硅基复合金属氧化物的合成及BAEYER-VILLIGER催化性能的研究
发布时间:2019-01-01 09:47
【摘要】:介孔硅材料作为一种新型的纳米材料,具有三维立方相的孔道结构、较大的比表面积、孔体积和可调节的孔径尺寸。基于这些优点,介孔材料在吸附分离、催化等领域受到了极大的关注。本文致力于介孔硅材料的合成及改性研究,目的在于合成出非均相Baeyer-Villiger催化氧化反应中的高效催化剂。核壳磁性介孔硅材料经过金属铜纳米颗粒的改性,提高了材料的催化活性,形成垂直径向的孔道结构促进催化剂材料与溶液中有机物分子的接触,加快了非均相Baeyer-Villiger催化反应的进行。双金属掺杂的介孔硅材料由于双金属之间具有协同作用,使得此类催化剂材料在非均相Baeyer-Villiger催化氧化反应中表现出较好的催化性能。本文具体研究内容如下:1.溶胶凝胶法和水热合成法制备出金属铜纳米颗粒掺杂的核壳磁性介孔硅材料,通过XRD、TEM、VSM和N2吸附-脱附等温线表征可以看出,催化剂材料具有核-壳-壳三层结构和较大的比表面积和孔体积,金属纳米颗粒分布均匀和超顺磁性的特点,有利于催化活性位点和反应物的充分接触以及材料的回收利用。从而使催化剂材料在BV催化氧化反应中表现出较好的催化性能和重复使用性。2.使用低温镁热反应和酸性刻蚀的方法,合成出介孔硅材料,再利用浸渍法制备出双金属铁钼掺杂的介孔硅材料FeMo@MPSi。通过XRD、SEM、TEM和N2吸附-脱附等温线表征方法可以得出,与SBA-15材料相比,介孔硅在保持原来有序三维立体孔道结构的基础上,孔径、比表面积和孔体积有所增加,这样提供了大量的催化活性位点。同时,在B-V催化氧化反应中,这种介孔结构有利于大分子酮类和酯类物质的进出。铁钼双金属掺杂之后,由于双金属的协同作用,可以同时激活酮类反应物上羰基碳原子,加快B-V催化氧化反应的速度,从而使催化剂材料在B-V反应中表现出较好的催化反应性能。
[Abstract]:As a new nano material, mesoporous silicon has three-dimensional cubic pore structure, large specific surface area, pore volume and adjustable pore size. Based on these advantages, mesoporous materials have attracted great attention in the fields of adsorption, separation, catalysis and so on. This paper is devoted to the synthesis and modification of mesoporous silicon materials with the aim of synthesizing highly efficient catalysts for heterogeneous Baeyer-Villiger catalytic oxidation. The core-shell magnetic mesoporous silicon material was modified by metal copper nanoparticles, and the catalytic activity of the material was improved, and the vertical radial pore structure was formed to promote the contact between the catalyst material and the organic molecules in the solution. The heterogeneous Baeyer-Villiger catalytic reaction was accelerated. Bimetallic doped mesoporous silicon materials exhibit good catalytic performance in heterogeneous Baeyer-Villiger oxidation due to the synergistic effect between bimetallic materials. The main contents of this paper are as follows: 1. The core-shell magnetic mesoporous silicon materials doped with copper nanoparticles were prepared by sol-gel method and hydrothermal synthesis method. It can be seen by XRD,TEM,VSM and N2 adsorption-desorption isotherms. The catalyst material has the characteristics of core-shell three-layer structure, large specific surface area and pore volume, uniform distribution of metal nanoparticles and superparamagnetism, which is conducive to the full contact of catalytic active sites and reactants and the recovery and utilization of materials. Thus, the catalyst material showed good catalytic performance and reusability in BV catalytic oxidation reaction. 2. Mesoporous silicon material was synthesized by low temperature magnesium thermal reaction and acid etching, and bimetallic ferromolybdenum doped mesoporous silicon material FeMo@MPSi. was prepared by impregnation method. By means of XRD,SEM,TEM and N2 adsorption-desorption isotherm characterization, it can be concluded that compared with SBA-15 materials, the pore size, specific surface area and pore volume of mesoporous silicon increase on the basis of maintaining the original ordered three-dimensional pore structure. This provides a large number of catalytic active sites. At the same time, the mesoporous structure is favorable to the entry and exit of macromolecular ketones and esters in the B-V catalytic oxidation reaction. After iron-molybdenum bimetallic doping, the carbonyl carbon atoms on ketones can be activated at the same time because of the synergistic effect of bimetallic, and the reaction rate of B-V catalytic oxidation can be accelerated. Thus, the catalyst material showed better catalytic performance in B-V reaction.
【学位授予单位】:天津工业大学
【学位级别】:硕士
【学位授予年份】:2017
【分类号】:O643.36
本文编号:2397378
[Abstract]:As a new nano material, mesoporous silicon has three-dimensional cubic pore structure, large specific surface area, pore volume and adjustable pore size. Based on these advantages, mesoporous materials have attracted great attention in the fields of adsorption, separation, catalysis and so on. This paper is devoted to the synthesis and modification of mesoporous silicon materials with the aim of synthesizing highly efficient catalysts for heterogeneous Baeyer-Villiger catalytic oxidation. The core-shell magnetic mesoporous silicon material was modified by metal copper nanoparticles, and the catalytic activity of the material was improved, and the vertical radial pore structure was formed to promote the contact between the catalyst material and the organic molecules in the solution. The heterogeneous Baeyer-Villiger catalytic reaction was accelerated. Bimetallic doped mesoporous silicon materials exhibit good catalytic performance in heterogeneous Baeyer-Villiger oxidation due to the synergistic effect between bimetallic materials. The main contents of this paper are as follows: 1. The core-shell magnetic mesoporous silicon materials doped with copper nanoparticles were prepared by sol-gel method and hydrothermal synthesis method. It can be seen by XRD,TEM,VSM and N2 adsorption-desorption isotherms. The catalyst material has the characteristics of core-shell three-layer structure, large specific surface area and pore volume, uniform distribution of metal nanoparticles and superparamagnetism, which is conducive to the full contact of catalytic active sites and reactants and the recovery and utilization of materials. Thus, the catalyst material showed good catalytic performance and reusability in BV catalytic oxidation reaction. 2. Mesoporous silicon material was synthesized by low temperature magnesium thermal reaction and acid etching, and bimetallic ferromolybdenum doped mesoporous silicon material FeMo@MPSi. was prepared by impregnation method. By means of XRD,SEM,TEM and N2 adsorption-desorption isotherm characterization, it can be concluded that compared with SBA-15 materials, the pore size, specific surface area and pore volume of mesoporous silicon increase on the basis of maintaining the original ordered three-dimensional pore structure. This provides a large number of catalytic active sites. At the same time, the mesoporous structure is favorable to the entry and exit of macromolecular ketones and esters in the B-V catalytic oxidation reaction. After iron-molybdenum bimetallic doping, the carbonyl carbon atoms on ketones can be activated at the same time because of the synergistic effect of bimetallic, and the reaction rate of B-V catalytic oxidation can be accelerated. Thus, the catalyst material showed better catalytic performance in B-V reaction.
【学位授予单位】:天津工业大学
【学位级别】:硕士
【学位授予年份】:2017
【分类号】:O643.36
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