铜系金属有机骨架构筑及其催化性能研究
发布时间：2018-08-23 11:07
【摘要】：金属有机骨架(MOFs)材料是指金属离子与有机配体通过配位作用自组装形成的一类具有周期性结构的有机-无机杂化多孔材料。这种MOFs多孔材料具有规则、均匀的孔径及结构可调性等优势,使其在气体储存、吸附分离及催化领域等方面具有潜在的研究价值。本文致力于设计合成新型高效多孔MOFs催化材料:一方面通过对MOFs材料进行合成后修饰负载金属盐配位化合物,制备负载型非均相催化材料;另一方面通过在磁性纳米粒子表面包覆金属有机骨架材料MOFs,并引入催化活性组分形成具有独特MOFs核壳结构的非均相催化材料,实现了多级结构磁性纳米催化材料的可控设计及功能化组装;其次,我们在传统的高分子聚合物材料中加入多孔MOFs,制备形成MOFs/聚合物混合基质膜催化材料,并探索了其苯甲醛缩醛化反应的催化效果。本论文的研究包括三种不同类型和结构的铜系金属有机骨架催化材料,研究了此类催化材料的构筑及其在催化领域的应用,主要研究内容和结果如下:(1)以UiO-66-NH2(Zr-MOF)为主体,采用氨基合成后修饰的方法制备出UiO-66-Sal载体材料,再负载三种二价铜盐作为主要的催化活性组分,制备得到UiO-66-Sal-CuX2(X=Cl-,NO3-,CH3COO-)负载型非均相催化材料。在以该种催化材料为催化剂,分子氧为绿色氧源条件下,实现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微球为核,通过溶剂热法在Fe3O4(PAA)的表面包覆一层聚4-乙烯基吡啶(P4VP),接着通过层层自组装的方法在最外层包覆一定厚度的多孔ZIF-8金属有机骨架,为了得到所需的高效率铜催化活性位点,我们采用不同类型的二价铜盐置换壳层ZIF-8骨架中的锌离子节点,从而得到 Copper-doped Fe3O4@P4VP@ZIF-8(Cu-FPZ)催化材料。该非均相催化材料在催化苯甲醇及其衍生物和烯烃环氧化反应中均表现出优异的催化活性和循环稳定性。其中,Fe3O4(PAA)磁核可以实现催化材料的快速分离回收;铜离子作为催化活性位点,一方面通过化学键与有机配体络合,有效防止了铜活性组分的流失;另一方面,铜离了分散在Copper-doped Fe3O4@P4VP@ZIF-8磁性核壳催化材料表面,使得催化底物分子可以自由进入MOF骨架中,显著提高了苯甲醇催化氧化反应的turnover number(TON)和 turnover frequency(TOF)。(3)由于MOFs材料的晶体特性,使其不像有机聚合物材料一样,具有可塑性,因此限制了其可操作性及可加工型,而MOFs膜的研究极大的拓展了 MOF材料的应用范围,在气体吸附与分离、液体分离、有机催化等领域显示出诱人的应用前景。本章以经典Cu3(BTC)2金属有机骨架结合聚合物醋酸纤维素制备了一种Cu3(BTC)2/CA混合基质膜并将其用于苯甲醛的缩醛化反应。结果显示,多孔(Cu3(BTC)2晶体均匀分布于混合基质膜中。制备出的Cu3(BTC)2-0.6MMM具有较大的比表面积,为459 m2/g。同时,制备出的Cu3(BTC)2-0.6混合基质膜具有良好的催化性能,其中Cu3(BTC)2起到催化组分的作用。在此流体催化反应中,缩醛反应在常温常压下进行,其中,苯甲醛的转化率可以达到94%,苯甲醛二乙缩醛的选择性可以达到99%。在自组装的流体催化装置中,苯甲醛可以实现连续24小时不间断转化。
[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.
【学位授予单位】：北京科技大学
【学位级别】：博士
【学位授予年份】：2017
【分类号】：O643.36
本文编号：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.
【学位授予单位】：北京科技大学
【学位级别】：博士
【学位授予年份】：2017
【分类号】：O643.36
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