高效多羟胺有机催化剂选择性催化分子氧氧化研究进展（英文）

发布时间：2018-03-05 09:19

本文选题：分子氧　切入点：N-羟基邻苯二甲酰亚胺　出处：《催化学报》2017年04期 　论文类型：期刊论文

【摘要】：基于氧气(空气)为氧源的选择性催化分子氧氧化技术在制备含氧精细化学品或食品添加剂与医药等的重要中间体方面一直受到科学界的广泛关注.由于碳氢化合物中碳氢键的反应惰性和分子氧的自旋禁阻作用,设计与开发高效催化剂或催化体系以实现碳氢化合物的选择性氧化是当前催化氧化领域的研究热点.在已发展的过渡金属盐、仿生催化剂、有机催化剂、酶、碳材料和卤化物等众多催化剂中,以羟基邻苯二甲酰亚胺(NHPI)为代表的羟胺有机催化剂由于在温和条件下的卓越催化性能而备受瞩目.尽管基于羟胺有机催化剂的催化体系具有良好的工业应用前景,但仍存在催化剂高温易分解、使用量较大和可回收性较差等缺点.近年来,许多实验与理论工作围绕改进这些缺点展开,设计了一系列羟胺有机催化剂及其协同催化体系,如在NHPI结构中修饰疏水链基团、吸电子基团、N-烷氧基团和离子液体,或固载金属-有机框架材料、无机物和聚合物,或组合光催化剂.尽管已有大量综述总结了相关研究进展,但尚未见到有关近年来发展的多羟胺有机催化剂及其高效催化氧化性能的综述报道.本文综述了近15年来多羟胺有机催化剂选择性催化分子氧氧化碳氢化合物的研究进展.首先,简要概述了二羟基邻苯二甲酰亚胺(NDHPI)和三羟基异氰基尿酸(THICA)两种多羟胺有机催化剂的合成方法,系统介绍了它们在各类碳氢化合物氧化中的高效催化性能,并与普遍应用的NHPI的催化性能进行对比.由于NDHPI与THICA具有多羟胺的独特结构,它们只需要比NHPI更少的用量便可获得比NHPI更高的催化氧化效率,可以直接利用高压空气实现对碳氢化合物的选择性催化氧化,并且在较高温度下依然具有较好的催化效果.在此基础上,介绍了联系实验与理论之间的重要工作,总结了多羟胺有机催化剂的合理设计策略.理论计算研究揭示了NDHPI与THICA的催化性能优于NHPI的主要原因是具有类似于吸电子效应的多羟胺与多氮氧自由基结构能显著增强催化剂的夺氢活性.通过对NDHPI结构的进一步修饰和夺氢活性研究,提出了该类催化剂的合理设计策略:在芳环体系中增加共轭的羟胺基团数量,或在NDHPI苯环中掺杂N原子或引入离子对基团都能提高催化剂的夺氢活性;增大芳环共轭体系对催化剂的夺氢活性影响较小,但该活性仍高于NHPI.这也为基于碳材料的非均相共轭多羟胺有机催化剂的开发提供了理论依据.最后,结合羟胺有机催化剂的发展现状和上述设计策略,设计了基于金属卟啉/席夫碱等仿生催化剂、(含离子对结构)聚合物、非均相碳材料和多N-烷氧基团等几种具有潜在发展前景的模型多羟胺有机催化剂,分别讨论了这些催化剂的优点和局限性,并展望了多羟胺有机催化剂的可能应用及其在催化氧化过程中仍需系统研究的方向.
[Abstract]:Selective catalytic molecular oxygen oxidation based on oxygen (air) has been widely concerned in the preparation of fine chemicals containing oxygen or important intermediates such as food additives and pharmaceuticals. The reaction inertness of carbon-hydrogen bond and the spin interdiction of molecular oxygen in the complex, The design and development of efficient catalysts or catalytic systems for the selective oxidation of hydrocarbons is a hot topic in the field of catalytic oxidation. Among many catalysts, such as carbon materials and halides, Hydroxylamine organic catalysts, represented by hydroxy phthalimide (NHPI), have attracted much attention due to their excellent catalytic performance under mild conditions. However, there are still some disadvantages such as high temperature decomposition of catalyst, large amount of catalyst used and poor recoverability. In recent years, many experiments and theoretical work have been carried out around improving these shortcomings, and a series of hydroxylamine organic catalysts and their synergistic catalytic systems have been designed. For example, modification of hydrophobic chain groups, electron absorbing groups, N-alkoxy groups and ionic liquids in NHPI structures, or immobilization of metal-organic framework materials, inorganic compounds and polymers, or combination photocatalysts. However, there have not been any reports on the recent development of polyhydroxylamine organic catalysts and their high performance in catalytic oxidation. In this paper, the selective catalytic activity of polyhydroxylamine organic catalysts for molecular oxygen oxidation of hydrocarbons in recent 15 years has been reviewed. Research progress. First of all, The synthesis methods of two kinds of polyhydroxylamine organic catalysts, dihydroxyphthalimide (NDHPI) and trihydroxyisocyanuric acid (THICA), were briefly reviewed, and their high performance in the oxidation of various hydrocarbons were systematically introduced. Because NDHPI and THICA have the unique structure of polyhydroxylamine, they only need less amount than NHPI to obtain higher catalytic oxidation efficiency than NHPI. The selective catalytic oxidation of hydrocarbons can be realized directly by using high pressure air, and it still has good catalytic effect at higher temperature. On the basis of this, the important work between experiment and theory is introduced. The reasonable design strategy of polyhydroxylamine organic catalyst was summarized. The theoretical calculation results showed that the main reason for the performance of NDHPI and THICA to be superior to that of NHPI was that the structure of polyhydroxylamine and polyazo free radical, similar to the electron absorption effect, was obvious. To enhance the activity of the catalyst for hydrogen capture. Further modification of the structure of NDHPI and study of its hydrogen capture activity were carried out. The reasonable design strategy of this kind of catalyst was put forward: increasing the number of conjugated hydroxylamine groups in the aromatic ring system or doping N atom or introducing ion pair group in the NDHPI benzene ring could improve the hydrogen capture activity of the catalyst; Increasing the aromatic ring conjugation system has little effect on the activity of the catalyst, but the activity is still higher than that of the NHPI. this also provides a theoretical basis for the development of heterogeneous conjugated polyhydroxylamine organic catalyst based on carbon materials. Based on the development of hydroxylamine organic catalyst and the above design strategy, the polymer based on metalloporphyrin / Schiff base bionic catalyst (containing ion-pair structure) was designed. Several potential models of polyhydroxylamine organic catalysts, such as heterogeneous carbon materials and polyN-alkoxy groups, are discussed. The advantages and limitations of these catalysts are discussed. The possible applications of polyhydroxylamine organic catalysts and the direction of systematic research in the process of catalytic oxidation are also prospected.
【作者单位】：浙江工商大学食品与生物工程学院;浙江新和成股份有限公司;
【基金】：supported by the China Postdoctoral Science Foundation (2014M551746)~~
【分类号】：O643.36

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