分子筛固体碱催化剂在有机合成中的应用

综述了近年来以分子筛制备固体碱催化剂的研究进展,包括X型、Y型、L型等微孔分子筛和MCM-41、SBA-15等介孔分子筛经改性得到的固体碱,以及分子筛固体碱催化剂在双键异构化、酯化、酯交换、Knoevenagel缩合、Aldol缩合和Michael加成等有机反应中的应用。     

V/SBA-15的水热合成法制备及其催化氧化性能研究

为了制备负载型介孔分子筛V/SBA-15并研究其在乙苯制苯乙酮反应中的催化性能,以P123(三嵌段共聚物)为模板剂,正硅酸乙酯为硅源,柠檬酸氧钒配合物为前驱体,在酸性条件下采用水热法一步合成了V/SBA-15有序介孔材料,利用XRD,BET,FT-IR等手段对所合成的V/SBA-15材料进行了结构表征,并在乙苯制苯乙酮反应中以苯乙酮选择性和收率来验证催化剂的催化性能。实验结果表明:此合成材料具有类似于SBA-15的高度有序的六方介孔结构,活性组分钒均匀分散在介孔氧化硅基体中;在催化氧化乙苯制苯乙酮反应的优化条件下,苯乙酮选择性和收率分别为80.87%,35.26%。     

介孔分子筛KF-SBA-15的制备及其催化Knoevenagel反应

以P123、正硅酸四乙酯、KF为原料制备了介孔分子筛SBA-15及KF-SBA-15，使用XRD、IR、BET和TG等确证结构。在以苯甲醛和丙二腈为探针的Knoevenagel缩合反应中考察其催化性能，单因素实验法优化反应条件，探究催化剂类型及用量、溶剂、原料物质的量之比等对产率的影响，筛选出最适宜条件为：n（苯甲醛）：n（丙二腈）为1：1，催化剂用量为醛的10%（摩尔分数，下同），室温反应30 min产率可达93.6%。     

SBA-15分子筛负载氮化碳催化二氧化碳与环氧化合物环加成反应

二氧化碳的催化活化是其作为C1资源利用的关键。为了开发高效二氧化碳活化催化剂,将二聚氰胺通过浸渍法负载到介孔分子筛SBA-15孔道中,高温焙烧后,得到SBA-15负载的石墨相氮化碳g-C3N4催化剂。采用透射电镜、X射线衍射、N2吸附和X射线光电子能谱对催化剂进行表征。结果表明,负载g-C3N4后,SBA-15分子筛的介孔结构未发生明显变化,g-C3N4以纳米态分布于SBA-15分子筛的孔道中。将g-C3N4/SBA-15催化剂用于催化二氧化碳与环氧化合物环加成反应制备环状碳酸酯,考察催化剂组成和反应条件对催化性能的影响。结果表明,g-C3N4/SBA-15催化剂有效催化二氧化碳与环氧化合物环加成反应。以g-C3N4/SBA-15为催化剂,在反应温度140℃、反应压力3.5 MPa、反应时间4 h、Zn Br2物质的量分数为1.0%和二聚氰胺负载质量分数为20%条件下,环状碳酸酯产率达91.6%,g-C3N4/SBA-15催化剂制备工艺简单,原料价廉,催化性能优异。     

SBA-15分子筛形成过程的介观动力学模拟及实验研究

为了研究三嵌段共聚物的自组装过程和SBA-15的形成机理,采用介观动力学(MesoDyn)方法模拟介孔分子筛SBA-15形成过程中模板剂P123与硅源试剂TEOS的协同自组装过程,并通过向体系引入稳恒剪切力来代替实际外力模拟了SBA-15六角介观相的形成过程,直观地展现了P123/硅酸物种超分子聚集体在SBA-15结构形成过程中的作用。模拟结果表明,P123与TEOS在水溶液中通过协同作用能够自组装形成尺寸均一的球状超分子聚集体,这是硅基有序介孔分子筛SBA-15形成过程中的前驱体:疏水的PPO嵌段团缩在该超分子聚集体的内部,在SBA-15分子筛形成中起决定性的致孔作用;亲水的PEO嵌段与包裹在胶束外部的TEOS相互交织在一起,其使得SBA-15在制备后期脱除模板剂后形成一些与主介孔相互连接的无规则微孔。在引入剪切力作用后,该P123/TEOS超分子聚集体不再自组装形成球状胶束,而是被拉扯成圆柱状的胶束,并且最终排列成为具有规则的六角形状的聚集结构,这一六角介观相则是介孔分子筛SBA-15的结构基础。今采用模拟条件,用水热法合成了高质量的SBA-15分子筛,通过XRD和高分辨透射电镜分析表明,模拟SBA-15形成过程的结果与实验合成的SBA-15具有相互吻合的完美二维六方结构。     

调控表面活性剂浓度制备单分散SBA-15介孔材料

采用溶胶-凝胶水热法,调控反应参数和反应工艺制备SBA-15介孔材料。通过扫描电镜、透射电镜、X射线衍射以及氮气吸附-脱附分析表征表明,在一定范围,随着表面活性剂浓度增加,介孔材料SBA-15形貌出现由球形、陀螺形到米粒状的变化,介观有序度提高。在反应物料P123与Si物质的量比为0.012时,介孔材料的物性常数如晶面间距、比表面积、孔体积和最可几孔径较小。采用静态陈化-水热法研究不同表面活性剂浓度对介孔材料形貌演变的影响,为有效调控SBA-15介孔材料形貌提供必要依据。     

晶化温度对介孔材料SBA-15结构与形貌的影响

以P123嵌段共聚物表面活性剂为模板剂,在不同晶化温度下合成了不同孔径和比表面积的六方相介孔氧化硅SBA-15,通过XRD, SEM, N2吸附-脱附及TEM等手段系统考察了不同晶化温度对SBA-15晶胞参数、比表面积、孔径及形貌的影响,得到反应最佳晶化温度为120℃. 随着晶化温度的升高,SBA-15的孔径增大,比表面积下降,团聚体颗粒打开形成散落短棒状. 同时还对温度影响SBA-15结构和形貌的机理进行了探讨.     

有序介孔CeO2的合成及其催化性能

以介孔氧化硅（SBA-15）为模板,采用水热法合成有序介孔CeO2。利用X射线衍射仪、N2吸附脱附仪、透射电子显微镜和热重分析仪对样品进行表征。研究了SBA-15与硝酸铈摩尔比对介孔CeO2结构和性能的影响,并对所制备的介孔CeO2进行储放氧性能（oxygen storage/release capacity,OSC）...     

高温下碳对SBA-15结构的影响研究

以介孔分子筛SBA-15为考察对象,蔗糖为碳源,浓硫酸为碳化剂,制备了C/SBA-15复合材料.在氩气氛下进行热处理,考察了在碳存在的情况下,热处理温度对SBA-15物相、组成和结构的影响规律.采用X射线衍射分析(XRD)、N2吸附-脱附等温线、扫描电镜(SEM)等测试手段对产物的晶相、化学组成和形貌进行分析.结果表明,经800～1200℃高温处理,SBA-15主要以无定型氧化硅存在,有序介孔孔道均有部分保持,同时,随着热处理温度升高,SBA-15孔道的有序度降低,比表面、孔容和孔径逐渐减小.当温度升高到1300℃时,碳不仅起到支撑孔道的作用,也作为反应物与氧化硅反应生成碳化硅.而没有碳支撑的SBA-15在1000℃介孔结构完全消失,在1200℃即开始生成方石英相,1300℃完全转为方石英.碳在SBA-15热处理的过程中不仅起到对介孔结构的支撑作用,且能抑制无定形二氧化硅向晶体方石英的转变.     

介孔材料TiO2/SBA-15制备及光催化性能研究

以三嵌段共聚物P123为结构导向剂、甘油作为助溶剂合成了孔道长度可控的六方介孔硅基材料SBA-15,随后在绿色溶媒超临界二氧化碳中合成介孔材料TiO2/SBA-15,利用XRD、N2吸附-脱附、SEM、TEM和EDX等技术对其结构进行分析表征。结果表明甘油的加入可以有效调控SBA-15的孔道长度,TiO2纳米颗粒负载之后,SBA-15六方介孔结构可以得到保持。以染料亚甲基蓝作为模拟污染物对其进行光催化降解测试,合成的负载材料TiO2/SBA-15的降解效果要远远超过纳米TiO2颗粒,同时SBA-15孔道长度越短,其降解效果越好。     

Characterization and catalytic performance of poly(4-vinylpyridine) supported on mesoporous carbon: comparison with poly(4-vinylpyridine) supported on mesoporous silica

In this study, the synthesis of poly(4-vinylpyridine) (P4VP) supported on mesoporous carbon (CMK-3) by in situ polymerization of 4-vinylpyridine in the presence of CMK-3 has been investigated. The structural properties of the P4VP/CMK-3 were investigated by FT-IR, XRD, BET, TGA, SEM and TEM techniques. The catalytic activity of this new heterogeneous basic catalyst was tested for Knoevenagel reaction. Excellent yields at room temperature in aqueous media and solvent-free conditions were obtained. The catalytic activity of this purely organic hybrid catalyst was compared with P4VP/SBA-15 to clarify the advantages of mesoporous carbon on mesoporous silica as support. The results showed that the stability of P4VP/CMK-3 was excellent and could be reused 10 times without much loss of activity in Knoevenagel reaction. Surprisingly, the composite prepared by mesoporous carbon showed much higher activity than that of P4VP/SBA-15. This unique result opens new perspectives for application of mesoporous carbons as structurally defined hydrophobic catalyst support in catalytic reactions.     

Applications of Amine-functionalized Mesoporous Silica in Fine Chemical Synthesis

SBA-15 silica containing homogeneously distributed amine-functional groups and of fiber or platelet morphology was prepared through a modified co-condensation method using P123 copolymer as template under acidic condition. Synthetic factors which led to well-ordered mesoporous materials with high loadings of various amine groups were discussed. The resultant mesoporous materials were efficient base catalysts in Knoevenagel and Claisen–Schmidt addition reactions. The activities over SBA-15 materials with different amino-functional groups are compared. Moreover, the advantage of ordered large mesopores of SBA-15 in catalyzing liquid phase reactions was demonstrated, and the reaction rate could be further increased when SBA-15 was with platelet morphology and short mesochannels.     

Activity of amino-functionalised mesoporous solid bases in microwave-assisted condensation reactions

Aminopropylated functionalised hexagonal mesoporous silicas (HMS) and SBA-15 materials with different amino-loadings (5–30 wt.% NH₂) were synthesized, characterised and their catalytic activities were subsequently investigated in the microwave-assisted Knoevenagel condensation of cyclohexanone and ethyl cyanoacetate as well as in the Michael reaction between 2-cyclohexen-1-one and nitromethane. The effects of the quantity of the catalyst in the reaction as well as a variety of microwave parameters including the power, temperature and time of microwave irradiation were optimised. High activities and selectivities to the condensation product could be achieved at short times of microwave irradiation for both base-catalysed processes. The low loaded HMS-5%NH₂ and higher loaded SBA-15-20%NH₂ were found to give the best activities in the reactions. This observation seems to be related to the significant deterioration observed in textural properties of HMS materials at amino-loadings larger than 10%.     

Control of amine functionality distribution in polyvinylamine/SBA-15 hybrid catalysts for Knoevenagel condensation

Poly(N-vinylformamide) was deposited on the surface of highly ordered hexagonal mesoporous silica SBA-15 by in situ polymerization. Acid-catalyzed hydrolysis followed by neutralization with NaOH (pH = 7.0–10.0) allowed obtaining the poly(vinylamine)/SBA-15 hybrid materials with various distributions of N-containing species, which were determined by XPS and DRIFT spectroscopy. The changes in the form of deposited polymer as well as its interaction with the silica support were discussed. The poly(vinylamine)/SBA-15 materials were tested as catalysts of Knoevenagel condensation of benzaldehyde with ethyl cyanoacetate, ethyl acetoacetate and diethyl malonate. It was found that the sample neutralized at pH = 9.0 showed the best catalytic performance, which was attributed to a high content of accessible NH₂ groups.     

Impact of surface loading on catalytic activity of regular and low micropore SBA-15 in the Knoevenagel condensation

The mesopores of SBA-15 are well-suited for immobilizing catalytic aminosilanes for converting substrates for fine chemicals, but these materials have micropores that could impact the observed reaction rate of immobilized catalysts. Materials are synthesized with conventional methods that produce micropores (Regular Micropore SBA-15; REG) and compared to materials with limited to no micropore volume (NMP SBA-15). These materials are functionalized with aminosilanes for testing in the Knoevenagel condensation. For low amine loadings, NMP materials have a higher observed reaction rate compared to REG materials, achieving twice the conversion in the same time. As the surface density increases, the reaction rate for NMP materials decreases since organosilane functionalization consumes surface silanols that interact cooperatively with the amine. Regardless of surface density, the NMP materials have higher observed reaction rate than the REG materials. These results demonstrate the importance of reducing micropore volume to create highly active catalytic materials.     

Influence of initial Si/Al ratios on the structural,acidic and catalytic properties of nanosized-ZSM-5/SBA-15 analog composites prepared from ZSM-5 precursors

Nano-ZSM-5/SBA-15 analog composites (ZSC) were prepared in a two-step process from ZSM-5 precursors with different Si/Al molar ratios (10–50) via high-temperature synthesis in mildly acidic media (200 °C, pH 3.5) aiming to evaluate the influence of the initial Si/Al ratio on their structural, acidic and catalytic properties. The resulting materials were characterized by SAXS, XRD, FTIR, TEM, N₂ sorption, ²⁷Al solid state-NMR, NH₃-TPD, FTIR spectroscopy of adsorbed pyridine, AAS and ICP-AES. Under the applied synthesis conditions, a ZSC material with controlled distribution of nano-ZSM-5 and SBA-15 analog phases can be prepared from ZSM-5 precursors by adjusting the initial Si/Al ratio in the range of 20–30. Increasing the initial Si/Al ratio to 50, only ZSM-5 nanocrystals were obtained whereas reducing the initial Si/Al ratio to 10 led to the formation of a disordered mesoporous SBA-15 analog. The total acidity increases with the crystallinity of the ZSM-5 phase as varying the Si/Al ratio from 10 to 30 despite the decreased amount of incorporated aluminum. However, the acidity declines slightly when raising the Si/Al ratio to 50 because of the low incorporated aluminum. The catalytic performance of the ZSC materials compared to the reference materials, i.e. purely mesoporous Al-SBA-15 and purely microporous H-ZSM-5 was assessed in the gas phase cracking of cumene and 1,3,5-tri-isopropylbenzene (TIPB) as test reactions. The results show that a balanced ratio of nano-ZSM-5 and SBA-15 analog phases obtained by tuning the initial Si/Al ratio is crucial to achieve superior catalytic performance of the ZSC materials in the cracking of both cumene and TIPB.     

Structure and catalytic properties of Pd encapsulated in mesoporous silica SBA-15 fabricated by two-solvent strategy

The two-solvent method was employed to prepare Pd encapsulated in mesoporous silica (Pd/SBA-15). A 3.01 wt% Pd loading was achieved without the loss of pore ordering. Highly dispersed and uniform palladium nanoparticles could be detected using transmission electron microscopy confirming also the absence of large particles outside the mesopore silica. The catalytic activities of the Pd/SBA-15 nanocomposites were investigated in Heck coupling reactions with activated and non-activated aryl substrates. The Pd/SBA-15 nanocomposite exhibits excellent catalytic activities and reuse ability in air for the Heck carbon–carbon coupling reactions.     

La-Ni2P/SBA-15/堇青石整体式催化剂及加氢脱硫性能

以介孔分子筛SBA-15为载体,制备一系列不同La含量的La-Ni₂P/SBA-15催化剂前驱体,将La-Ni₂P/SBA-15前驱体涂覆在预处理的整体式载体堇青石上,在H2气氛程序升温还原,制备不同La含量的La-Ni2P/SBA-15/堇青石整体式催化剂。对合成的催化剂进行X射线衍射和N2吸附-脱附结构表征,并评价对二苯并噻吩的加氢脱硫活性。结果表明,Ni₂P存在于所有的La-Ni2P/SBA-15/堇青石整体式催化剂中,且随着La含量的增加,La-Ni2P/SBA-15/堇青石整体式催化剂的比表面积和孔体积均有一定程度的提高,催化活性也提高。对于Ni2P/SBA-15/堇青石整体式催化剂,在300 ℃和380 ℃时,二苯并噻吩加氢脱硫转化率仅为27.2%和91.3%;而1.5%La-Ni₂P/SBA-15/堇青石催化剂在300 ℃和380 ℃时,二苯并噻吩转化率分别为36.8%和96.3%,显示出较好的二苯并噻吩加氢脱硫活性。La-Ni₂P/SBA-15/堇青石整体式催化剂在对二苯并噻吩的加氢脱硫过程中,以直接脱硫和加氢脱硫两种脱硫方式同时进行,并且以直接脱硫为主。