核-壳结构磁性纳米颗粒负载离子液体的合成方法及应用*

离子液体具有良好的溶解能力、稳定性、结构可调性、无明显的蒸汽压等优点,使其可以作为良好的有机反应介质和催化剂,但由于其价格昂贵且不易从反应体系中分离,应用受到限制。以超顺磁性纳米颗粒作为催化剂载体,利用其所提供的磁学特性,可通过外磁场对催化剂进行简单有效的分离。不过,超顺磁性纳米颗粒具有的高比表面能以及粒子间的偶极距作用,使其容易团聚,不能稳定分散于反应体系。若在磁性纳米颗粒表面包裹一层有机物或无机物形成核-壳结构复合材料,就既可以阻止其团聚又可以对其进行表面功能化。因此,将离子液体固载到核-壳结构磁性纳米颗粒表面,制备可回收并循环使用的多相催化剂的工作受到广泛关注。本文综述了近十年来核-壳结构磁性纳米颗粒负载离子液体催化剂的制备方法及其在有机合成方面的应用,并对其未来的应用前景进行了展望。     

可循环磁性Pt/Fe_3O_4-MCNT催化剂上的肉桂醛选择性加氢反应

采用多步法依次将制备的Fe3O4纳米颗粒和Pt纳米颗粒负载到多壁碳纳米管(MCNT)上得到Pt/Fe3O4-MCNT磁性催化剂,以X射线衍射(XRD)、透射电镜(TEM)、超导量子干涉磁强计(SQUID)和热重-差热分析(TG-DTA)对Pt/Fe3O4-MCNT磁性催化剂的结构和磁性质进行了表征。研究发现预制备的Fe3O4纳米颗粒与Pt纳米颗粒均匀地分散于MCNT上,新制备以及多次使用后的Pt/Fe3O4-MCNT室温下都具有良好的超顺磁性。研究了Pt/Fe3O4-MCNT磁性催化剂上的肉桂醛选择性加氢反应,结果显示催化剂具有良好的C=O加氢活性,肉桂醛转化率在50%左右时,肉桂醇选择性可达96%以上。尺寸均一的Pt粒子均匀的分散在催化剂上可能是催化剂具有良好的C=O加氢选择性的重要原因。在外加磁场作用下催化剂可以高效地从液相反应体系中分离,经多次循环使用后仍具有良好的催化性能。     

超顺磁性纳米颗粒为催化剂载体的研究*

如何结合催化剂的制备找到一条新的催化剂分离与回收途径,已成为均相催化剂以及近十年快速发展的纳米催化剂研究中的一项重要内容。近年来,基于超顺磁性纳米颗粒作为催化剂载体来制备新型纳米催化剂的工作因此受到广泛关注。利用超顺磁性纳米颗粒所提供的磁学特性进行磁分离,不仅有效地解决了分离与重复使用问题,而且因其尺度处于纳米级,保持了以上催化剂的高活性、高选择性等动力学优点。本文从超顺磁性纳米载体的制备、催化剂的制备与活性评价等角度对近几年的研究工作进行综述,并对其发展前景进行展望。     

磁性贵金属纳米催化剂

磁性贵金属纳米颗粒因具有高效的催化性能和可重复利用性而受到广泛关注。本文描述了磁性贵金属纳米颗粒的基本结构,介绍了磁性贵金属催化剂的基本组成部分,概括了磁性贵金属纳米颗粒的制备方法,阐述了国内外磁性贵金属纳米颗粒的创新研究,指出了发展磁性贵金属纳米催化剂亟待解决的问题,并对磁性贵金属纳米颗粒的应用前景进行了展望。     

磁性纳米Pd/Fe_3O_4催化剂的制备及其在Heck反应中的应用（英文）

通过使用聚乙烯吡咯烷酮作为稳定剂,合成了磁性Pd/Fe_3O_4纳米颗粒催化剂。对该催化剂进行粉末X射线衍射、透射电子显微镜、感应耦合等离子体和磁性表征。将Pd/Fe_3O_4催化剂用于Heck反应,检测其催化性能。测试结果表明Pd纳米颗粒负载在Fe_3O_4纳米颗粒上,而且催化剂的尺寸20 nm,并在Heck反应中表现了极好的催化性能。此外,催化剂可以通过磁场回收利用,且催化活性没有显著的降低。     

磁性纳米颗粒负载钯催化剂对Heck反应的催化活性

采用水热法合成了碳包埋磁性纳米复合颗粒C/(Au@Fe),并以之为载体制备了纳米钯催化剂,利用透射电镜、X射线光电子能谱和振动样品磁强计等手段对催化剂进行了表征,评价了催化剂对Heck反应的催化活性.结果表明,催化剂的平均粒径约为300nm,表面覆盖着一层粒径为12nm的钯颗粒,整个催化剂呈现超顺磁性.对于碘代苯与丙烯酸之间的Heck反应,在乙酸钠或三乙胺碱性条件下反应4h,碘代苯转化率可达95%以上.催化剂重复使用10次时仍可保持很高的催化活性(碘代苯转化率88%).对于其他不同反应底物之间的Heck反应,催化剂同样显示有较高的催化活性.催化剂可稳定分散于反应体系中,并可在外磁场作用下快速与反应体系分离.     

磁性氧化铝负载Pd催化剂对硝基苯加氢催化活性的研究

采用微乳法室温下合成了γ-Al2O3/SiO2/Fe3O4磁性复合颗粒为载体负载的纳米钯催化剂.利用透射电镜、x射线光电子能谱和振动样品磁强计等手段对催化剂进行表征,评价了催化剂对硝基苯加氢制苯胺反应的催化活性.结果表明,通过调控反应条件,可在平均粒径为200nm左右的磁性载体上负载10m左右均匀分散的Pd纳米颗粒,整个催化剂呈现超顺磁性;在催化剂磁含量为8%、Pd负载量1%、反应时间40min、反应温度50℃,反应压力0.5MPa条件下,硝基苯的转化率可以达到100%,催化剂重复使用10次时仍可保持很高的催化活性,并可在外磁场作用下快速分离与回收.     

溶剂化金属原子浸渍法制备高分散负载型催化剂——Ⅸ.K-Fe/硅沸石催化剂的XRD、TEM、XPS和磁测定表征

用溶剂化金属原子浸渍(SMAI)法和普通浸渍(CI)法两种不同的方法制备了组成相同的K-Fe/硅沸石催化剂。TEM,XRD,XPS和磁测定结果表明,SMAI K-Fe/硅沸有催化剂中铁的分散度和还原度都大于CI催化剂,SMAI催化剂中金属颗粒直径小于4nm,具有超顺磁性,而CI催化剂中金属颗粒较大,表现铁磁性。两种方法制备的催化剂反应前后金属的状态发生明显的改变,对CO+H_2反应的催化性质不同。     

兼具MRI显影增强及pH敏感释药性能的载药Fe_3O_4纳米颗粒

以聚丙烯酸(PAA)修饰的超顺磁性Fe_3O_4纳米颗粒(MNPs-PAA)为基础,利用pH敏感的腙键将抗肿瘤药物阿霉素(DOX)与磁性颗粒表面的PAA链偶联,制备了载药Fe_3O_4磁性纳米颗粒(MNPs-DOX)。通过透射电镜、X射线衍射、紫外、红外、热失重以及体外磁共振显影(MRI)等手段对MNPs-DOX的形貌、结构、MRI及载释药效果进行了表征。结果证实,MNPsDOX具有超顺磁性,在MRI中具备良好的横向弛豫(T2)显影增强效果。此外,其DOX负载率达15%(质量分数),且在pH=5.0的酸性环境中药物释放量明显高于pH=7.4的中性环境,具有对环境pH的敏感性。     

铁氧体磁性纳米催化剂的制备及其在资源能源领域的应用

随着石油开采技术的不断提高,石油资源的开发和利用规模逐渐增大,然而现存的石油资源组成复杂、黏度高,使用常规的催化剂进行改质存在利用率低、回收困难等问题。生物质能已成为化石燃料的潜在替代品,生物质的催化转化是制备各种商品化学品或液体燃料的主要途径之一。然而生物质催化转化中常用的均相催化剂及非均相催化剂同样具有难回收再利用以及分离损失大等问题,限制了其应用。磁性纳米催化剂不仅具有高催化活性,在外加磁场作用下还能实现催化剂的回收与重复利用,在工业生产得以连续化的同时,也降低了生产成本,提高了生产效率。本综述介绍了铁氧体磁性纳米催化剂的制备方法,阐述了近年来铁氧体磁性纳米催化剂在催化脱硫、生物质催化转化为化学品、生物柴油的制备、煤液化领域的研究进展,指出了铁氧体磁性纳米催化剂在资源能源领域应用存在的问题,并对铁氧体磁性纳米颗粒的应用前景进行了展望。     

磁性纳米粒子负载钯催化有机合成反应研究进展

磁性纳米粒子负载钯催化的有机合成反应,由于具有催化活性高,催化剂在外加磁场作用下即可快速分离和重复使用等特点,已引起了人们的广泛关注.综述了近年来磁性纳米粒子负载钯催化有机合成反应的研究进展,载体包括Fe3O4纳米粒子、有机小分子修饰的磁性纳米粒子、SiO2包覆的磁性纳米粒子、碳修饰磁性纳米粒子、羟基磷灰石包覆的磁性纳米粒子和有机高分子修饰的磁性纳米粒子等.     

Nano-organocatalyst: magnetically retrievable ferrite-anchored glutathione for microwave-assisted Paal-Knorr reaction, aza-Michael addition, and pyrazole synthesis

Postsynthetic surface modification of magnetic nanoparticles by glutathione imparts desirable chemical functionality and enables the generation of catalytic sites on the surfaces of ensuing organocatalysts. In this article, we discuss the developments, unique activity, and high selectivity of nano-organocatalysts for microwave-assisted Paal-Knorr reaction, aza-Michael addition, and pyrazole synthesis. Their insoluble character coupled with paramagnetic nature enables easy separation of these nano-catalysts from the reaction mixture using external magnet, which eliminates the requirement of catalyst filtration.     

Recent advances in catalysts immobilized on magnetic nanoparticles

Unsupported nanoparticles are often less stable, and usually coagulation is unavoidable during the catalytic reactions. To generate stable nanoparticles with good activity, stabilizing the surface is required. Protection has been performed by the addition of polymers or long-chain alkyl surfactants with polar functional groups that attached to the nanoparticle surface via covalent or electrostatic interactions. Alternatively, nanoparticles have been immobilized or grafted onto inorganic supports to improve their stabilization and recycling ability. In this article, the green catalytic processes and recent advances in organic transformations catalyzed by magnetically retrievable catalysts are reviewed. Prior to this, methods for the synthesis of catalysts immobilized on magnetic nanoparticles are addressed briefly.     

巯基功能化介孔材料高效锚定钯负载型催化剂的制备及其苯酚加氢催化性能

以含巯基官能团有机硅烷修饰的介孔材料MCM-41和SBA-15为载体, 采用浸渍-氢气还原法制备了高分散和高活性的负载型Pd催化剂. X射线衍射、N₂吸附-脱附和透射电子显微镜表征结果显示, 所制Pd催化剂Pd-SH-MCM-41和Pd-SH-SBA-15具有很好的长程有序结构、分布均匀的孔径、高比表面积及高度分散的Pd颗粒. 苯酚加氢反应结果表明, 以Pd-SH-MCM-41和Pd-SH-SBA-15为催化剂时, 在80℃, 1.0MPa反应1h, 苯酚转化率达99%以上, 环己酮选择性为98%. 它们的催化活性为商业Pd/C催化剂的5倍, Pd/MCM-41和Pd/SBA-15催化剂的3倍. 这可归因于介孔材料表面修饰的巯基官能团对Pd的锚定作用, 避免了Pd颗粒的团聚, 使其高度分散在介孔材料上.     

CuFe2O4 nanomaterials: Current discoveries in synthesis,catalytic efficiency in coupling reactions,and their environmental applications

In the last few decades, there has been enormous growth in ferrite nanoparticles. Magnetic, optical, and electrical properties of ferrites gain consideration due to their use in various applications such as rechargeable lithium batteries, medical diagnostics, solar energy devices, and so forth. A vast increase in interest in ferrite nanoparticles has led them to be used as catalysts in various applications as they possess a large surface area-to-volume ratio. Furthermore, iron-based magnetic characteristics make it simple to retrieve catalysts by using an external magnet. Iron's catalytic potential, however, is far less than copper's. Therefore, the catalytic scope is substantially increased by substituting copper within the crystal lattice. Recently copper ferrite nanoparticles have caught the interest of numerous researchers due to low-cost magnetic material, stability under diverse conditions, and ease at which catalyst can be retrieved using an external magnetic field and utilized repeatedly. This review of data from year 2010 through 2022 emphasizes the synthesis method, structure, application in dyes degradation, catalytic potential in the number of coupling reactions, recyclability, and reusability of the magnetic catalyst.     

Active and Recyclable Gold Metal Nanoparticles Catalyst Supported on Nitrogen-Doped Mesoporous Carbon for Chemoselective Hydrogenation of Cinnamaldehyde to Cinnamyl Alcohol

Several supported gold metal catalysts with different Au nanoparticles sizes were prepared and evaluated for the chemoselective hydrogenation of cinnamaldehyde (CA) to cinnamyl alcohol (CAL). To investigate the structure-activity relationship, stability of catalyst, heterogeneity and recyclability, the structural characteristics of materials and Au catalysts (fresh and spent catalysts) were studied by employing variety of physico-chemical techniques. The interrelationship among Au nanoparticles size (nm) with turnover frequency (h⁻¹) of Au catalysts has also been explored. Among the various Au catalysts tested, nitrogen-doped mesoporous carbon (NMC) supported Au catalyst having homogeneously dispersed (78.8%) Au nanoparticles (1.6 nm) synthesized by sol-immobilization method (Au-NMC-SI) demonstrated improved catalytic activity affording 78% CAL selectivity and 94.2% CA conversion without using any promoter. Moreover, Au-NMC-SI catalyst exhibited good recyclability and stability. The catalyst synthesis approach described in this investigation opens up a novel strategy for the design of highly efficient metal nano-catalysts supported on NMC materials.     

Reusable shuttles for exchangeable functional cargos: Reversibly assembled,magnetically powered organocatalysts for asymmetric aldol reactions

A supramolecular approach has been followed to support adamantyl substituted proline organocatalysts onto the surface of magnetite nanoparticles decorated with a β-cyclodextrin motif. The resulting magnetic nanoparticles (ca. ∼10 nm diameter) were used as modular, magnetically recyclable catalysts in the asymmetric aldol reaction of aromatic aldehydes with cyclic ketones in water. The catalytic assemblies can be easily dismantled in organic media, and the recovered nanoparticles (magnetically powered chemical shuttles) re-complexed with another suitably substituted catalytic unit (replaceable functional cargo).     

Preparation of Organic Nanoacid Catalyst for Urethane Formation

Metal-free catalysts are preferred during these days in organic synthesis or in polymerizations.Sulfonic acid is reported to be efficient in catalyzing reactions between isocyanates and alcohols.In this work,synthesis of sulfonic acid immobilized organic nanoparticles (nanoacid) and its application in catalyzing urethane formation,are elaborated.The nanoacid can be simply prepared by miniemulsion polymerization with a reactive surfactant,namely sodium 4-((perfluoronon-8-en-1-yl) oxy) benzenesulfonate,followed by an acidification.From the images of scanning electron microscope,the nanoacid obtained is found to be narrowly dispersed and the average diameter is around 90 nm.The measured sulfur content is 0.5%,from which the content of sulfonic acid in the nanoparticles is calculated to be 0.16 mmol/g.When catalyzing urethane formation based on hexamethylene diisocyanate and n-butanol,the nanoacid catalyst exhibits considerable efficiency.     

Synthesis of novel magnetic nanoparticles with urea or urethane moieties: Applications as catalysts in the Strecker synthesis of α‐aminonitriles

Four novel magnetic nanoparticle catalysts with urea or urethane moieties are reported. The silica‐coated magnetic nanoparticles were simply functionalized via addition of 3‐(triethoxysilyl)propylisocyanate (TESPIC), amine or amino alcohol. TESPIC with dual labile functional groups was used as a suitable precursor for the synthesis of urethane‐based catalysts. The newly synthesized catalysts were fully characterized using a variety of techniques. These functionalized magnetic nanoparticles were used as reusable catalysts in the Strecker synthesis of α‐aminonitrile derivatives under solvent‐free conditions at 50 °C.     

Bimetallic dendrimer-encapsulated nanoparticles as catalysts: a review of the research advances

Bimetallic dendrimer-encapsulated nanoparticles (DENs) are important materials, because they have demonstrated improvement in performance compared to the monometallic DENs in many systems when they are used as catalysts. This tutorial review focuses on the recent research advances in bimetallic DENs with respect to their synthesis, characterization, and applications as catalysts. Bimetallic DENs can be made mainly via three routes: co-complexation, sequential loading, and partial displacement. The research in bimetallic DENs has been significantly promoted by the advancement of characterization instruments. The performances of bimetallic DENs as homogeneous and heterogeneous catalysts in organic synthesis have been compared with both monometallic DENs and their physical mixtures. It is concluded that the synergistic electronic effect in bimetallic nanoparticles enhances their catalytic activities.