负载固相的铑基催化剂应用于烯烃氢甲酰化反应的研究进展

负载固相的催化剂因其简便的分离循环操作以及可观的催化性能而广受关注,但存在反应活性较差、金属流失量较大、催化剂制备成本较高等问题。本文首先从不同负载材料的角度综述了近年来该类催化剂最新的研究进展,主要探讨了载体的表面性质、催化剂的制备方法、膦配体等对催化性能的影响;最后介绍了新型的单原子催化剂所取得的突破性进展。分析表明：具有"类均相"特点的多孔有机聚合物的催化活性很好,而超支化聚合物功能化的磁性纳米催化剂的稳定性更佳。另外还对负载型铑催化剂未来的研究方向进行了展望：需要进一步加深对多孔有机聚合物的化学结构的理解,以便对其更好地表征;借助一些先进的表征技术如高角环状暗场扫描透射电镜和密度泛函理论的计算来深入研究载体结构对单原子催化剂的催化性能的影响。     

多孔有机聚合物催化研究进展

多孔有机聚合物是一类新型多孔材料,由于其较高的比表面积、可控的孔径尺寸、较高的稳定性以及易修饰等优点,该类材料被广泛用于多相催化的应用研究。在介绍多孔有机聚合物设计与合成的基础上,着重阐述了多孔有机聚合物负载金属离子、金属纳米颗粒以及手性分子用于多相催化的研究进展。     

Cp2TiCl2/坡缕石黏土负载型催化剂催化乙烯聚合的特性

利用浸渍法制备了两种二氯二茂钛（Cp₂TiCl₂）/坡缕石黏土负载型催化剂Cat-A 和Cat-B,并进行了乙烯淤浆聚合评价。对热活化黏土进行表征的结果表明,坡缕石黏土在热活化过程中由于配位结晶水的脱除表面主要由Lewis酸性位占据。黏土载体所具有的表面酸性使其具有完全不同于硅胶载体的负载茂金属催化剂聚合行为。在相同的聚合条件下,直接负载型催化剂的活性高于载体化学修饰型催化剂,甚至高于均相Cp₂TiCl₂催化剂。直接负载催化剂所得聚合产物的分子量和熔点低于载体化学修饰催化剂,且其产物性质受温度影响更为显著。以硅胶负载型茂金属催化剂作为对比,分析了表面具有较强Lewis酸性的载体活性中心性质,以此解释了直接负载型催化剂的乙烯聚合特性。对直接负载型催化剂不同时间段的聚合产物形态进行了扫描电镜观察,发现最终聚合产物中聚合物“纤维”和“纤维”聚集体形态的形成,并进一步分析了聚合物形态演化过程的特点。     

三齿配体过渡金属烯烃聚合催化剂研究新进展

介绍了三齿配体结构、中心金属原子、助催化剂、负载化等对催化剂性能的影响;综述了三齿配体过渡金属烯烃聚合催化剂在乙烯齐聚、乙烯聚合、丙烯聚合以及极性单体聚合方面的应用以及三齿配体过渡金属烯烃聚合催化剂的催化机理方面的研究进展。     

有机载体负载茂金属催化剂研究进展

综述了近年来天然高分子、聚合物等有机载体用于负载茂金属催化剂的研究现状,评述了有机载体型茂金属催化剂的特点、负载方式、负载化对催化烯烃聚合性能和聚合物性能的影响。分析表明,进一步提高有机载体型茂金属催化剂的活性、改善有机载体的形态和结构仍是值得探索的课题。     

非均相茂金属催化剂载体的研究进展

文章介绍了茂金属催化剂载体的研究新进展,着重介绍了无机载体和有机载体用于茂金属催化剂负载化的研究现状。分别陈述了无机和有机载体的一些常见载体类型,例如硅胶载体和聚苯乙烯载体;并对比了无机载体和有机载体的颗粒形态,强度,表面基团等物理化学性质的差异。研究表明,载体材料本身结构及其物理化学性质对聚合活性,聚合物形态和堆积密度有着直接的作用。进一步探索载体的结构性能与聚合动力学的关系,将对对进一步提高聚合活性,改善聚合物颗粒形态具有深远的意义。     

负载型烯烃氢甲酰化反应催化剂研究进展

因催化剂与产物不易分离的问题，氢甲酰化反应催化剂固载化研究受到广泛关注。本文从分子筛、二氧化硅、碳材料、金属氧化物、磁性纳米粒子、有机聚合物和离子液体这些不同负载材料的角度综述了过去十年来的相关研究结果，并对不同载体的优缺点和发展前景进行了简要分析。固载型催化剂分为3种不同的构建方式：载体与配体连接、载体与金属连接以及载体同时与配体和金属连接。第3种构建方式制备的催化剂更稳定，常在二氧化硅作为载体中使用。第一种构建方式为催化剂制备提供了多样性，在无机物和有机物作为载体中都有广泛使用，其中，含磷的有机聚合物在提供良好催化剂效果的同时，也提高了催化剂的稳定性，对未来的研究方向有一定的指导意义。     

多孔碳纳米球及其负载金属催化剂的研究进展

多孔碳纳米球由于可实现尺寸、形貌、孔结构以及表面基团等的可控合成制备,其负载/镶嵌的金属粒子又兼具高活性和高热稳定性等,在多相催化领域中受到越来越多的关注。本文追溯了多孔碳纳米球形貌调控的发展历程及其负载金属催化剂在催化反应领域中的应用。归纳了不同形貌的多孔碳纳米球及其制备方法和原理,详细对比了各个方法的优缺点;阐述了多孔碳纳米球负载金属催化剂的性能和碳球结构与形貌之间的构效关系;总结了目前碳球作为催化剂载体亟需解决的问题是碳球的多孔结构及其负载尺寸可控和空间匀称分布的金属粒子的可控合成,并展望了其发展方向是进一步研究和探索结构可调、经济可行的碳纳米球制备方法,真正实现工业化应用。     

烯烃配位聚合非茂前过渡金属催化剂研究进展

介绍了非茂前过渡金属催化剂作为高效烯烃聚合催化剂的发展和应用情况。根据催化剂中配位原子的性质将非茂前过渡金属催化剂分为配住原子为N、配住原子为O、配位原子为N和O的三大类进行讨论。重点评述了配体空间结构和电性能对催化活性及聚合物性能的影响。     

联萘酚纳米孔道配位聚合物催化剂的研究进展

纳米多孔材料可用作催化剂、气体储存材料和光电子器件,是目前新型多孔材料的研究热点之一。手性联萘酚配体所修饰的催化剂是一种很优异的C2轴对称手性诱导源,可以催化各种α,β-不饱和羰基化合物,具有良好的催化活性和对映选择性。本文对由手性联萘酚类配体所修饰的小分子催化剂、聚合物负载的催化剂和自负载催化剂,在不饱和羰基化合物催化不对称环氧化反应中的应用进行了综述。本文介绍了对手性联萘酚纳米多孔配位聚合物的研究。     

Asymmetric Catalysis with Chiral Porous Metal–Organic Frameworks

This paper provides a brief overview of recent progress in the design and synthesis of chiral metal–organic frameworks (CMOFs) and their applications in heterogeneous asymmetric catalysis. Catalytically active CMOFs can be synthesized using two distinct strategies, either by post-synthetic activation of pre-synthesized porous MOFs or by directly linking well-designed catalytically competent bridging ligands with metal ion or metal cluster nodes. Heterogeneous asymmetric catalysis with very high activity and enantioselectivity has been achieved with CMOFs. The intrinsic tunability of CMOFs promises to lead to the design and synthesis of a variety of practically useful heterogeneous asymmetric catalysts for many organic transformations.     

Synthese phosphorhaltiger Monomere,Oligomere und Polymere aus Methylolderivaten des Phosphors

Phosphorus-containing polymers are known to have valuable properties, primarily the ability of self-extinction. Most favorable results were obtained with substances including phosphorus and chlocrine in their molecules. However, up to now attention was given predominantly to polymers having C O P bonds. The present paper describes the synthesis of phosphorus and phosphorus and chlorine containing polymers with C P bonds using methylol derivatives of phosphorus. Bis-(p-carbomethoxyphenoxymethyl) methylphosphinoxide was used as a phosphine oxide derivative. This phosphorus-containing dicarboxylic acid was reacted with glycols to give phosphorus-containing polyesters and copolyesters. With glycols in excess the reaction led to phosphorus-containing and mixed oligomers which after reaction with diisocyanates yielded polyurethanes, copolyurethanes and urethane block copolymers. Esterification of bis(hydroxymethyl)phosphonic acid with acrylic and methacrylic acid yielded monomers which, when subjected to polymerisation, gave phosphorus-containing polyesteracrylates and methacrylates and, in addition, could be copolymerised with acrylic and methacrylic acid. Mono- and dicondensation products of hypophosphorous acid with chloral, being considered as chlorine-containing methylol derivatives of phosphinic and phosphonic acids, led to polyurethanes.     

Gold-Nanoparticle-Decorated Metal-Organic Frameworks for Anticancer Therapy

Confinement of Au nanoparticles (NPs) within the porous materials with few nanometers (2-3 nm) has been a well established research area in the past decades in heterogeneous catalysis mainly due to the unique behaviour of Au NPs than its bulk counterpart. In this aspect, Au NPs encapsulated within the pore volumes of metal−organic frameworks (MOFs) have been intensively explored as heterogeneous solid catalysts for wide range of reactions. In recent years, Au NPs confined within the porous MOFs along with the photosensitizer or drug have been effectively used for the treatment of tumor cells through the generation of reactive oxygen species via cascade reactions. This work highlights the benefits of MOFs pores in the preparation of nanomedicine with high efficiency by assembling Au NPs, photosensitizer/drug with the combination of laser either for imaging or treatment of tumor cells. Further, the existing literature is grouped based on the nature of porous materials employed in the preparation of nanomedicine. The final section comments on our view on future developments in the field.     

Carbon aerogels for catalysis applications: An overview

Carbon aerogels are nanostructured carbons obtained from the carbonization of organic aerogels, which are prepared from the sol-gel polycondensation of certain organic monomers. These materials have a great versatility both at the nanoscopic level in terms of their pore texture and at the macroscopic level in terms of their form. Thus, the surface area, pore volume, and pore size distribution are tuneable surface properties related to the synthesis and processing conditions, which can produce a wide spectrum of materials with unique properties. In addition, carbon aerogels can be obtained in the form of monoliths, beads, powders or thin films. All these properties make them promising materials for application in adsorption and catalysis. Metal-doped monolithic organic aerogels can be easily prepared by following three main strategies: by addition of the metal precursor to the initial mixture, by ion-exchange or by deposition of the metal precursor on the organic or the carbon aerogel by one of various methods. These metal-doped carbon aerogels have been used as catalysts and as electrodes for electrical double-layer capacitors. This article shows the preparation of metal-doped carbon aerogels, their physico-chemical surface properties and their applications as catalysts in various reactions.     

Catalysis by molecular design

The possibilities of molecular design in the development of new catalysts and catalytic technologies are discussed with the data obtained recently at the Boreskov Institute of Catalysis as particular examples. Examples from the following areas are presented: homogeneous catalysis with metal complexes, heterogeneous catalysis with anchored metal complexes, heterogeneous catalysis with catalysts prepared via anchored metal complexes and organometallics, catalysis of olefin polymerization, catalysis by metals, catalysis by oxides, catalysis by zeolites, catalysis by heteropolyacids, catalysis with nontraditional oxidants and biomimetic catalysis.     

Self-supported chiral catalysts for heterogeneous asymmetric catalysis

A conceptually new strategy for chiral catalyst immobilization, self-supported catalysts, in heterogeneous asymmetric catalysis is highlighted in the present article. Various homochiral metal-organic polymers with diverse structures have been designed and readily prepared through coordination assembly of modular polytypic/polyfunctional ligands and metal ions without using any supports. These polymers have been successfully employed as chiral catalysts in a variety of heterogeneous asymmetric ractions, including hydrogenation, epoxidation, sulfoxidation, carbonyl-ene reactions, diethylzinc addition, and Michael addition. The self-supported heterogeneous chiral catalysts showed activity and enanioselectivity comparable or even superior to those obtained with their corresponding homogeneous counterparts, and could be readily recovered and reused several times without significant loss of activity or enantioslectivity.     

有机配体对加氢处理催化剂的影响进展

简述了近些年来有机配体对加氢处理催化剂的影响研究情况。添加有机配体可以提高加氢处理催化剂活性,从有机配体对加氢处理催化剂的制备及硫化过程的影响角度对文献的研究结果进行了综述,并对有机配体的作用机理进行了分析讨论。文中总结指出,有机配体与活性金属、载体的作用改变了金属与载体的相互作用,影响了金属组分的分散和硫化,从而有利于高活性CoMoS相的生成。     

Advanced metal oxide (supported) catalysts: Synthesis and applications

A variety of metal oxides catalysts are used in heterogeneous catalysis for chemical processes and have now been developed for their catalytic performance and durability. The heterogeneous catalysis is the most important technology in chemical industry as well as other environmental, energy applications, etc. This review examines recent advances at the preparation and applications of metal oxide particles, especially pertaining to catalytic enhancements for current and future chemical process such as Fischer–Tropsch process, alkylation, and transesterification and environmental applications such as the oxidation of volatile organic compounds and the reduction of NO_x.