硅基復(fù)合金屬氧化物的合成及BAEYER-VILLIGER催化性能的研究
發(fā)布時(shí)間：2019-01-01 09:47
【摘要】：介孔硅材料作為一種新型的納米材料,具有三維立方相的孔道結(jié)構(gòu)、較大的比表面積、孔體積和可調(diào)節(jié)的孔徑尺寸�；谶@些優(yōu)點(diǎn),介孔材料在吸附分離、催化等領(lǐng)域受到了極大的關(guān)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催化氧化反應(yīng)中的高效催化劑。核殼磁性介孔硅材料經(jīng)過金屬銅納米顆粒的改性,提高了材料的催化活性,形成垂直徑向的孔道結(jié)構(gòu)促進(jìn)催化劑材料與溶液中有機(jī)物分子的接觸,加快了非均相Baeyer-Villiger催化反應(yīng)的進(jìn)行。雙金屬摻雜的介孔硅材料由于雙金屬之間具有協(xié)同作用,使得此類催化劑材料在非均相Baeyer-Villiger催化氧化反應(yīng)中表現(xiàn)出較好的催化性能。本文具體研究內(nèi)容如下:1.溶膠凝膠法和水熱合成法制備出金屬銅納米顆粒摻雜的核殼磁性介孔硅材料,通過XRD、TEM、VSM和N2吸附-脫附等溫線表征可以看出,催化劑材料具有核-殼-殼三層結(jié)構(gòu)和較大的比表面積和孔體積,金屬納米顆粒分布均勻和超順磁性的特點(diǎn),有利于催化活性位點(diǎn)和反應(yīng)物的充分接觸以及材料的回收利用。從而使催化劑材料在BV催化氧化反應(yīng)中表現(xiàn)出較好的催化性能和重復(fù)使用性。2.使用低溫鎂熱反應(yīng)和酸性刻蝕的方法,合成出介孔硅材料,再利用浸漬法制備出雙金屬鐵鉬摻雜的介孔硅材料FeMo@MPSi。通過XRD、SEM、TEM和N2吸附-脫附等溫線表征方法可以得出,與SBA-15材料相比,介孔硅在保持原來有序三維立體孔道結(jié)構(gòu)的基礎(chǔ)上,孔徑、比表面積和孔體積有所增加,這樣提供了大量的催化活性位點(diǎn)。同時(shí),在B-V催化氧化反應(yīng)中,這種介孔結(jié)構(gòu)有利于大分子酮類和酯類物質(zhì)的進(jìn)出。鐵鉬雙金屬摻雜之后,由于雙金屬的協(xié)同作用,可以同時(shí)激活酮類反應(yīng)物上羰基碳原子,加快B-V催化氧化反應(yīng)的速度,從而使催化劑材料在B-V反應(yīng)中表現(xiàn)出較好的催化反應(yīng)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.
【學(xué)位授予單位】：天津工業(yè)大學(xué)
【學(xué)位級別】：碩士
【學(xué)位授予年份】：2017
【分類號】：O643.36
本文編號：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.
【學(xué)位授予單位】：天津工業(yè)大學(xué)
【學(xué)位級別】：碩士
【學(xué)位授予年份】：2017
【分類號】：O643.36
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