發(fā)布時(shí)間：2018-03-26 17:08

  本文選題：金屬有機(jī)配位聚合物　切入點(diǎn)：原位組裝　出處：《山東師范大學(xué)》2017年碩士論文

【摘要】：金屬機(jī)配位聚合物新穎的結(jié)構(gòu)和獨(dú)特的性質(zhì),使其在非均相催化領(lǐng)域具有廣泛地應(yīng)用。本文分別通過原位組裝、負(fù)載活性客體分子和后合成修飾這三種方式合成了基于金屬有機(jī)配位聚合物的非均相催化劑,并分別對(duì)其多功能催化、催化串聯(lián)反應(yīng)和協(xié)同催化的性質(zhì)進(jìn)行了研究。I.從課題組前期工作中篩選出兩例基于Cu(I)的金屬有機(jī)配位聚合物,其中化合物1是1D鋸齒形結(jié)構(gòu),兩種Cu金屬中心間存在弱的Cu···Cu相互作用,[Cu Br2]-作為反荷陰離子懸掛在1D鏈的外面。化合物2是1D梯形鏈狀結(jié)構(gòu),[Cu2Br4]2-作為反荷陰離子,位于兩條鏈中間,連接兩條相鄰的1D鏈。將這兩例化合物分別作為非均相催化劑催化了酚乙酰化反應(yīng)和A3(炔+醛+胺)偶聯(lián)反應(yīng)。經(jīng)研究發(fā)現(xiàn)化合物1均可以高效催化這兩類反應(yīng),催化劑可循環(huán)使用至少五次,并且其催化效率遠(yuǎn)遠(yuǎn)高于化合物2的催化效率,證明了化合物1結(jié)構(gòu)中裸露的[Cu Br2]-作為催化活性中心,減小了反應(yīng)的位阻,有利于反應(yīng)的進(jìn)行。II.利用已知結(jié)構(gòu)的3D Cu4I4-MOF實(shí)現(xiàn)了對(duì)I2的可逆吸附,得到了負(fù)載非金屬單質(zhì)的多孔復(fù)合材料0.75I2@Cu4I4-MOF。0.75I2@Cu4I4-MOF不僅可以高效催化縮醛脫保護(hù)反應(yīng)和醛與吲哚的傅-克烷基化反應(yīng),還可催化縮醛與吲哚的傅-克烷基化串聯(lián)反應(yīng),并取得了很好的催化效果,催化劑循環(huán)使用五次后催化活性并無大幅度降低且仍保持自身結(jié)構(gòu)和形貌穩(wěn)定,首次實(shí)現(xiàn)了非金屬@MOF高效催化有機(jī)串聯(lián)反應(yīng)。III.以結(jié)構(gòu)和性質(zhì)穩(wěn)定的Ui O-66-NH2為基質(zhì),通過后合成修飾的方式引入硫脲官能團(tuán)得到Ui O-66-Thiourea,轉(zhuǎn)化率為38.4%,并通過紅外、質(zhì)譜、PXRD等對(duì)其性質(zhì)進(jìn)行了表征。UiO-66-Thiourea被應(yīng)用于催化芳醛的硅氰化反應(yīng),轉(zhuǎn)化率均在95%以上,催化劑在重復(fù)使用五次后催化效率并無明顯降低,實(shí)現(xiàn)了MOF與有機(jī)小分子間的協(xié)同催化。研究表明,通過原位組裝、負(fù)載活性客體分子以及后合成修飾得到的金屬有機(jī)配位聚合物催化劑均可以對(duì)有機(jī)合成反應(yīng)實(shí)現(xiàn)高效催化,豐富了催化劑的種類,為合成新型高效的非均相催化劑提供了新思路。
[Abstract]:Metal coordination polymers are widely used in heterogeneous catalysis due to their novel structure and unique properties. Heterogeneous catalysts based on metal-organic coordination polymers were synthesized by supported active guest molecules and post-synthetic modification. The properties of catalytic series reaction and synergistic catalysis were studied. I. two metal-organic coordination polymers based on Cui were selected from the previous work of our group, in which compound 1 was a 1D zigzag structure. There is a weak Cu Cu interaction between the centers of two Cu metals. [Cu Br2]-is suspended outside the 1D chain as countercharge anions. Compound 2 is a 1D trapezoidal chain structure, and [Cu2Br4] 2- is a reverse charge anion located between the two chains. The two compounds were used as heterogeneous catalysts to catalyze the acetylation of phenol and the coupling reaction of A _ 3 (acetylaldehyde amine). It was found that compound 1 could efficiently catalyze these two reactions. The catalyst can be reused for at least five times, and its catalytic efficiency is much higher than that of compound 2. It is proved that the exposed [Cu Br2]-in compound 1 structure acts as the catalytic active center and reduces the steric resistance of the reaction. The reversible adsorption of I _ 2 was achieved by using 3D Cu4I4-MOF with known structure. The porous composite 0.75I2@Cu4I4-MOF.0.75I2@Cu4I4-MOF supported on non-metallic materials could not only catalyze the deprotection reaction of acetal and the Friede-gram alkylation of aldehyde with indole, but also could effectively catalyze the deprotection of acetal and the alkylation of aldehyde with indole. It can also catalyze the Friede-gram alkylation of acetal and indole in series, and obtain a good catalytic effect. The catalytic activity does not decrease significantly and the structure and morphology of the catalyst remain stable after five cycles. For the first time, the high performance organic series reaction of non-metallic @ MOF was realized. The Ui O-66-NH2 with stable structure and properties was used as the substrate. The Ui O-66-Thioureawas obtained by introducing thiourea functional group by post-synthesis modification. The conversion was 38.4% and the conversion was 38.4%, and the Ui O-66-Thioureawas obtained by IR. Its properties were characterized by PXRD. UiO-66-Thiourea was used to catalyze the silicocyanic reaction of aromatic aldehydes. The conversion rate was above 95%. The catalytic efficiency of the catalyst was not significantly decreased after the repeated use of the catalyst for five times. The synergistic catalysis between MOF and small organic molecules has been realized. The results show that the organometallic coordination polymer catalysts can efficiently catalyze the organic synthesis by in situ assembly, loading of active guest molecules and modification of organometallic coordination polymers. It enriches the kinds of catalysts and provides a new idea for the synthesis of new and efficient heterogeneous catalysts.
【學(xué)位授予單位】：山東師范大學(xué)
【學(xué)位級(jí)別】：碩士
【學(xué)位授予年份】：2017
【分類號(hào)】：O641.4;O643.36
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本文編號(hào)：1668779