金属有机骨架基催化剂在加氢反应中的应用（英文）

发布时间：2018-02-22 09:38

本文关键词： 金属有机骨架加氢多相催化纳米颗粒化学选择性协同效应　出处：《催化学报》2017年07期 　论文类型：期刊论文

【摘要】：加氢是现代化工产业中的一类主干反应,广泛应用于精细化学品、药物、食品、染料、功能聚合物及香料等制造产业中.高效催化剂的引入使得加氢反应能够在相对温和的条件下还原各类不饱和化合物.金属催化剂在加氢反应中活性高,所需的反应温度较低,适用性广,但是容易和S,N,As和P等元素结合而"中毒"失去反应活性.金属氧化物催化剂和金属硫化物催化剂具有一定的抗毒性,但活性相对较差,通常需要采用高温高压的反应条件,对催化剂本身和反应器的要求较为苛刻.传统催化剂在反应中具有一定的局限性,所以亟需开发新一代高效的加氢催化剂,在保证高活性和高选择性催化效果的同时,降低对能源的消耗和对环境的负面影响.金属有机骨架(MOFs)作为一种新型的多孔材料在过去二十年中受到相当大的关注,并在催化、气体存储和分离、传感器、发光材料和药物输送等众多领域的应用中表现出卓越的性能.利用MOF材料良好的相容性,将MOF和其它功能材料结合形成新的复合材料可以在更大程度上扩大MOF材料的应用领域.与传统的催化剂相比,MOF基材料具有优异的物理化学特性和结构可调性,通过合理的设计能够满足不同的催化加氢过程:(1)MOF基催化剂具有多样且特异性的活性位点.除了组成MOF材料的金属离子/簇和功能有机配体之外,MOF材料可通过封装其他活性物质或者被活性物质包裹等方式引入其他类型的催化位点,进一步扩大MOF基催化剂在不同催化加氢中的适应性.此外,不同的活性位点之间的协同作用又能特异性地促进反应的进行,对提高反应的选择性起到重要的作用.(2)活性位点的尺寸大小和空间分布可以被有效控制.这能影响到催化剂在催化反应过程中的活性和选择性,并且通过MOF材料的限域效应,同时能增强活性位点的稳定性和耐久性.(3)高比表面积能提高MOF基催化剂的催化活性.这种结构特性不仅可以增加MOF基催化剂的活性位点,而且能够吸附反应物和还原剂达到扩大其局部浓度的效果.(4)反应分子的扩散可通过调节MOF基催化剂的结构实现控制.通过调整MOF材料的孔窗口和通道的尺寸,能够改变反应物在催化剂内部的扩散途径,影响底物和活性位点的接触,能进一步影响反应的活性和选择性.本文总结了近几年来MOF基材料在不同的催化加氢反应中的应用,其中包括烯烃、炔烃、芳硝基化合物、肉桂醛、糠醛和苯等化合物的加氢反应.首先介绍了MOF基材料中不同类型的活性位点,除了MOF材料自身的金属离子/簇和功能有机配体外,MOF基复合材料中的金属纳米颗粒?金属硫化物?金属氧化物?均相催化剂等活性位点可以通过封装或包裹的方式引入.在不同加氢反应中,着重介绍了MOF基催化剂中不同类型活性位点的加氢过程中的催化方式、催化剂本身的结构优化及催化剂与反应底物之间的相互作用,以及这些因素之间的协同作用对反应活性和选择性的影响.最后,讨论了MOF基材料在加氢反应中应用存在的问题以及未来发展展望.
[Abstract]:Hydrogen is a kind of main reaction of modern chemical industry, widely used in fine chemicals, pharmaceutical, food, dye, functional polymer and spices and other manufacturing industries. The catalysts that hydrogenation can restore all kinds of unsaturated compounds under relatively mild conditions. The metal catalyst activity in the hydrogenation of high, the required reaction temperature is low, wide applicability, but easily and S, N, As and P elements in combination of "poisoning" lose reactivity. Metal oxide catalyst and metal sulfide catalysts with anti toxicity, but the activity is relatively poor, usually by high temperature and high pressure reaction conditions, the catalyst itself and the reactor requirements are more demanding. The traditional catalyst has certain limitations in the reaction, so it is necessary to develop a new generation of highly efficient hydrogenation catalyst, while ensuring high activity and high selectivity catalytic effect Fruit at the same time, reduce the negative impact on energy consumption and the environment. The metal organic framework (MOFs) as a new type of porous materials has received much attention in the past twenty years, and in catalysis, gas storage and separation, sensors, to demonstrate the superior performance of the materials used in many fields and drug delivery etc. light. Using the good biocompatibility of MOF material, the combination of MOF and other functional materials to form new composite materials can expand the application field of MOF material to a greater extent. Compared with the traditional catalyst, MOF based materials have excellent physical and chemical properties and structure adjustability, through reasonable design can meet the catalytic the hydrogenation process of different: (1) MOF catalyst is the active site of diversity and specificity. In addition to metal ion / MOF materials composed of clusters and functional organic ligands, MOF can encapsulate other materials The catalytic sites of active substances or active substances into other types of packages, to further expand the adaptability of MOF based catalysts in different catalytic hydrogenation in. In addition, the synergy between the different active sites and can promote the reaction specificity, an important role to improve the reaction selectivity (2). The active site size and spatial distribution can be controlled effectively. It can affect the activity and selectivity of the catalyst in the catalytic reaction process, and the confinement effect of MOF material, and can enhance the active site stability and durability. (3) high surface area can enhance the catalytic activity of MOF catalysts. This structure can not only increase the active sites of MOF catalysts, and can adsorb the reactants and reducing agent to expand its local concentration effect. (4) by molecular diffusion reaction The structure adjustment of MOF based catalyst for control. Through hole window and channel adjustment of MOF material size, diffusion of reactants in the catalyst can change the way the effects of substrate and active site contact, can further influence the activity and selectivity of the reaction. This paper summarizes the application of MOF based materials in catalytic hydrogenation reaction in different in recent years, including alkenes, alkynes, aromatic nitro compounds, cinnamaldehyde hydrogenation of furfural and benzene compounds. It firstly introduces the different types of active sites of MOF based materials, in addition to the metal ion / MOF material of their clusters and organic coordination function in vitro, metal nanoparticles MOF composites the metal sulfide metal oxide??? Homogeneous catalyst active sites can be introduced through the package or packages in different ways. The hydrogenation reaction, emphatically introduces the different types of MOF based catalytic agent The catalytic hydrogenation process mode of the active site of the interaction between the catalyst structure optimization and catalyst and reaction substrate, and the synergistic effect between these factors on the reaction activity and selectivity. Finally, discusses the application of MOF based materials in the presence of hydrogenation reaction problems and future development prospects.

【作者单位】：华南理工大学化学与化工学院广东省燃料电池技术重点实验室;
【基金】：supported by the National Natural Science Foundation of China(21322606,21436005,21576095) China Postdoctoral Science Foundation(2016M590771) Guangdong Natural Science Foundation(2016A030310413,2013B090500027,2014A030310445,2016A050502004)~~
【分类号】：O643.36

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