含过渡金属配合物有机—无机杂化材料的制备及催化环氧化反应性能
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摘要
环氧化合物是一类用途极广的有机合成中间体,可以通过选择性开环或者官能团的转化,生成一系列有价值的化合物,在医药,农药,香料等精细化学品的合成上具有非常重要的意义。目前工业上合成环氧化合物的方法主要有Ag/Al2O3/O2 (EO)体系,氯醇法(PO)和Halcon法(PO)。Ag/Al2O3/O2 (EO)体系对乙烯环氧化具有高的效率,但是催化高级烯烃环氧化效果则不理想；氯醇法工艺虽然投资少,产率高,但是在生产过程中产生大量含卤污水,环境污染严重;Halcon法虽然克服氯醇法污染严重问题,但是也存在工艺流程长,联产物多,对设备腐蚀严重等缺点。所以开发高效低污染的环氧化新工艺是具有非常意义的工作。
研究发现一些仿生类金属配合物,如手性金属卟啉、手性席夫碱金属配合物、金属肽睛、邻菲罗啉金属配合物、联吡啶金属配合物等,在烯烃环氧化反应和烯烃不对称环氧化中表现出高的活性及立体选择性,且同时具有烯烃底物适用范围广、反应条件温和等优点。然而,这类金属配合物作为均相催化剂使用时通常存在回收困难、成本高,且在反应过程中易形成惰性的二聚(低聚)体等问题,从而限制了其发展和实际应用。相比之下,多相催化剂可以克服上述缺点,易于回收和循环使用。近年来,人们围绕均相配合物催化剂的多相化研究开展了大量研究工作,即把金属配合物(或有机金属化合物)和固体载体(如含硅的无机介孔材料)相结合构筑出即具有高的催化活性又易于回收和循环使用的有机-无机杂化材料催化剂。针对烯烃环氧化反应,目前已经有多种性能较为优异的有机-无机杂化材料催化剂体系被相继报道出来,显示出良好的发展前景。在这一领域,研究和开发出性能更加优异、环境友好的新型有机-无机杂化材料多相环氧化催化体系仍是备受关注的课题。
基于上述情况,本论文开展了不同类型金属配合物功能化的有机-无机杂化材料的合成、表征及催化环氧化反应性能研究工作。通过选择适当的金属阳离子和有机配体,结合一些无机载体的使用,合成出多种新型高效多相环氧化催化剂体系。在反应评价过程中系统地考察了烯烃种类,氧化剂类型,反应介质等因素对催化剂性能的影响,同时结合各种表征对催化剂结构、表面性质进行了研究,探讨了催化剂活性中心性质和催化作用机制等问题。主要研究内容和结果概述如下：
1.MnⅡ吡啶联吡唑配合物功能化的SBA-15杂化材料的制备及催化性能
通过共价键嫁接的方法将[MnⅡ(l)2](OAc)2 (l=3-(2-吡啶基)-1-吡哗))固载到介孔SBA-15表面上制成杂化材料。催化反应结果表明：这类杂化材料在以间氯过氧苯甲酸(m-CPBA)为氧化剂时,对多种烯烃(包括一些难氧化的端基类烯烃,如1-辛烯)表现出非常高的低温催化活性、选择性及稳定性。氧化剂类型和溶剂类型的选择也会显著影响催化剂的性能。当分别以叔丁基过氧化氢和间氯过氧苯甲酸为氧化剂时,由于m-CPBA的氯苯基的吸电子能力要比t-BuOOH的叔丁基强,使两种氧化剂在催化剂上的活化方式和途径产生差异。当t-BuOOH作为氧化剂时,所形成t-BuOO-MnⅡ加合物中O-O键容易均裂产生HO-MnⅢ中间体和自由基(RO·),使得反应产生大量副产物(如醛)；而当m-CPBA作为氧化剂时,形成的加合物中的O-O键容易发生异裂而产生高价O=MnⅣ中间体,从而有利于环氧化物的生成。此外,相对于质子型溶剂(如乙醇),在非质子型溶剂(如乙腈)中,催化剂通常会表现出更高的活性和选择性。原位UV-vis光谱等表征结果证实在乙腈为溶剂时,MnⅡ-更易于与氧化剂(m-CPBA)作用生成高价的O=MnⅣ中间体,这应该是催化剂表现出高活性和高的环氧化物选择性的主要原因。
2.过氧化钨配合物功能化的介孔材料的制备及催化性能
通过后嫁接法合成了过氧化钨配合物WO(O2)2L(L=3-(2-吡啶基)-1-吡唑(1);3-(2-氨乙基)-氨丙基(2)、咪唑(3)或4.4’-联吡啶(4))功能化的介孔SBA-15材料(记为WO5(n)-SBA-15)。这几种有机-无机杂化材料催化剂在以双氧水为氧化剂时,均对环辛烯环氧化反应中表现出较高的活性及选择性。然而,由配体2-4合成的催化剂的稳定性较差,在循环使用过程中催化活性明显下降,推测主要原因是由于活性钨物种的配位环境发生一定变化而导致的。而WO5(l)-SBA-15催化剂在六次循环反应中活性基本保持不变,且中断实验结果也证实该反应确实是多相催化反应,显示出很高的稳定性：另外该催化剂还具有很高的双氧水利用率(99.5%以上),性能明显优于其它类型金属配合物催化剂。WO5(l)-SBA-15表现出高稳定性可主要归结于两方面因素：一是由于配体和SBA-15的表面有很强的共价键连接,二是由于含氮双齿配体具有很强的配位能力,可以和过氧化钨物种形成稳定的配合物。此外,通过对比不同类型的无机载体还发现载体上存在大的孔道有利于反应活性的提高,并且载体中存在适量的路易斯酸中心也会提高催化剂的反应活性。
3.过氧化钨吡啶基吡唑配合物功能化的炭材料的制备及催化性能
通过共价键嫁接的方法将WO5(1)配合物固载到炭化蔗糖(SC)和介孔炭材料(NC-2)得多相环氧化催化剂(记为WO5(l)-SC和WO5(l)-NC-2),并考察了其对以双氧水为氧化剂的烯丙基醇环氧化反应的催化性能。结果表明：WO5(l)-SC和WO5(l)-NC-2催化剂的性能受溶剂影响很大。当一些常用的有机溶剂(如乙腈)为反应介质时,两种催化剂的均表现出非常低的反应活性;而当水为反应介质时,两种催化剂的反应活性均显著提高。结合一些表征结果,可以认为炭载体表面存在的大量含氧官能团使催化剂表面具有一定的极性(亲水性)从而使其在水体系中为表现出较高的催化活性。相比之下,WO5(l)-NC-2的催化活性要高于WO5(l)-SC,一方面可能是由于两种载体的表面性质(极性)有一定的差异所致,另一方面也可能是由于NC-2具有更高的比表面积,使活性中心能够更加均匀的高分散在载体表面上。值得一提的是,在不添加其它任何溶剂的条件下,WO5(l)-NC-2对一些烯丙基醇环氧化表现出非常高的催化活性(TOF,10125h-1per W site)和环氧化物选择性,且催化剂在反应过程中没有发生活性物种流失、可多次循环使用,显示出良好的稳定性。
4. MnⅢ(salen)配合物功能化的介孔磷酸铝材料的制备及其在烯烃不对称环氧化反应中的应用
通过氨丙基轴向嫁接的方法将手性MnⅢ(salen)配合物固载到介孔磷酸铝材料上,通过调变磷/铝比可以得到不同孔道结构的多相手性MnⅢ(salen)催化剂(分别记为Salen-Mn-AP-AlP0.9O,Salen-Mn-AP-AlP1.0O和Salen-Mn-AP-AlP1.1O)。并分别考察了其在次氯酸钠/4-苯基氧化吡啶(NaClO/PPNO)和间氯过氧苯甲酸/N-甲基吗啉氮氧化物(m-CPBA/NMO)体系下对烯烃(如：苯乙烯和α-甲基苯乙烯,反式-1,2-二苯乙烯)不对称环氧化的催化性能。实验结果表明通过调变磷/铝比增大载体的纳米孔径可以提高催化剂的手性选择性(ee%),在苯乙烯和α-甲基苯乙烯的不对称环氧化反应中可以得到与均相催化剂相近的ee%。
Synthesis and Catalytic Properties in Alkene Epoxidation
Epoxides are a class of highly versatile intermediates in organic synthesis, which can be converted to other valuable compounds by selective ring opening or functional groups transformation, it is very important in medicine, pesticides, fragrances and other fine chemicals synthesis. The current industry methods for the synthesis of epoxides are Ag/Al2O3/O2 (Ethylene oxide). Halcon (Propylene oxide) and halogenohydrin (Propylene oxide). However, Ag/Al2O3/O2 (EO) systems showed lower efficiency for other alkenes. For the halogenohydrin process, the production of large amounts of chlorine-containing waste water leads to severely environmental pollution. In Halcon process, many side-products are produced, which suffers from the costly material consumption and equipment cauterization. Therefore, the development of high efficiency and low pollution epoxidation process is very meaningful work.
Some biomimetic catalysts (such as chiral metalloporphyrin, chiral Schiff base metal complexes, metal peptide eye, phenanthroline metal complexes, bipyridyl metal complexes and other multi-nitrogen, nitrogen-oxygen organic metal complexes and so on) were found as efficient homogeneous catalysts for the epoxidation of alkenes. However, it is difficult to recover and reuse those homogeneous metal complexes, and the catalytic activity of these homogeneous catalysts decreases due to the formation of inactive dimericμ-oxo species, which has restricted their wide applications in industrial and laboratory synthesis. One way to overcome this problem is to immobilize them on solid supports to synhesis organic-inorganic hybrid materials. In comparison with the homogeneous counterparts, heterogeneous systems show many advantages such as easy separation and recovery of the catalyst from reaction media, higher stability of catalytic species and catalyst protection against destruction. For olefin epoxidation. many good performance of the organic-inorganic hybrid materials have been reported. In this area, it is still an interesting and significant subject to develop more excellent performance and environmentally friendly organic-inorganic hybrid heterogeneous epoxidation catalyst systems.
Based on the above, in this thesis, we try to prepare and characterization novel transition metal complexes functionalized organic-inorganic hybrid materials, and study their catalytic properties in alkene epoxidation. By selecting appropriate metal ions and organic ligands, combined with the use of certain inorganic supports, we synthesis a variety of new highly efficient hetergeneous epoxidation catalysts. In the epoxidation reaction text, the influence of different reaction parameters-such as the alkenes. oxidants and solvents-on the catalytic performance of the hybrid materials has been studied and discussed, and combined with a variety of characterization of the catalyst structure and surface properties to study the nature of catalyst active center and catalytic mechanism. The main contents and results are summarized as follows:
1. Mesoporous SBA-15 Modified with Manganese Pyrazolylpyridine Complexes: preparation and catalytic properties
A manganese-based hybrid mesoporous material was synthesized by covalent grafting of [MnⅡ(1)2](OAc)2 (1=[3-(2-pyridyl) pyrazol-1-yl]aceticacid amide) onto the surface of SBA-15. Catalytic tests showed that the hybrid material could act as an efficient heterogeneous catalyst for the epoxidation of a wide range of alkenes (including terminal ones) under mild reaction conditions when peracids (e.g.. meta-chloroperbenzoic acid) are used as oxidants. Moreover, the catalytic performance of the hybrid materal is oxidant-dependent, these contrasting mechanistic behaviors can be rationalized on the basis of the physical parameters of the substitutes on O-O bond in these two oxidants (t-BuOOH and m-CPBA). The chlorophenyl group of m-CPBA has a stronger ability to withdraw electron density from the peroxo unit alkyl group in t-BuOOH. This feature may result in an easy homolytic cleavage of the O-O bond (radical pathway) after the formation of a t-BuOO-MnⅡfragment, while a heterolytic cleavage of the O-O bond is dominant in the m-CPBA case. It exhibits higher catalytic activity and selectivity towards epoxides in the presence of an aprotic solvent (e.g.. CH3CN). UV-vis measurements revealed that high-valent O=MnⅣ-species are easily formed during the reaction course, when meta-chloroperbenzoic acid is used as oxidant and CH3CN is used as solvent, being probably the reason for the high activity of the hybrid material and its selectivity towards epoxide formation.
2. Mesoporous materials modified with oxodiperoxo tungsten complexes: preparation and catalytic properties
A hybrid mesoporous SBA-15 material containing an oxodiperoxo tungsten complex of the type [WO(O2)21] (1=[3-(2-pyridyl) pyrazol-1-yl] aceticacid amide) was synthesized by a post-grafting route (WO5(I)-SBA-15). The catalytic property of the heterogeneous oxodiperoxo tungsten complex catalyst in the epoxidation of cyclooctene with H2O2 as the oxidant was investigated in comparison with other three kinds of hybrid tungsten containing SBA-15 materials bearing ethylenediamine (2), imidazole (3) or 4,4'-bipyridine (4) ligands. It was found that all oxodiperoxo tungsten catalysts were active at the reaction temperature of 55℃with CH3CN as solvent. However, only the catalyst with the pyrazolylpyridine ligand showed good recoverability and relatively high stability against leaching of active tungsten species. Moreover, this catalyst showed very high efficiency for H2O2 utilization (>99.5%). The high stability of WO5(1)-SBA-15 can be attributed to two factors:First, there is strong covalent grafting between the organic ligand system and the inorganic mesoporous material; second, the nitrogen-containing bidentate ligand has strong coordination ability, can form strong binding between the WO(O2)2 unit and the chelating ligand. In addition, by comparing with different types of inorganic supports it was found that the presence of large the pores on the support are favoring the increase of catalytic activity, and the existence of appropriate Lewis acid in supports can also increase the catalytic activity.
3. Carbon-supported oxodiperoxo tungsten Pyrazolylpyridine Complexes: preparation and catalytic properties
Carbon materials SC and NC-2 supported oxodiperoxo tungsten complex of the type [WO(O2)21] (1=[3-(2-pyridyl) pyrazol-1-yl] aceticacid amide) was synthesized by a post-grafting route (WO5(1)-SC and WO5(1)-NC-2). The catalytic property of the two catalysts in the epoxidation of allylic alcohols with H2O2 as the oxidant was investigated. The catalytic performance of the catalysts are solvent-dependent. When using common organic solvents (such as acetonitrile) as reaction medium, the two catalysts showed very low reactivity, when water was used as the reaction medium, the activity of the catalysts can be significantly improved. Combined with some characterization results, the oxygen groups presence on the surface of the carbon supports making the catalysts show high catalytic activity in the water system. In contrast. WO5(1)-NC-2 catalytic activity is higher than WO5(1)-SC. on the one hand, it may be due to the differences of surface properties (polar) of the two carbon supports; On the other hand. NC-2 has higher surface (>800m2/g) and active species can be uniform, highly dispersed on the support surface. These catalysts can efficiently catalyze allylic alcohols with high yields under mild solvent-free conditions without any additives. Of significant practical importance. WO5(1)-NC-2 shows excellent activity (TOF up to 10125 h-1 per W site). Furthermore. WO5(1)-SC and WO5(1)-NC-2 can be easily separated by simple filtration and reused for at least six times with no apparent loss of activity.
4. Chiral MnⅢ(salen) complex Modified mesoporous aluminum phosphate: preparation and catalytic properties of asymmetric epoxidation of alkenes.
Through the method of grafting, the aminopropyl axial chiral MnⅢ(salen) complexes was immobilized on the mesoporous aluminum phosphate, hetergeneous chiral MnⅢ(salen) catalyst with different pore structure (Salen-Mn-AP-AlP0.9O, Salen-Mn-AP-AlP1.0O and Salen-Mn-AP-AlP1.1O) can be obtained through the modulation of P/Al ratio. Catalytic tests showed that the hybrid materials could act as efficient heterogeneous catalysts for the asymmetric epoxidation olefins (such as: styrene andα-methyl styrene. trans-1.2-styrene) with NaClO/PPNO (or m-CPBA/NMO). Moreover, the catalyst with large pore size favoring the improved selectivity of the chiral catalyst (ee%). Salen-Mn-AP-AlP1.1O catalyst can give similar ee value with the homogeneous catalysts for asymmetric epoxidation of styrene (orα-methyl styrene).
研究发现一些仿生类金属配合物,如手性金属卟啉、手性席夫碱金属配合物、金属肽睛、邻菲罗啉金属配合物、联吡啶金属配合物等,在烯烃环氧化反应和烯烃不对称环氧化中表现出高的活性及立体选择性,且同时具有烯烃底物适用范围广、反应条件温和等优点。然而,这类金属配合物作为均相催化剂使用时通常存在回收困难、成本高,且在反应过程中易形成惰性的二聚(低聚)体等问题,从而限制了其发展和实际应用。相比之下,多相催化剂可以克服上述缺点,易于回收和循环使用。近年来,人们围绕均相配合物催化剂的多相化研究开展了大量研究工作,即把金属配合物(或有机金属化合物)和固体载体(如含硅的无机介孔材料)相结合构筑出即具有高的催化活性又易于回收和循环使用的有机-无机杂化材料催化剂。针对烯烃环氧化反应,目前已经有多种性能较为优异的有机-无机杂化材料催化剂体系被相继报道出来,显示出良好的发展前景。在这一领域,研究和开发出性能更加优异、环境友好的新型有机-无机杂化材料多相环氧化催化体系仍是备受关注的课题。
基于上述情况,本论文开展了不同类型金属配合物功能化的有机-无机杂化材料的合成、表征及催化环氧化反应性能研究工作。通过选择适当的金属阳离子和有机配体,结合一些无机载体的使用,合成出多种新型高效多相环氧化催化剂体系。在反应评价过程中系统地考察了烯烃种类,氧化剂类型,反应介质等因素对催化剂性能的影响,同时结合各种表征对催化剂结构、表面性质进行了研究,探讨了催化剂活性中心性质和催化作用机制等问题。主要研究内容和结果概述如下：
1.MnⅡ吡啶联吡唑配合物功能化的SBA-15杂化材料的制备及催化性能
通过共价键嫁接的方法将[MnⅡ(l)2](OAc)2 (l=3-(2-吡啶基)-1-吡哗))固载到介孔SBA-15表面上制成杂化材料。催化反应结果表明：这类杂化材料在以间氯过氧苯甲酸(m-CPBA)为氧化剂时,对多种烯烃(包括一些难氧化的端基类烯烃,如1-辛烯)表现出非常高的低温催化活性、选择性及稳定性。氧化剂类型和溶剂类型的选择也会显著影响催化剂的性能。当分别以叔丁基过氧化氢和间氯过氧苯甲酸为氧化剂时,由于m-CPBA的氯苯基的吸电子能力要比t-BuOOH的叔丁基强,使两种氧化剂在催化剂上的活化方式和途径产生差异。当t-BuOOH作为氧化剂时,所形成t-BuOO-MnⅡ加合物中O-O键容易均裂产生HO-MnⅢ中间体和自由基(RO·),使得反应产生大量副产物(如醛)；而当m-CPBA作为氧化剂时,形成的加合物中的O-O键容易发生异裂而产生高价O=MnⅣ中间体,从而有利于环氧化物的生成。此外,相对于质子型溶剂(如乙醇),在非质子型溶剂(如乙腈)中,催化剂通常会表现出更高的活性和选择性。原位UV-vis光谱等表征结果证实在乙腈为溶剂时,MnⅡ-更易于与氧化剂(m-CPBA)作用生成高价的O=MnⅣ中间体,这应该是催化剂表现出高活性和高的环氧化物选择性的主要原因。
2.过氧化钨配合物功能化的介孔材料的制备及催化性能
通过后嫁接法合成了过氧化钨配合物WO(O2)2L(L=3-(2-吡啶基)-1-吡唑(1);3-(2-氨乙基)-氨丙基(2)、咪唑(3)或4.4’-联吡啶(4))功能化的介孔SBA-15材料(记为WO5(n)-SBA-15)。这几种有机-无机杂化材料催化剂在以双氧水为氧化剂时,均对环辛烯环氧化反应中表现出较高的活性及选择性。然而,由配体2-4合成的催化剂的稳定性较差,在循环使用过程中催化活性明显下降,推测主要原因是由于活性钨物种的配位环境发生一定变化而导致的。而WO5(l)-SBA-15催化剂在六次循环反应中活性基本保持不变,且中断实验结果也证实该反应确实是多相催化反应,显示出很高的稳定性：另外该催化剂还具有很高的双氧水利用率(99.5%以上),性能明显优于其它类型金属配合物催化剂。WO5(l)-SBA-15表现出高稳定性可主要归结于两方面因素：一是由于配体和SBA-15的表面有很强的共价键连接,二是由于含氮双齿配体具有很强的配位能力,可以和过氧化钨物种形成稳定的配合物。此外,通过对比不同类型的无机载体还发现载体上存在大的孔道有利于反应活性的提高,并且载体中存在适量的路易斯酸中心也会提高催化剂的反应活性。
3.过氧化钨吡啶基吡唑配合物功能化的炭材料的制备及催化性能
通过共价键嫁接的方法将WO5(1)配合物固载到炭化蔗糖(SC)和介孔炭材料(NC-2)得多相环氧化催化剂(记为WO5(l)-SC和WO5(l)-NC-2),并考察了其对以双氧水为氧化剂的烯丙基醇环氧化反应的催化性能。结果表明：WO5(l)-SC和WO5(l)-NC-2催化剂的性能受溶剂影响很大。当一些常用的有机溶剂(如乙腈)为反应介质时,两种催化剂的均表现出非常低的反应活性;而当水为反应介质时,两种催化剂的反应活性均显著提高。结合一些表征结果,可以认为炭载体表面存在的大量含氧官能团使催化剂表面具有一定的极性(亲水性)从而使其在水体系中为表现出较高的催化活性。相比之下,WO5(l)-NC-2的催化活性要高于WO5(l)-SC,一方面可能是由于两种载体的表面性质(极性)有一定的差异所致,另一方面也可能是由于NC-2具有更高的比表面积,使活性中心能够更加均匀的高分散在载体表面上。值得一提的是,在不添加其它任何溶剂的条件下,WO5(l)-NC-2对一些烯丙基醇环氧化表现出非常高的催化活性(TOF,10125h-1per W site)和环氧化物选择性,且催化剂在反应过程中没有发生活性物种流失、可多次循环使用,显示出良好的稳定性。
4. MnⅢ(salen)配合物功能化的介孔磷酸铝材料的制备及其在烯烃不对称环氧化反应中的应用
通过氨丙基轴向嫁接的方法将手性MnⅢ(salen)配合物固载到介孔磷酸铝材料上,通过调变磷/铝比可以得到不同孔道结构的多相手性MnⅢ(salen)催化剂(分别记为Salen-Mn-AP-AlP0.9O,Salen-Mn-AP-AlP1.0O和Salen-Mn-AP-AlP1.1O)。并分别考察了其在次氯酸钠/4-苯基氧化吡啶(NaClO/PPNO)和间氯过氧苯甲酸/N-甲基吗啉氮氧化物(m-CPBA/NMO)体系下对烯烃(如：苯乙烯和α-甲基苯乙烯,反式-1,2-二苯乙烯)不对称环氧化的催化性能。实验结果表明通过调变磷/铝比增大载体的纳米孔径可以提高催化剂的手性选择性(ee%),在苯乙烯和α-甲基苯乙烯的不对称环氧化反应中可以得到与均相催化剂相近的ee%。
Synthesis and Catalytic Properties in Alkene Epoxidation
Epoxides are a class of highly versatile intermediates in organic synthesis, which can be converted to other valuable compounds by selective ring opening or functional groups transformation, it is very important in medicine, pesticides, fragrances and other fine chemicals synthesis. The current industry methods for the synthesis of epoxides are Ag/Al2O3/O2 (Ethylene oxide). Halcon (Propylene oxide) and halogenohydrin (Propylene oxide). However, Ag/Al2O3/O2 (EO) systems showed lower efficiency for other alkenes. For the halogenohydrin process, the production of large amounts of chlorine-containing waste water leads to severely environmental pollution. In Halcon process, many side-products are produced, which suffers from the costly material consumption and equipment cauterization. Therefore, the development of high efficiency and low pollution epoxidation process is very meaningful work.
Some biomimetic catalysts (such as chiral metalloporphyrin, chiral Schiff base metal complexes, metal peptide eye, phenanthroline metal complexes, bipyridyl metal complexes and other multi-nitrogen, nitrogen-oxygen organic metal complexes and so on) were found as efficient homogeneous catalysts for the epoxidation of alkenes. However, it is difficult to recover and reuse those homogeneous metal complexes, and the catalytic activity of these homogeneous catalysts decreases due to the formation of inactive dimericμ-oxo species, which has restricted their wide applications in industrial and laboratory synthesis. One way to overcome this problem is to immobilize them on solid supports to synhesis organic-inorganic hybrid materials. In comparison with the homogeneous counterparts, heterogeneous systems show many advantages such as easy separation and recovery of the catalyst from reaction media, higher stability of catalytic species and catalyst protection against destruction. For olefin epoxidation. many good performance of the organic-inorganic hybrid materials have been reported. In this area, it is still an interesting and significant subject to develop more excellent performance and environmentally friendly organic-inorganic hybrid heterogeneous epoxidation catalyst systems.
Based on the above, in this thesis, we try to prepare and characterization novel transition metal complexes functionalized organic-inorganic hybrid materials, and study their catalytic properties in alkene epoxidation. By selecting appropriate metal ions and organic ligands, combined with the use of certain inorganic supports, we synthesis a variety of new highly efficient hetergeneous epoxidation catalysts. In the epoxidation reaction text, the influence of different reaction parameters-such as the alkenes. oxidants and solvents-on the catalytic performance of the hybrid materials has been studied and discussed, and combined with a variety of characterization of the catalyst structure and surface properties to study the nature of catalyst active center and catalytic mechanism. The main contents and results are summarized as follows:
1. Mesoporous SBA-15 Modified with Manganese Pyrazolylpyridine Complexes: preparation and catalytic properties
A manganese-based hybrid mesoporous material was synthesized by covalent grafting of [MnⅡ(1)2](OAc)2 (1=[3-(2-pyridyl) pyrazol-1-yl]aceticacid amide) onto the surface of SBA-15. Catalytic tests showed that the hybrid material could act as an efficient heterogeneous catalyst for the epoxidation of a wide range of alkenes (including terminal ones) under mild reaction conditions when peracids (e.g.. meta-chloroperbenzoic acid) are used as oxidants. Moreover, the catalytic performance of the hybrid materal is oxidant-dependent, these contrasting mechanistic behaviors can be rationalized on the basis of the physical parameters of the substitutes on O-O bond in these two oxidants (t-BuOOH and m-CPBA). The chlorophenyl group of m-CPBA has a stronger ability to withdraw electron density from the peroxo unit alkyl group in t-BuOOH. This feature may result in an easy homolytic cleavage of the O-O bond (radical pathway) after the formation of a t-BuOO-MnⅡfragment, while a heterolytic cleavage of the O-O bond is dominant in the m-CPBA case. It exhibits higher catalytic activity and selectivity towards epoxides in the presence of an aprotic solvent (e.g.. CH3CN). UV-vis measurements revealed that high-valent O=MnⅣ-species are easily formed during the reaction course, when meta-chloroperbenzoic acid is used as oxidant and CH3CN is used as solvent, being probably the reason for the high activity of the hybrid material and its selectivity towards epoxide formation.
2. Mesoporous materials modified with oxodiperoxo tungsten complexes: preparation and catalytic properties
A hybrid mesoporous SBA-15 material containing an oxodiperoxo tungsten complex of the type [WO(O2)21] (1=[3-(2-pyridyl) pyrazol-1-yl] aceticacid amide) was synthesized by a post-grafting route (WO5(I)-SBA-15). The catalytic property of the heterogeneous oxodiperoxo tungsten complex catalyst in the epoxidation of cyclooctene with H2O2 as the oxidant was investigated in comparison with other three kinds of hybrid tungsten containing SBA-15 materials bearing ethylenediamine (2), imidazole (3) or 4,4'-bipyridine (4) ligands. It was found that all oxodiperoxo tungsten catalysts were active at the reaction temperature of 55℃with CH3CN as solvent. However, only the catalyst with the pyrazolylpyridine ligand showed good recoverability and relatively high stability against leaching of active tungsten species. Moreover, this catalyst showed very high efficiency for H2O2 utilization (>99.5%). The high stability of WO5(1)-SBA-15 can be attributed to two factors:First, there is strong covalent grafting between the organic ligand system and the inorganic mesoporous material; second, the nitrogen-containing bidentate ligand has strong coordination ability, can form strong binding between the WO(O2)2 unit and the chelating ligand. In addition, by comparing with different types of inorganic supports it was found that the presence of large the pores on the support are favoring the increase of catalytic activity, and the existence of appropriate Lewis acid in supports can also increase the catalytic activity.
3. Carbon-supported oxodiperoxo tungsten Pyrazolylpyridine Complexes: preparation and catalytic properties
Carbon materials SC and NC-2 supported oxodiperoxo tungsten complex of the type [WO(O2)21] (1=[3-(2-pyridyl) pyrazol-1-yl] aceticacid amide) was synthesized by a post-grafting route (WO5(1)-SC and WO5(1)-NC-2). The catalytic property of the two catalysts in the epoxidation of allylic alcohols with H2O2 as the oxidant was investigated. The catalytic performance of the catalysts are solvent-dependent. When using common organic solvents (such as acetonitrile) as reaction medium, the two catalysts showed very low reactivity, when water was used as the reaction medium, the activity of the catalysts can be significantly improved. Combined with some characterization results, the oxygen groups presence on the surface of the carbon supports making the catalysts show high catalytic activity in the water system. In contrast. WO5(1)-NC-2 catalytic activity is higher than WO5(1)-SC. on the one hand, it may be due to the differences of surface properties (polar) of the two carbon supports; On the other hand. NC-2 has higher surface (>800m2/g) and active species can be uniform, highly dispersed on the support surface. These catalysts can efficiently catalyze allylic alcohols with high yields under mild solvent-free conditions without any additives. Of significant practical importance. WO5(1)-NC-2 shows excellent activity (TOF up to 10125 h-1 per W site). Furthermore. WO5(1)-SC and WO5(1)-NC-2 can be easily separated by simple filtration and reused for at least six times with no apparent loss of activity.
4. Chiral MnⅢ(salen) complex Modified mesoporous aluminum phosphate: preparation and catalytic properties of asymmetric epoxidation of alkenes.
Through the method of grafting, the aminopropyl axial chiral MnⅢ(salen) complexes was immobilized on the mesoporous aluminum phosphate, hetergeneous chiral MnⅢ(salen) catalyst with different pore structure (Salen-Mn-AP-AlP0.9O, Salen-Mn-AP-AlP1.0O and Salen-Mn-AP-AlP1.1O) can be obtained through the modulation of P/Al ratio. Catalytic tests showed that the hybrid materials could act as efficient heterogeneous catalysts for the asymmetric epoxidation olefins (such as: styrene andα-methyl styrene. trans-1.2-styrene) with NaClO/PPNO (or m-CPBA/NMO). Moreover, the catalyst with large pore size favoring the improved selectivity of the chiral catalyst (ee%). Salen-Mn-AP-AlP1.1O catalyst can give similar ee value with the homogeneous catalysts for asymmetric epoxidation of styrene (orα-methyl styrene).
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