本文選題：雜多酸 + 金屬有機(jī)框架��； 參考：《吉林農(nóng)業(yè)大學(xué)》2015年碩士論文

【摘要】：金屬-有機(jī)框架(metal-organic frameworks,MOFs)化合物是由金屬離子與有機(jī)配體通過自組裝過程雜化生成的一類具有周期性多維網(wǎng)狀結(jié)構(gòu)的多孔晶體材料。雜多酸(Heteropolyacid),也稱多金屬氧簇,是一類由氧原子橋接金屬原子形成的金屬-氧簇化合物。前者作為一種多孔的結(jié)晶材料在催化、吸附分離、傳感、磁性和其他方面具有廣泛的潛在應(yīng)用。后者由于其組成和結(jié)構(gòu)的多樣,性質(zhì)的可調(diào)性,在光、電、磁學(xué)、催化和藥物等領(lǐng)域有著重要的應(yīng)用。鑒于上面的現(xiàn)狀,包含雜多酸的金屬-有機(jī)框架雜化膜材料的研究將成為人們關(guān)注的熱點(diǎn)課題,并且其成膜的可能性已得到了實(shí)驗(yàn)和理論的證實(shí)。本文制備了四種包含不同雜多酸的金屬-有機(jī)框架膜材料,并對(duì)其合成方法、形貌特征、化學(xué)結(jié)構(gòu)、催化性能進(jìn)行了深入探討,主要研究結(jié)果如下:1、四種雜多酸的合成在環(huán)境開放的條件下,通過酸化加熱乙醚萃取的方法合成了四種經(jīng)典的keggin型的雜多酸,分別是H3PW12O40、H3PMo12O40、H3SiW12O40、H3Si Mo12O40。這四種雜多酸具有類似的化學(xué)結(jié)構(gòu)、性質(zhì)特征和結(jié)構(gòu)穩(wěn)定性,是高效的雙功能催化劑,既是酸催化劑,又是氧化還原催化劑。并且可以應(yīng)用在非均相催化和均相催化反應(yīng)中,具有良好的環(huán)境友好性,對(duì)環(huán)境無污染。2、分別含有四種多金屬氧酸的金屬-有機(jī)框架膜材料的制備本論文選擇被廣泛研究的多孔金屬有機(jī)框架化合物HKUST-1(Cu3(BTC)2)作為框架材料。采用原位晶化法,在常溫條件下以銅網(wǎng)為載體合成了四種包含不同雜多酸的金屬有機(jī)框架膜材料,PMo@Cu3(BTC)2、SiMo@Cu3(BTC)2、PW@Cu3(BTC)2、SiW@Cu3(BTC)2。合成的膜材料厚度在8μm左右,表面晶粒尺寸均一。銅網(wǎng)在合成過程中既是載體又是銅離子源,采用的溶劑是水和乙醇體積比為1:1的混合溶劑,這樣有利于雜多酸和均苯三甲酸的充分溶解。在合成過程創(chuàng)新性的中加入了過氧化氫,能夠有效的加快膜材料的生長(zhǎng)進(jìn)程。并且對(duì)過氧化氫的最適添加量做出了探索。3、金屬-有機(jī)框基膜材料的催化氧化性能研究以羅丹明B為目標(biāo)降解物,四種金屬有機(jī)框架膜材料都表現(xiàn)出了高效的催化性能,在反應(yīng)進(jìn)行到100min時(shí),催化降解率都在96%以上,并且能夠良好的重復(fù)使用,使用多次催化性能無明顯下降。這類催化劑結(jié)合了多酸和金屬有機(jī)框架化合物的優(yōu)點(diǎn),與傳統(tǒng)催化劑相比具有以下優(yōu)點(diǎn):具有明確的X-ray晶體學(xué)結(jié)構(gòu);更高的催化效率;克服了流失和鈍化現(xiàn)象;均勻的孔道結(jié)構(gòu)可以選擇性的催化化學(xué)反應(yīng);穩(wěn)定的框架結(jié)構(gòu)和在載體上的牢固負(fù)載更有利于催化劑的回收和循環(huán)利用。
[Abstract]:Metal-organic framework metal-organic frameworks (MOFs) compounds are a kind of porous crystal materials with periodic multi-dimensional network structure formed by self-assembly process of metal ions and organic ligands. Heteropoly acido, also called polymetallic oxygen cluster, is a kind of metal-oxygen cluster compound formed by oxygen atom bridging metal atom. The former as a porous crystalline material has a wide range of potential applications in catalysis, adsorption, separation, sensing, magnetic and other fields. The latter has important applications in the fields of light, electricity, magnetics, catalysis and medicine because of its diverse composition and structure and adjustable properties. In view of the above situation, the study of metal-organic frame hybrid membrane materials containing heteropoly acids will become a hot topic, and the possibility of membrane formation has been confirmed by experiments and theories. In this paper, four kinds of metal-organic framework membrane materials containing different heteropoly acids were prepared, and their synthesis methods, morphology, chemical structure and catalytic properties were discussed. The main results are as follows. Four kinds of heteropoly acids, H3PW12O40H3PMo12O40H3SiW12O40H3SiMo12O40H3SiMo12O40H3SiMo12O40H3SiMo12O40H3SiMo12O40H3SiMo12O40H3SiMo12O40H3SiMo40H3SiMo40H3SiMo40H3SiMo40H3SiMo40H3SiMo40H3SiMo40H3SiMo@@ These four heteropoly acids have similar chemical structure, properties and structural stability. They are highly effective bifunctional catalysts, both acid catalyst and redox catalyst. And can be used in heterogeneous catalysis and homogeneous catalytic reactions, with good environmental friendliness, Preparation of metal-organic framework membrane materials containing four kinds of polyoxometallic acids without environmental pollution. In this paper, the porous organometallic framework compound HKUST-1Cu3BT-2 was selected as the framework material. Four kinds of metal-organic frame membrane materials containing different heteropoly acids were synthesized by in situ crystallization under normal temperature with copper mesh as the carrier. Four kinds of metal-organic framework membrane materials containing different heteropoly acids were synthesized. The thickness of the synthesized film is about 8 渭 m and the surface grain size is uniform. Copper mesh is both a carrier and a copper ion source in the process of synthesis. The solvent used is a mixture of water and ethanol at 1:1 volume ratio, which is beneficial to the full dissolution of heteropoly acid and terephthalic acid. The addition of hydrogen peroxide into the synthesis process can effectively accelerate the growth process of the membrane materials. The optimum addition amount of hydrogen peroxide was explored. The catalytic oxidation performance of metal-organic frame membrane materials was studied. Rhodamine B was taken as the target degradation material. The four kinds of organometallic frame membrane materials showed high catalytic performance. The catalytic degradation rate was above 96% when the reaction was carried out to 100min, and it could be reused well. This kind of catalyst combines the advantages of polyacid and organometallic framework compounds, and has the following advantages compared with traditional catalysts: clear X-ray crystallographic structure, higher catalytic efficiency, overcome loss and passivation phenomena; The uniform pore structure can selectively catalyze the chemical reaction, and the stable frame structure and the solid loading on the support are more favorable to the recovery and recycling of the catalyst.
【學(xué)位授予單位】：吉林農(nóng)業(yè)大學(xué)
【學(xué)位級(jí)別】：碩士
【學(xué)位授予年份】：2015
【分類號(hào)】：TB383.2

【共引文獻(xiàn)】

相關(guān)碩士學(xué)位論文 前4條

1 陳震宇;席夫堿銅配合物的合成及模擬加氧酶催化性能研究[D];浙江理工大學(xué);2013年

2 宋文峰;過渡金屬取代的多金屬氧酸鹽的合成及催化氧化研究[D];蘭州大學(xué);2012年

3 徐淵;有機(jī)高價(jià)碘試劑催化氧化芐基sp~3C-H鍵的應(yīng)用研究[D];浙江工業(yè)大學(xué);2013年

4 汪海艷;雜多酸鹽/有機(jī)配合物雜化材料催化Suzuki偶聯(lián)反應(yīng)研究[D];西北師范大學(xué);2014年

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本文編號(hào)：1787511