【摘要】：催化是現(xiàn)代化學(xué)工業(yè)的基石,分子印跡及其高選擇性催化作用是當(dāng)前催化技術(shù)取得的最重要進(jìn)展之一。然而,催化的實(shí)際應(yīng)用通常涉及多步驟反應(yīng)及選擇性可調(diào)的催化作用過(guò)程,現(xiàn)有印跡聚合物及催化劑無(wú)法迎合這一時(shí)代發(fā)展的需求。本文從分子設(shè)計(jì)著手,迎合這一挑戰(zhàn),發(fā)展出可分別進(jìn)行連續(xù)催化的分子印跡催化劑及選擇性可調(diào)的分子印跡催化劑。為實(shí)現(xiàn)連續(xù)催化反應(yīng),本文將金屬納米粒子與功能分子印跡聚合物結(jié)合起來(lái),制備出了可連續(xù)催化水解和還原的分子印跡催化劑。研究以2-丙烯酰胺-2-甲基丙磺酸(磺酸根為酸性活性中心)為功能單體,以對(duì)硝基苯酚及雙(對(duì)硝基苯酚)碳酸酯為雙模板,以Au納米粒子為金屬活性中心,制得了可連續(xù)催化的分子印跡催化劑。其酸中心則允許雙(對(duì)硝基苯酚)碳酸酯進(jìn)行水解,其金屬中心則允許后續(xù)還原得以進(jìn)行,由此實(shí)現(xiàn)了連續(xù)的催化作用。同時(shí),由于載體為分子印跡聚合物,故合成的催化劑不僅具有連續(xù)催化的功能,而且具有高選擇性的特性。在此基礎(chǔ)上,本文還為了克服當(dāng)前分子印跡研究中選擇性可調(diào)的困境,以9-癸烯酸為功能單體,以對(duì)羥基苯甲醛為模板分子,以Ag納米粒子為金屬活性中心制備出了選擇性可調(diào)的分子印跡催化劑。其中,9-癸烯酸中的鏈結(jié)構(gòu)為合成的分子印跡催化劑構(gòu)筑了可流動(dòng)分子鏈,從而對(duì)底物通道構(gòu)成調(diào)制作用。低溫條件下,合成聚合物中的分子鏈被凍結(jié),故合成的印跡聚合物對(duì)特異性底物對(duì)羥基苯甲醛具有分子識(shí)別的能力,允許其抵近Ag納米粒子,從而使催化成為可能;反之,高溫條件下,印跡聚合物內(nèi)分子鏈熱運(yùn)動(dòng)的加強(qiáng),造成了印跡聚合物中的識(shí)別位點(diǎn)被破壞,合成的印跡聚合物對(duì)特異性底物分子識(shí)別能力無(wú)法體現(xiàn),選擇性下降,故其對(duì)特異性底物的還原與對(duì)底物類似物的還原作用基本相似,無(wú)選擇性差別。從而,以這種獨(dú)特的方式,合成的印跡聚合物催化劑呈現(xiàn)出選擇性/非選擇性-可調(diào)節(jié)的催化特性。通過(guò)以上二部分較系統(tǒng)的工作,本文發(fā)展出了可分別進(jìn)行連續(xù)催化的分子印跡催化劑及選擇性可調(diào)的分子印跡催化劑,闡明了分子印跡催化劑催化作用的規(guī)律,為更有效地使用分子印跡聚合物催化劑提供了必要的理論及實(shí)驗(yàn)依據(jù)。
[Abstract]:Catalysis is the cornerstone of modern chemical industry. Molecular imprinting and its high selective catalysis are one of the most important advances in current catalytic technology. However, the practical application of catalysis usually involves multistep reactions and selective and adjustable catalytic processes. The existing imprinted polymers and catalysts are unable to meet the needs of the development of this era. In order to achieve continuous catalytic reaction, this paper combines metal nanoparticles with functional molecularly imprinted polymers to prepare molecules that can catalyze hydrolysis and reduction continuously in order to achieve continuous catalytic reaction. 2- acrylamide -2- methyl propane sulfonic acid (acidic active center of sulfonic acid) was used as a functional monomer, with p-nitrophenol and bis (p-nitrophenol) carbonate as a double template and Au nanoparticles as the metal active center, a continuous catalytic molecular imprinting catalyst was prepared. Its acid center allowed double (p-nitrophenol). At the same time, as the carrier is a molecularly imprinted polymer, the catalyst not only has a continuous catalytic function, but also has a high selectivity. On this basis, this paper also overcame the molecular imprinting research. In the study, a selective and adjustable molecular imprinting catalyst was prepared by using 9- decenoic acid as a functional monomer, with P hydroxybenzaldehyde as a template molecule and Ag nanoparticles as the metal active center. The chain structure of 9- decenoic acid was used as a molecularly imprinted catalyst to construct a mobile molecular chain, thus the substrate was made to the substrate. The molecular chain in the synthetic polymer is frozen at low temperature, so the synthetic imprinted polymer has the ability to identify the specific substrate to hydroxybenzaldehyde, allowing it to close to the Ag nanoparticles, thus making it possible; conversely, the thermal movement of the molecular chain within the imprinted polymer is strengthened under high temperature conditions. The recognition site in the imprinted polymer is destroyed, and the synthetic imprinted polymer is unable to reflect the specific substrate molecular recognition ability and the selectivity decreases. Therefore, the reduction of the specific substrate is basically similar to the reduction of the substrate analogues, and there is no selective difference. From this, the imprinted polymer is synthesized in this unique way. The catalyst exhibits selective / non selective catalytic properties. Through the systematic work of the above two parts, the molecular imprinting catalyst and the selective and adjustable molecular imprinting catalyst, which can be catalyzed by continuous catalysis, are developed. The law of the catalytic action of the molecular imprinting catalyst is clarified, so as to use the molecules more effectively. The imprinted polymer catalyst provides the necessary theoretical and experimental basis.
【學(xué)位授予單位】：江蘇大學(xué)
【學(xué)位級(jí)別】：碩士
【學(xué)位授予年份】：2017
【分類號(hào)】：O643.36;O631.3

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本文編號(hào)：2139433