銅系金屬有機(jī)骨架構(gòu)筑及其催化性能研究
發(fā)布時間：2018-08-23 11:07
【摘要】：金屬有機(jī)骨架(MOFs)材料是指金屬離子與有機(jī)配體通過配位作用自組裝形成的一類具有周期性結(jié)構(gòu)的有機(jī)-無機(jī)雜化多孔材料。這種MOFs多孔材料具有規(guī)則、均勻的孔徑及結(jié)構(gòu)可調(diào)性等優(yōu)勢,使其在氣體儲存、吸附分離及催化領(lǐng)域等方面具有潛在的研究價值。本文致力于設(shè)計合成新型高效多孔MOFs催化材料:一方面通過對MOFs材料進(jìn)行合成后修飾負(fù)載金屬鹽配位化合物,制備負(fù)載型非均相催化材料;另一方面通過在磁性納米粒子表面包覆金屬有機(jī)骨架材料MOFs,并引入催化活性組分形成具有獨特MOFs核殼結(jié)構(gòu)的非均相催化材料,實現(xiàn)了多級結(jié)構(gòu)磁性納米催化材料的可控設(shè)計及功能化組裝;其次,我們在傳統(tǒng)的高分子聚合物材料中加入多孔MOFs,制備形成MOFs/聚合物混合基質(zhì)膜催化材料,并探索了其苯甲醛縮醛化反應(yīng)的催化效果。本論文的研究包括三種不同類型和結(jié)構(gòu)的銅系金屬有機(jī)骨架催化材料,研究了此類催化材料的構(gòu)筑及其在催化領(lǐng)域的應(yīng)用,主要研究內(nèi)容和結(jié)果如下:(1)以UiO-66-NH2(Zr-MOF)為主體,采用氨基合成后修飾的方法制備出UiO-66-Sal載體材料,再負(fù)載三種二價銅鹽作為主要的催化活性組分,制備得到UiO-66-Sal-CuX2(X=Cl-,NO3-,CH3COO-)負(fù)載型非均相催化材料。在以該種催化材料為催化劑,分子氧為綠色氧源條件下,實現(xiàn)了高效催化氧化苯甲醇及其衍生物。(2)以聚丙烯酸功能化的磁性Fe3O4微球為核,通過溶劑熱法在Fe3O4(PAA)的表面包覆一層聚4-乙烯基吡啶(P4VP),接著通過層層自組裝的方法在最外層包覆一定厚度的多孔ZIF-8金屬有機(jī)骨架,為了得到所需的高效率銅催化活性位點,我們采用不同類型的二價銅鹽置換殼層ZIF-8骨架中的鋅離子節(jié)點,從而得到 Copper-doped Fe3O4@P4VP@ZIF-8(Cu-FPZ)催化材料。該非均相催化材料在催化苯甲醇及其衍生物和烯烴環(huán)氧化反應(yīng)中均表現(xiàn)出優(yōu)異的催化活性和循環(huán)穩(wěn)定性。其中,Fe3O4(PAA)磁核可以實現(xiàn)催化材料的快速分離回收;銅離子作為催化活性位點,一方面通過化學(xué)鍵與有機(jī)配體絡(luò)合,有效防止了銅活性組分的流失;另一方面,銅離了分散在Copper-doped Fe3O4@P4VP@ZIF-8磁性核殼催化材料表面,使得催化底物分子可以自由進(jìn)入MOF骨架中,顯著提高了苯甲醇催化氧化反應(yīng)的turnover number(TON)和 turnover frequency(TOF)。(3)由于MOFs材料的晶體特性,使其不像有機(jī)聚合物材料一樣,具有可塑性,因此限制了其可操作性及可加工型,而MOFs膜的研究極大的拓展了 MOF材料的應(yīng)用范圍,在氣體吸附與分離、液體分離、有機(jī)催化等領(lǐng)域顯示出誘人的應(yīng)用前景。本章以經(jīng)典Cu3(BTC)2金屬有機(jī)骨架結(jié)合聚合物醋酸纖維素制備了一種Cu3(BTC)2/CA混合基質(zhì)膜并將其用于苯甲醛的縮醛化反應(yīng)。結(jié)果顯示,多孔(Cu3(BTC)2晶體均勻分布于混合基質(zhì)膜中。制備出的Cu3(BTC)2-0.6MMM具有較大的比表面積,為459 m2/g。同時,制備出的Cu3(BTC)2-0.6混合基質(zhì)膜具有良好的催化性能,其中Cu3(BTC)2起到催化組分的作用。在此流體催化反應(yīng)中,縮醛反應(yīng)在常溫常壓下進(jìn)行,其中,苯甲醛的轉(zhuǎn)化率可以達(dá)到94%,苯甲醛二乙縮醛的選擇性可以達(dá)到99%。在自組裝的流體催化裝置中,苯甲醛可以實現(xiàn)連續(xù)24小時不間斷轉(zhuǎn)化。
[Abstract]:Metallo-organic frameworks (MOFs) are a class of organic-inorganic hybrid porous materials with periodic structure formed by self-assembly of metal ions and organic ligands through coordination interaction. The MOFs porous materials have the advantages of regularity, uniform pore size and adjustable structure, which make them suitable for gas storage, adsorption, separation and catalysis. This paper is devoted to the design and synthesis of novel highly efficient porous MOFs catalytic materials: on the one hand, the supported heterogeneous catalytic materials are prepared by modifying the metal salt coordination compounds on the MOFs after synthesis; on the other hand, the metal organic framework material MOFs is coated on the surface of magnetic nanoparticles and the catalysis is introduced. Heterogeneous catalytic materials with unique MOFs core-shell structure were formed by chemical active components, which realized the controllable design and functional assembly of multi-stage magnetic nano-catalytic materials. Secondly, we added porous MOFs into traditional polymer materials to prepare MOFs/polymer mixed matrix membrane catalytic materials and explored their benzoyls. The catalytic effect of aldehyde acetalization is studied in this paper, including three different types and structures of copper-based metal-organic framework catalytic materials. The structure of these catalytic materials and their application in catalytic field are studied. The main research contents and results are as follows: (1) UiO-66-NH2 (Zr-MOF) is used as the main body and modified by amino synthesis. UiO-66-Sal supported heterogeneous catalytic materials were prepared by loading three divalent copper salts as the main catalytic active components, and then UiO-66-Sal-CuX2 (X=Cl-, NO3-, CH3COO-) supported heterogeneous catalytic materials were prepared. Poly (4-vinylpyridine) (P4VP) was coated on the surface of Fe_3O_4 (PAA) using polyacrylic acid functionalized magnetic Fe_3O_4 microspheres as nuclei. Then, a porous ZIF-8 metal-organic framework with a certain thickness was coated on the outer layer by layer-by-layer self-assembly method. In order to obtain the desired high-efficiency copper catalytic active sites, different types of catalysts were used. Copper-doped Fe_3O_4@P4VP@ZIF-8 (Cu-FPZ) catalytic material was obtained by substituting the zinc ion nodes in the shell ZIF-8 framework with a type of divalent copper salt. The heterogeneous catalytic material exhibited excellent catalytic activity and cyclic stability in the epoxidation of benzyl alcohol, its derivatives and olefins. Rapid separation and recovery of catalytic materials; copper ions as catalytic active sites, on the one hand, through chemical bonds with organic ligands, effectively prevent the loss of copper active components; on the other hand, copper was separated and dispersed on the surface of Copper-doped Fe3O4@P4VP@ZIF-8 magnetic core-shell catalytic materials, enabling the free entry of catalytic substrate molecules into the MOF framework. The turnover number (TON) and turnover frequency (TOF) of the catalytic oxidation of benzyl alcohol were significantly improved. (3) Because of the crystalline properties of MOFs, they are not as plasticity as organic polymer materials, so their maneuverability and machinability are limited. The research of MOFs film greatly expands the application range of MOF materials. Gas adsorption and separation, liquid separation, organic catalysis and other fields show attractive application prospects. In this chapter, a kind of Cu3 (BTC) 2/CA mixed matrix membrane was prepared by the classical Cu3 (BTC) 2 metal-organic framework-bound polymer cellulose acetate and used for acetalization of benzaldehyde. The results showed that the porous (Cu3 (BTC) 2 crystals were uniformly distributed in the mixed matrix. Cu3 (BTC) 2-0.6 MMM has a large specific surface area of 459 m2/g. At the same time, the Cu3 (BTC) 2-0.6 mixed matrix membrane has good catalytic performance, in which Cu3 (BTC) 2 plays a catalytic role. In this fluid catalytic reaction, acetal reaction is carried out at room temperature and atmospheric pressure, in which the conversion of benzaldehyde can be achieved. The selectivity of benzaldehyde diethylacetal can reach 94% and 99%. Benzaldehyde can be converted continuously for 24 hours in a self-assembled fluid catalytic unit.
【學(xué)位授予單位】：北京科技大學(xué)
【學(xué)位級別】：博士
【學(xué)位授予年份】：2017
【分類號】：O643.36
本文編號：2198896
[Abstract]:Metallo-organic frameworks (MOFs) are a class of organic-inorganic hybrid porous materials with periodic structure formed by self-assembly of metal ions and organic ligands through coordination interaction. The MOFs porous materials have the advantages of regularity, uniform pore size and adjustable structure, which make them suitable for gas storage, adsorption, separation and catalysis. This paper is devoted to the design and synthesis of novel highly efficient porous MOFs catalytic materials: on the one hand, the supported heterogeneous catalytic materials are prepared by modifying the metal salt coordination compounds on the MOFs after synthesis; on the other hand, the metal organic framework material MOFs is coated on the surface of magnetic nanoparticles and the catalysis is introduced. Heterogeneous catalytic materials with unique MOFs core-shell structure were formed by chemical active components, which realized the controllable design and functional assembly of multi-stage magnetic nano-catalytic materials. Secondly, we added porous MOFs into traditional polymer materials to prepare MOFs/polymer mixed matrix membrane catalytic materials and explored their benzoyls. The catalytic effect of aldehyde acetalization is studied in this paper, including three different types and structures of copper-based metal-organic framework catalytic materials. The structure of these catalytic materials and their application in catalytic field are studied. The main research contents and results are as follows: (1) UiO-66-NH2 (Zr-MOF) is used as the main body and modified by amino synthesis. UiO-66-Sal supported heterogeneous catalytic materials were prepared by loading three divalent copper salts as the main catalytic active components, and then UiO-66-Sal-CuX2 (X=Cl-, NO3-, CH3COO-) supported heterogeneous catalytic materials were prepared. Poly (4-vinylpyridine) (P4VP) was coated on the surface of Fe_3O_4 (PAA) using polyacrylic acid functionalized magnetic Fe_3O_4 microspheres as nuclei. Then, a porous ZIF-8 metal-organic framework with a certain thickness was coated on the outer layer by layer-by-layer self-assembly method. In order to obtain the desired high-efficiency copper catalytic active sites, different types of catalysts were used. Copper-doped Fe_3O_4@P4VP@ZIF-8 (Cu-FPZ) catalytic material was obtained by substituting the zinc ion nodes in the shell ZIF-8 framework with a type of divalent copper salt. The heterogeneous catalytic material exhibited excellent catalytic activity and cyclic stability in the epoxidation of benzyl alcohol, its derivatives and olefins. Rapid separation and recovery of catalytic materials; copper ions as catalytic active sites, on the one hand, through chemical bonds with organic ligands, effectively prevent the loss of copper active components; on the other hand, copper was separated and dispersed on the surface of Copper-doped Fe3O4@P4VP@ZIF-8 magnetic core-shell catalytic materials, enabling the free entry of catalytic substrate molecules into the MOF framework. The turnover number (TON) and turnover frequency (TOF) of the catalytic oxidation of benzyl alcohol were significantly improved. (3) Because of the crystalline properties of MOFs, they are not as plasticity as organic polymer materials, so their maneuverability and machinability are limited. The research of MOFs film greatly expands the application range of MOF materials. Gas adsorption and separation, liquid separation, organic catalysis and other fields show attractive application prospects. In this chapter, a kind of Cu3 (BTC) 2/CA mixed matrix membrane was prepared by the classical Cu3 (BTC) 2 metal-organic framework-bound polymer cellulose acetate and used for acetalization of benzaldehyde. The results showed that the porous (Cu3 (BTC) 2 crystals were uniformly distributed in the mixed matrix. Cu3 (BTC) 2-0.6 MMM has a large specific surface area of 459 m2/g. At the same time, the Cu3 (BTC) 2-0.6 mixed matrix membrane has good catalytic performance, in which Cu3 (BTC) 2 plays a catalytic role. In this fluid catalytic reaction, acetal reaction is carried out at room temperature and atmospheric pressure, in which the conversion of benzaldehyde can be achieved. The selectivity of benzaldehyde diethylacetal can reach 94% and 99%. Benzaldehyde can be converted continuously for 24 hours in a self-assembled fluid catalytic unit.
【學(xué)位授予單位】：北京科技大學(xué)
【學(xué)位級別】：博士
【學(xué)位授予年份】：2017
【分類號】：O643.36
【參考文獻(xiàn)】
相關(guān)期刊論文 前3條
1 SONG Quan;JIA ManKe;MA WanHong;FANG YanFen;HUANG YingPing;;Heterogeneous degradation of toxic organic pollutants by hydrophobic copper Schiff-base complex under visible irradiation[J];Science China(Chemistry);2013年12期
2 申艷霞;江煥峰;汪朝陽;;縮醛化反應(yīng)研究進(jìn)展[J];有機(jī)化學(xué);2008年05期
3 紀(jì)紅兵,錢宇;清潔氧化反應(yīng)關(guān)鍵技術(shù)基礎(chǔ)研究的進(jìn)展[J];自然科學(xué)進(jìn)展;2004年02期
，本文編號：2198896
本文鏈接：http://www.sikaile.net/kejilunwen/huaxue/2198896.html
最近更新
教材專著
