aromatics side chains and allyl alkenes is achieved. And has good substrate adaptability and functional tolerance.
【學位授予單位】：南京航空航天大學
【學位級別】：碩士
【學位授予年份】：2017
【分類號】：O643.36;O621.3

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