MIL-101负载金属纳米催化剂的制备及其绿色催化研究

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英文题名：Synthesis of Metal Nanocatalysts Supported on MIL-101and Their Applications in Green Synthesis 作者：刘宏利 论文级别：博士 学科专业名称：应用化学 中文关键词：多相催化 ; 金属有机骨架材料 ; 氧化反应 ; 氢化反应 ; C-H键活化 英文关键词：heterogeneous catalysis ; metal-organic frameworks ; oxidation ; hydrogenation ; C-H activation 学位年度：2013 导师：李映伟 学科代码：081704 学位授予单位：华南理工大学 论文提交日期：2013-04-01

摘要

金属有机骨架(MOFs)是通过有机配体与金属离子自组装而成的一类新型有机-无机杂化多孔材料。与其它多孔材料相比，MOFs具有大的比表面积、高的孔隙率以及结构和性质可调等特性，这些优良性质使其在非均相催化领域具有良好的应用前景。但是，具有高效高活性的MOFs催化剂的设计制备仍然是该领域的一个难题。本论文基于MOFs材料的结构特点和性质，探索了在这类材料上修饰催化活性位的方法，旨在设计合成出应用于一些绿色催化合成反应的新型高效MOFs基催化剂，并研究揭示MOFs基催化剂的结构性质与催化性能之间的构效关系。论文的主要研究内容和研究结果如下：
     (1)以PVP为保护剂，HAuCl_4为原料，通过简单的溶胶凝胶法制备出MIL-101负载Au材料(Au/MIL-101(CD/PVP))。该催化剂在不添加碱的条件下能够高效催化一系列醇的有氧氧化反应。在160°C和无溶剂条件下，Au/MIL-101(CD/PVP)催化1-苯乙醇选择性氧化的TOF高达29300h-1，在相同的反应条件下其TOF值高于文献报道的最活泼的Au催化剂。这也是首次在溶液条件下制备出具有催化活性的MOFs负载Au催化剂。而且，Au/MIL-101(CD/PVP)具有良好的稳定性，重复使用多次后催化活性几乎没有发生改变，Au也没有发生团聚或流失现象。而另外采用葡萄糖作保护剂的溶胶凝胶法、沉淀沉积法和浸渍法三种液相方法负载的Au粒子高度聚集，在不添加碱的条件下对醇的有氧氧化反应不具有催化活性。机理研究表明，Au/MIL-101(CD/PVP)具有高催化活性的原因主要归因于高分散的Au纳米粒子以及MIL-101上芳环对装填在MIL-101孔道内的粒径小的Au纳米粒子的供电效应。
     (2) MIL-101具有很强的Lewis酸性，通过简单的浸渍法负载Pd，制备出既具有Lewis酸性又具有加氢活性的双功能Pd/MIL-101催化剂。研究发现，Pd/MIL-101在常温、常压条件下即可高效地催化苯酚加氢生成环己酮，苯酚的转化率达>99.9%，同时环己酮选择性也>99.9%。而且催化剂具有良好的稳定性，重复使用5次后催化活性没有改变。催机理研究表明，Pd纳米粒子可以活化H2；Lewis酸位可以活化苯环促进苯酚加氢反应，并通过与环己酮发生Lewis酸碱相互作用可有效抑制环己酮进一步加氢而获得高的环己酮选择性。Lewis酸和Pd的协同作用是催化剂具有优良反应活性和选择性的原因。
     (3)基于氧化催化剂的设计以及Lewis酸对芳香化合物的活化作用的发现，采用溶胶凝胶法制备出双金属负载的Au-Pd/MIL-101催化剂，并将其应用于芳香烃的SP~3C-H键选择性氧化制备芳香酯的反应。反应结果表明，Au-Pd/MIL-101能够有效地活化芳香烃，展现出良好的底物兼容性，在相同条件下所获得的TON值是文献报道催化剂的3-10倍，而且反应产物中没有检测到苯甲醇和苯甲酸，显示出优异的芳香酯选择性。机理研究表明，Au-Pd的双金属协同效应使其比单金属Au、Pd能够更加有效地活化O_2形成过氧物种；而Lewis酸位与芳香烃的相互作用使芳香烃上的甲基更易被过氧物种进攻生成苯甲醇；同时Lewis酸位与反应中间体苯甲醛的C=O基发生酸碱作用，不仅抑制了苯甲醛进一步氧化生成苯甲酸，而且也使苯甲醛的羰基C原子更容易发生亲核进攻形成半缩醛，随后半缩醛被进一步氧化成苯甲酸苄酯。
     (4) Au-Pd/MIL-101催化剂可以催化芳香烃与脂肪醇的直接氧化酯化合成芳香羧酸酯。反应结果显示，在120°C，底物/金属=2000，O_2为氧化剂的条件下，Au-Pd/MIL-101可催化各种烷基芳香烃与一系列脂肪醇的直接氧化酯化生成对应的芳香羧酸酯，烷基芳香烃转化率高达99%，目标产物选择性高达98.0%。机理研究表明，该催化反应历程没有自由基参与，主要经历SP~3C-H活化生成苯甲醇；苯甲醇进一步被氧化成苯甲醛；苯甲醛和甲醇形成半缩醛以及半缩醛被氧化得到芳香羧酸酯等四个反应步骤。
     (5)以MOF-253为催化剂，研究了其催化非活化芳烃的直接芳基化反应性能。结果发现，当配体2,2-联吡啶-5,5-二羧酸构建成MOF-253后，4-甲氧基联苯的收率从<1%提高到了50%。与文献报道的其它催化剂相比，用MOF-253作催化剂，产物的选择性得到了显著提高，尤其是位置选择性提高更为明显，位置选择性可达91%。机理研究表明，配体构建成MOF后，改变了配体中联吡啶的电子分布，从而提高了其催化活性；MOF结构中的联吡啶与反应中间体（芳基自由基）之间的π，π-堆积作用，以及MOF-253的空间位阻效应，有利于化学选择性的提高；MOF-253的孔径大小和反应分子的尺寸决定了反应分子进入孔道的方向以及方式，从而提高了目标产物的位置选择性。
Metal-organic frameworks (MOFs) are a new class of porous organic-inorganic hybridmaterials formed by the self-assembly of organic bridging ligands and metal ions. Theypossess large specific surface area and porosity as well as tunable structure and propertiescompared to other porous materials. Due to these outstanding properties, MOFs could behighly desirable and promising materials for applications in heterogeneous catalysis. However,the design and preparation of highly-efficient MOF-based catalysts remains a challengingresearch target. Based on the structural features and chemical properties of MOFs, a numberof efficient preparation methods have been developed in this thesis for tuning the catalyticactive sites of MOFs to synthesize new and highly active MOF-based catalysts. Theircatalytic performances in green synthesis reactions were investigated in detail and thestructure-performance relationships were explored. The main research contents andexperimental results are as follow:
     1) Au/MIL-101(CD/PVP) was prepared by a simple colloidal method withpolyvinylpyrrolidone (PVP) as protecting agent using HAuCl_4as the Au precursor. Thesupported gold catalyst has been shown to be highly efficient for liquid-phase aerobic alcoholoxidation in the absence of base. Au/MIL-101(CD/PVP) afforded a very high TOF of25000h-1for the conversion of1-phenylethanol under the solvent-free conditions at160°C, whichwas even higher than the values obtained on the most active Au catalysts reported in thecurrent literature under the same reaction conditions. This work also represents the firstexample of an active MOF supported Au catalyst prepared by a liquid-phase synthesis method.Moreover, the catalyst was highly stabilized against metal agglomeration and leaching,maintaining the high activities during a number of recycles. In contrast, the Au/MIL-101catalysts prepared by CD/glucose (colloidal deposition with glucose as protecting agent),DPSH (deposition-precipitation with sodium hydroxide), and IMP (impregnation) caused theagglomeration of Au nanoparticles, which were inactive for liquid-phase aerobic alcoholoxidation under base-free condition. Mechanistic studies indicate that the high catalyticperformance may be attributed to the high dispersion of Au NPs as well as the electron donation effects of aryl rings of MIL-101to the Au NPs in the large cages of the MIL-101support.
     2) The deposition of Pd nanoparticles on MIL-101with a strong Lewis acidity couldrender a bifunctional catalyst that combines Lewis acidity and hydrogenation activity. Theresults showed that Pd/MIL-101was able to effectively catalyze the selective hydrogenationof phenol to cyclohexanone in water even at atmospheric pressure and room temperaturewith>99.9%selectivity to cyclohexanone at phenol conversions>99.9%. Moreover, thecatalyst was found to be highly reusable, giving identical activities and selectivities after>5uses. Mechanistic studies indicated that Lewis acids activated aromatic rings of phenol whilePd activated H2, thereby facilitating the hydrogenation of phenol. Furthermore, acid-baseinteraction between the Lewis acid and cyclohexanone inhibited further hydrogenation tocyclohexanol. The exceptional catalytic activity and selectivity in phenols hydrogenationcould be attributed to the synergistic effect between the Lewis acidic sites and Pd on thecatalyst.
     3) Based on our previous findings on the effect of Lewis acidity on the activation ofaromatic rings, we designed and prepared a multifunctional Au-Pd/MIL-101catalyst by usinga colloidal method for the selective oxidation of SP~3C-H bonds to aromatic ester. The resultsshowed that Au-Pd/MIL-101was particularly active for aromatic hydrocarbons oxidation witha broad substrate tolorance. The TONs achieved on this catalyst were3-100times greater thanthose of previously reported catalysts under milder or at least comparable conditions. Inaddition, neither benzyl alcohol nor benzoic acid was detected in Au-Pd/MIL-101catalyzedtoluene. Mechanistic studies indicated that the synergistic effect for the Au-Pd made it morefavorable for the activation of O_2to form superoxo-like species than the correspondingmonometallic Au or Pd. At the same time, an interaction between the aromatic ring of toluenewith the Lewis acidic sites rendered toluene to be more easily attacked by the activatedoxygen species to form benzyl alcohol. On the other hand, the acid-base interaction betweenthe Lewis acid and benzaldehyde effectively suppressed the formation of benzoic acid, andalso facilitated a nucleophilic attack of the carbon atom of the carbonyl group by benzylalcohol to form the corresponding hemiacetal. Finally, the hemiacetal was further oxidized tobenzyl benzoate.
     4) Au-Pd/MIL-101could effectively catalyze the direct oxidative synthesis of aromaticmethyl esters from methyl aromatics with alcohols. The results showed that Au-Pd/MIL-101was able to accomplish the oxidative esterification of various methyl aromatics with alcoholto the corresponding ester products, up to99%conversions and98%selectivity to esters.Mechanistic studies indicated that free radical wasn’t involved in this transformation.Moreover, possible pathway for this oxidative esterification reaction involved four steps.Firstly, toluene was oxidised to benzyl alcohol via SP~3C-H bond activation over thebimetallic Au-Pd nanoparticles. The formed benzyl alcohol then undergoes a β-hydrideelimination to generate benzaldehyde. The intermediate aldehyde reacted with methanol toform the corresponding hemiacetal species which upon further oxidation provided thearomatic methyl esters.
     5) The catalytic performance of MOF-253in the direct arylation of unactivated areneswas studied. The results showed that the efficiency of bpydc ligands was dramaticallyincreased by assembling them within a MOF-253structure, and the yield of4-methoxybiphenyl increased from1%to50%. MOF-253afforded higher chemo-and regioselectivitiescompared to the other catalysts reported in related literature. Mechanistic studies indicatedthat the electron configuration of the2,2’-bipyridine moieties was changed after the ligandwas assembled into the MOF, and hence catalytic activity was improved. The improvement ofchemo-selectivity could be attributed to the steric hindrance of the micropores as well as theπ,π-stacking interactions between the2,2’-bipyridine moieties of MOF-253and the aromaticring of anisole. The pore size of the MOF-253and the dimensions of reactant moleculescaused reactant molecules to enter the pores along a certain direction, and hence theregioselectivities could be enhanced.

引文

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