杂多酸和桥联有机硅片段共修饰的氧化锆有机—无机杂化催化剂的形貌控制合成及其性能
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摘要
新型、高效和环境友好型催化剂的研究与发展是绿色化学研究的一个重要方面。杂多酸（heteropoly acids，HPAs）因其具有超强的Br nsted酸性和多变的结构，使其在酸催化、光催化和氧化催化等方面受到广泛的关注。但是，HPAs比表面积小（<10m2g1）、热稳定性差、易溶于极性溶剂、分离回收及重复使用困难等缺点，导致HPAs在催化领域的应用受到了限制。本文致力于设计由Keggin型杂多酸H3PW12O40、桥联有机硅片段和ZrO2构成的一系列孔道结构有序度和几何形貌可控的有机–无机杂化催化剂，并通过乙酰丙酸的酯化和以廉价非食用油（芸芥油和文冠果油）为原料制备生物柴油的反应，考察了所制备杂化催化剂的催化性能。具体内容如下：
1．以三嵌段共聚物F127为模板剂，通过溶胶–凝胶共缩合法并结合溶剂热技术，制备了一系列骨架中含有乙基桥联有机硅片段的三维交联介孔结构的H3PW12O40/ZrO2–Si(Et)Si有机–无机杂化催化剂。通过傅立叶红外光谱（FT-IR）、31P、13C和29Si固体核磁共振光谱（MAS NMR）、X射线粉末衍射、高分辨透射电镜（TEM）和氮气吸附孔隙率测定，对杂化催化剂的结构组成、孔形貌和表面物理化学性质进行了表征。选用以芸芥油为原料合成生物柴油的反应为模型，系统研究了功能组分的担载量和催化剂表面的疏水性对其催化活性的影响。此外，本文还详细分析了H3PW12O40/ZrO2–Si(Et)Si杂化催化剂高催化活性的原因。通过三次循环实验发现，杂化催化剂的催化活性和表面物理化学性质基本不变，且催化过程中未检测到H3PW12O40的溶脱，表明其催化稳定性好；
2．以三嵌段共聚物P123为结构导向剂，改变桥联有机硅单元的结构和初始Si/Zr摩尔比等条件，通过溶胶–凝胶共缩合法并结合水热技术，一步制备了具有二维六方有序介孔结构的H3PW12O40/ZrO2–Si(Ph)Si和三维交联介孔结构的H3PW12O40/ZrO2–Si(Et)Si及H3PW12O40/ZrO2–Si(Ph)杂化催化剂。通过傅立叶红外光谱（FT-IR）、31P、13C和29Si固体核磁共振光谱（MAS NMR）、X射线粉末衍射、高分辨透射电镜（TEM）和氮气吸附测定对杂化催化剂的结构组成、孔形貌、表面物理化学性质和功能组分与载体的作用方式进行了表征；同时，采用吡啶吸附原位红外光谱技术对杂化催化剂的酸性点类型进行了表征，采用酸碱滴定法对杂化催化剂的Br nsted酸性点密度进行了测定。以上表征结果显示，活性组分H3PW12O40和有机硅片段分别以Zr–O–W和–Zr–O–Si–R–Si–O–或–Zr–O–Si–R（R=–CH2CH2–、–C6H4–或–C6H5）共价键与载体ZrO2相连接而存在于材料的孔道和孔壁中，这些新键的形成既增强了功能组分与载体间的相互作用，又促进了聚阴离子中负电荷的离域，因而，与H3PW12O40或ZrO2相比，杂化催化剂的Br nsted酸性显著提高。通过乙酰丙酸与低级醇（甲醇、乙醇和正丁醇）的酯化反应，考察了反应物摩尔比、催化剂孔结构有序度和几何形貌及醇的种类对杂化催化剂活性的影响，并提出了不同酸性位点催化乙酰丙酸酯化反应的作用机理。通过三次循环使用情况，评价了杂化催化剂的稳定性；
3．在F127的结构导向及1,3,5-三甲基苯的共模板作用下，分别以1,2-双（三甲氧基）乙烷（BTMSE）和Zr(n-OBu)4作为桥联有机硅前驱体和锆源，经一步水解共缩合法，获得了一系列H3PW12O40和乙基桥联有机硅片段共修饰的ZrO2中空纳米球（H3PW12O40/ZrO2Et HNS）。改变BTMSE和Zr(n-OBu)4的摩尔比，可实现材料几何形貌由三维交联介孔结构向中空纳米球的转变。通过31P、13C和29Si固体核磁共振光谱（MAS NMR）、高分辨透射电镜（TEM）和氮气吸附测定以及酸碱滴定和吡啶吸附原位红外光谱技术，对有机无机杂化中空纳米球催化剂的物理化学性质和酸性质进行了表征。结果显示，乙基桥联有机硅基团修饰的H3PW12O40/ZrO2Et HNS中空纳米球具有内径约为612nm的中空腔和厚度约为2nm的壳层。分别以乙酰丙酸的酯化和文冠果油的酯交换反应，系统考察了H3PW12O40/ZrO2Et HNS的催化性能。研究发现，以上杂化中空纳米球催化剂的优异催化活性源于其强Br nsted酸性和Lewis酸性、独特的中空纳米球形貌和表面疏水性。最后，通过三次循环实验研究了杂化催化剂的可循环性。
Recently, the development of eco-friendly and high-efficiency catalysts is a vital topic ofgreen chemistry. Heteropolyacids (HPAs) have attracted extensive attention in the fields ofacid catalysis, photocatalysis and oxidation catalysis, due to their inherent propertiesincluding strong Br nsted acidity and discrete ionic structure. However, the disadvantages ofHPAs such as small BET surface area (<10m2g1), low thermal stability, high solubility inpolar media and hard to reuse limit their application in catalytic fields. In this dissertation, aseries of organic-inorganic hybrid materials with tunable pore structural ordering andmorphology functionalized by Keggin-type heteropoly acid, alkyl-bridged organosilicamoieties and ZrO2were prepared. The acid catalytic activities towards the esterification oflevulinic acid and biodiesel production from the low-cost non-edible oil (eruca sativa gars(ESG) oli and yellow horn oil) were investigated.
1. A series of3D wormhole-like H3PW12O40/ZrO2–Si(Et)Si with different percentages ofethane-bridged organosilica goups were prepared through one-step sol-gelco-condensation–hydrothermal treatment in the presence of a triblock copolymer surfactantF127. The structural composition, pore morphology and porosity of the hybrid catalysts werecharacterized by FT-IR,31P MAS NMR,13C CP-MAS NMR and29Si MAS NMR,transmission electron microscopy (TEM) and nitrogen porosimetry measurement. The acidcatalytic performances of the hybrid catalysts were evaluated by the transesterification ofESG oil under the mild conditons, and the influences of the contents of functionalcomponents and hydrophobicity on the catalytic activity were investigated systematically.Additionally, the improved catalytic activity of H3PW12O40/ZrO2–Si(Et)Si hybrid catalystswas analyzed in detail. After three recyclings, acid catalytic activity and textural properties ofhybrid materials were unchanged, moreover, the leaching of H3PW12O40was not detectedduring the catalytic process.
2. A series of mesostructured H3PW12O40/ZrO2–Si(R)Si and H3PW12O40/ZrO2–Si(R)(R=–CH2CH2–，–C6H4–or–C6H5) hybrid catalysts with controlled pore geometries andstructural orderings were produced through one-step sol-gel co-condensation–hydrothermaltreatment with a aid of P123.2D hexagonal (H3PW12O40/ZrO2–Si(Ph)Si) and3Dwormhole-like (H3PW12O40/ZrO2–Si(Et)Si and H3PW12O40/ZrO2–Si(Ph)) pore morphologywere obtained by adjusting the structure of the organosilica groups and initial Si/Zr molarratio. The structural composition, pore morphology, porosity and interaction of functionalcomponents and support were characterized by FT-IR,31P MAS NMR,13C CP-MAS NMRand29Si MAS NMR, TEM and nitrogen porosimetry measurement. Additionally, the acid capacity and the type of acid sites were determined by acid-base titration and pyridine-FTIR.The results suggest that H3PW12O40exists in the pore channel via Zr–O–W covalent linkedwith ZrO2, while the organosilica groups were introduced into the ZrO2farmework through–Zr–O–Si–R–Si–O–/–Zr–O–Si–R（R=–CH2CH2–，–C6H4–or–C6H5）linkages. The stronginteraction of the active component and support can facilitate the delocalization of negativecharge, ultimately leading to the enhanced Br nsted acidity. The effects of alcohol to acidmolar ratio, structural orderings and pore geometries as well as the type of alcohol werestudied through the esterification of levulinic acid with various alcohols (methanol, ethanoland n-butanol) under mild conditions. Based on the above results, the mechanism ofesterification of levulinic acid catalyzed by different types of acid sites was proposed. Theacid catalytic activity and stability of hybrid catalysts were evaluated through threeconsecutive cycles.
3. Single-micelle-templated preparation of heteropoly acid and ZrO2bifunctionalizedorganosilica hollow nanospheres (H3PW12O40/ZrO2-Et-HNS) was developed by co-hydrolysisand-condensation of bissilylated organic precursor,1,2-bis(trimethoxysilyl)ethane (BTMSE),with zirconium source (Zr(n-OBu)4) in the presence of H3PW12O40, triblock copolymersurfactant F127and1,3,5-trimethylbenzene (TMB) followed by boiling ethanol washing.Through tuning the molar ratio of BTMSE/Zr(n-OBu)4in the initial gel mixture, themorphology transformation from3D interconnected mesostructure to the hollow sphericalnanostructure was realized. The inner diameter of the H3PW12O40/ZrO2-Et-HNS materials isin the range of612nm, and their shell thickness is ca.2nm. As the novel organic-inorganichybrid catalysts, the catalytic activity of H3PW12O40/ZrO2-Et-HNS was evaluated by themodel reactions of esterification of levulinic acid with methanol to methyl levulinate andtransesterification of yellow horn seed oil with methanol to biodiesel under refluxingtemperature (65oC) and atmospheric pressure. The obtained excellent heterogeneous acidcatalytic activity of H3PW12O40/ZrO2-Et-HNS is explained in terms of their strong Br nstedand Lewis acid acidity, unique hollow nanospherical morphology and hydrophobic surface.Finally, the recyclability of the hybrid catalysts was tested through three consecutive catalyticruns.
1．以三嵌段共聚物F127为模板剂，通过溶胶–凝胶共缩合法并结合溶剂热技术，制备了一系列骨架中含有乙基桥联有机硅片段的三维交联介孔结构的H3PW12O40/ZrO2–Si(Et)Si有机–无机杂化催化剂。通过傅立叶红外光谱（FT-IR）、31P、13C和29Si固体核磁共振光谱（MAS NMR）、X射线粉末衍射、高分辨透射电镜（TEM）和氮气吸附孔隙率测定，对杂化催化剂的结构组成、孔形貌和表面物理化学性质进行了表征。选用以芸芥油为原料合成生物柴油的反应为模型，系统研究了功能组分的担载量和催化剂表面的疏水性对其催化活性的影响。此外，本文还详细分析了H3PW12O40/ZrO2–Si(Et)Si杂化催化剂高催化活性的原因。通过三次循环实验发现，杂化催化剂的催化活性和表面物理化学性质基本不变，且催化过程中未检测到H3PW12O40的溶脱，表明其催化稳定性好；
2．以三嵌段共聚物P123为结构导向剂，改变桥联有机硅单元的结构和初始Si/Zr摩尔比等条件，通过溶胶–凝胶共缩合法并结合水热技术，一步制备了具有二维六方有序介孔结构的H3PW12O40/ZrO2–Si(Ph)Si和三维交联介孔结构的H3PW12O40/ZrO2–Si(Et)Si及H3PW12O40/ZrO2–Si(Ph)杂化催化剂。通过傅立叶红外光谱（FT-IR）、31P、13C和29Si固体核磁共振光谱（MAS NMR）、X射线粉末衍射、高分辨透射电镜（TEM）和氮气吸附测定对杂化催化剂的结构组成、孔形貌、表面物理化学性质和功能组分与载体的作用方式进行了表征；同时，采用吡啶吸附原位红外光谱技术对杂化催化剂的酸性点类型进行了表征，采用酸碱滴定法对杂化催化剂的Br nsted酸性点密度进行了测定。以上表征结果显示，活性组分H3PW12O40和有机硅片段分别以Zr–O–W和–Zr–O–Si–R–Si–O–或–Zr–O–Si–R（R=–CH2CH2–、–C6H4–或–C6H5）共价键与载体ZrO2相连接而存在于材料的孔道和孔壁中，这些新键的形成既增强了功能组分与载体间的相互作用，又促进了聚阴离子中负电荷的离域，因而，与H3PW12O40或ZrO2相比，杂化催化剂的Br nsted酸性显著提高。通过乙酰丙酸与低级醇（甲醇、乙醇和正丁醇）的酯化反应，考察了反应物摩尔比、催化剂孔结构有序度和几何形貌及醇的种类对杂化催化剂活性的影响，并提出了不同酸性位点催化乙酰丙酸酯化反应的作用机理。通过三次循环使用情况，评价了杂化催化剂的稳定性；
3．在F127的结构导向及1,3,5-三甲基苯的共模板作用下，分别以1,2-双（三甲氧基）乙烷（BTMSE）和Zr(n-OBu)4作为桥联有机硅前驱体和锆源，经一步水解共缩合法，获得了一系列H3PW12O40和乙基桥联有机硅片段共修饰的ZrO2中空纳米球（H3PW12O40/ZrO2Et HNS）。改变BTMSE和Zr(n-OBu)4的摩尔比，可实现材料几何形貌由三维交联介孔结构向中空纳米球的转变。通过31P、13C和29Si固体核磁共振光谱（MAS NMR）、高分辨透射电镜（TEM）和氮气吸附测定以及酸碱滴定和吡啶吸附原位红外光谱技术，对有机无机杂化中空纳米球催化剂的物理化学性质和酸性质进行了表征。结果显示，乙基桥联有机硅基团修饰的H3PW12O40/ZrO2Et HNS中空纳米球具有内径约为612nm的中空腔和厚度约为2nm的壳层。分别以乙酰丙酸的酯化和文冠果油的酯交换反应，系统考察了H3PW12O40/ZrO2Et HNS的催化性能。研究发现，以上杂化中空纳米球催化剂的优异催化活性源于其强Br nsted酸性和Lewis酸性、独特的中空纳米球形貌和表面疏水性。最后，通过三次循环实验研究了杂化催化剂的可循环性。
Recently, the development of eco-friendly and high-efficiency catalysts is a vital topic ofgreen chemistry. Heteropolyacids (HPAs) have attracted extensive attention in the fields ofacid catalysis, photocatalysis and oxidation catalysis, due to their inherent propertiesincluding strong Br nsted acidity and discrete ionic structure. However, the disadvantages ofHPAs such as small BET surface area (<10m2g1), low thermal stability, high solubility inpolar media and hard to reuse limit their application in catalytic fields. In this dissertation, aseries of organic-inorganic hybrid materials with tunable pore structural ordering andmorphology functionalized by Keggin-type heteropoly acid, alkyl-bridged organosilicamoieties and ZrO2were prepared. The acid catalytic activities towards the esterification oflevulinic acid and biodiesel production from the low-cost non-edible oil (eruca sativa gars(ESG) oli and yellow horn oil) were investigated.
1. A series of3D wormhole-like H3PW12O40/ZrO2–Si(Et)Si with different percentages ofethane-bridged organosilica goups were prepared through one-step sol-gelco-condensation–hydrothermal treatment in the presence of a triblock copolymer surfactantF127. The structural composition, pore morphology and porosity of the hybrid catalysts werecharacterized by FT-IR,31P MAS NMR,13C CP-MAS NMR and29Si MAS NMR,transmission electron microscopy (TEM) and nitrogen porosimetry measurement. The acidcatalytic performances of the hybrid catalysts were evaluated by the transesterification ofESG oil under the mild conditons, and the influences of the contents of functionalcomponents and hydrophobicity on the catalytic activity were investigated systematically.Additionally, the improved catalytic activity of H3PW12O40/ZrO2–Si(Et)Si hybrid catalystswas analyzed in detail. After three recyclings, acid catalytic activity and textural properties ofhybrid materials were unchanged, moreover, the leaching of H3PW12O40was not detectedduring the catalytic process.
2. A series of mesostructured H3PW12O40/ZrO2–Si(R)Si and H3PW12O40/ZrO2–Si(R)(R=–CH2CH2–，–C6H4–or–C6H5) hybrid catalysts with controlled pore geometries andstructural orderings were produced through one-step sol-gel co-condensation–hydrothermaltreatment with a aid of P123.2D hexagonal (H3PW12O40/ZrO2–Si(Ph)Si) and3Dwormhole-like (H3PW12O40/ZrO2–Si(Et)Si and H3PW12O40/ZrO2–Si(Ph)) pore morphologywere obtained by adjusting the structure of the organosilica groups and initial Si/Zr molarratio. The structural composition, pore morphology, porosity and interaction of functionalcomponents and support were characterized by FT-IR,31P MAS NMR,13C CP-MAS NMRand29Si MAS NMR, TEM and nitrogen porosimetry measurement. Additionally, the acid capacity and the type of acid sites were determined by acid-base titration and pyridine-FTIR.The results suggest that H3PW12O40exists in the pore channel via Zr–O–W covalent linkedwith ZrO2, while the organosilica groups were introduced into the ZrO2farmework through–Zr–O–Si–R–Si–O–/–Zr–O–Si–R（R=–CH2CH2–，–C6H4–or–C6H5）linkages. The stronginteraction of the active component and support can facilitate the delocalization of negativecharge, ultimately leading to the enhanced Br nsted acidity. The effects of alcohol to acidmolar ratio, structural orderings and pore geometries as well as the type of alcohol werestudied through the esterification of levulinic acid with various alcohols (methanol, ethanoland n-butanol) under mild conditions. Based on the above results, the mechanism ofesterification of levulinic acid catalyzed by different types of acid sites was proposed. Theacid catalytic activity and stability of hybrid catalysts were evaluated through threeconsecutive cycles.
3. Single-micelle-templated preparation of heteropoly acid and ZrO2bifunctionalizedorganosilica hollow nanospheres (H3PW12O40/ZrO2-Et-HNS) was developed by co-hydrolysisand-condensation of bissilylated organic precursor,1,2-bis(trimethoxysilyl)ethane (BTMSE),with zirconium source (Zr(n-OBu)4) in the presence of H3PW12O40, triblock copolymersurfactant F127and1,3,5-trimethylbenzene (TMB) followed by boiling ethanol washing.Through tuning the molar ratio of BTMSE/Zr(n-OBu)4in the initial gel mixture, themorphology transformation from3D interconnected mesostructure to the hollow sphericalnanostructure was realized. The inner diameter of the H3PW12O40/ZrO2-Et-HNS materials isin the range of612nm, and their shell thickness is ca.2nm. As the novel organic-inorganichybrid catalysts, the catalytic activity of H3PW12O40/ZrO2-Et-HNS was evaluated by themodel reactions of esterification of levulinic acid with methanol to methyl levulinate andtransesterification of yellow horn seed oil with methanol to biodiesel under refluxingtemperature (65oC) and atmospheric pressure. The obtained excellent heterogeneous acidcatalytic activity of H3PW12O40/ZrO2-Et-HNS is explained in terms of their strong Br nstedand Lewis acid acidity, unique hollow nanospherical morphology and hydrophobic surface.Finally, the recyclability of the hybrid catalysts was tested through three consecutive catalyticruns.
引文
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