Metal Nanoparticles Syntheses on Ionic Liquids Functionalized Mesoporous Silica SBA‐15

Supported metal nanoparticles hold great promise in heterogeneous catalysis as active and reusable catalysts for various organic transformations. Preparation methods of metal nanoparticles with excellent control over size, shape, and morphology on supports has significantly advanced to improve the performances of the resulting catalysts. Here, we aim to discuss the development of supported metal nanoparticles on mesoporous silica SBA‐15 in the presence of immobilized ionic liquids mostly based on examples from the previously reported results. This review highlights the preparation methods for size‐controlled syntheses and the immobilization of metal nanoparticles on solid supports, especially SBA‐15 by various techniques.     

Polydimethylsiloxane Coating for a Palladium/MOF Composite: Highly Improved Catalytic Performance by Surface Hydrophobization

Surface wettability of active sites plays a crucial role in the activity and selectivity of catalysts. This report describes modification of surface hydrophobicity of Pd/UiO‐66, a composite comprising a metal–organic framework (MOF) and stabilized palladium nanoparticles (NPs), using a simple polydimethylsiloxane (PDMS) coating. The modified catalyst demonstrated significantly improved catalytic efficiency. The approach can be extended to various Pd nanoparticulate catalysts for enhanced activity in reactions involving hydrophobic reactants, as the hydrophobic surface facilitates the enrichment of hydrophobic substrates around the catalytic site. PDMS encapsulation of Pd NPs prevents aggregation of NPs and thus results in superior catalytic recyclability. Additionally, PDMS coating is applicable to a diverse range of catalysts, endowing them with additional selectivity in sieving reactants with different wettability.     

Organic nanoparticles from microemulsions: Formation and applications

Microemulsions have already been recognized as convenient templates for nanoparticle synthesis. Spontaneous formation of the compartmentalized domains within the microemulsions leads to facile and low-cost preparation processes.In the past, microemulsions were mainly explored as precursors for the synthesis of inorganic nanoparticles. However, there is a constantly growing number of publications offering to exploit these systems to produce organic nanoparticles, and in recent years, a variety of methods have emerged in this field. The aim of this review is to survey the methods recently used to produce organic nanomaterials from microemulsions, and to give a perspective on particle design possibilities that can be achieved by various techniques. The structure of the initial microemulsion system, the chemical and technical aspects of preparation, the nature of additives and surface active agents, as well as the possible outcomes in terms of final particle characteristics, will be discussed for the various methods.     

Cobalt Single-Atom Catalysts with High Stability for Selective Dehydrogenation of Formic Acid

Metal–organic framework (MOF)-derived Co-N-C catalysts with isolated single cobalt atoms have been synthesized and compared with cobalt nanoparticles for formic acid dehydrogenation. The atomically dispersed Co-N-C catalyst achieves superior activity, better acid resistance, and improved long-term stability compared with nanoparticles synthesized by a similar route. High-angle annular dark-field–scanning transmission electron microscopy, X-ray photoelectron spectroscopy, electron paramagnetic resonance, and X-ray absorption fine structure characterizations reveal the formation of Co^IIN_x centers as active sites. The optimal low-cost catalyst is a promising candidate for liquid H₂ generation.     

Supported colloidal nanoparticles in heterogeneous gas phase catalysis: on the way to tailored catalysts

Using colloidally synthesized nanoparticles for the preparation of supported catalysts offers several advantages (e.g. precise control of particle size and morphology) when compared to traditional preparation techniques. Although such nanoparticles have already been very successfully used for catalytic applications in the liquid phase, applications in heterogeneous gas phase catalysis are still scarce. One aspect, usually considered as a problem, is organic stabilizers typically employed during the nanoparticle synthesis since they or their decomposition products are supposed to block catalytically active sites on the nanoparticle surface. Thus, in many studies so far, the removal of the organic ligands prior to use in gas phase catalysis has been proposed. In this perspective article, however, we will discuss a number of benefits such ligand shells may have for heterogeneous gas phase catalysis, including the protection against chemical modification, prevention of sintering and tuning of SMSI effects.     

Apparent 'electrocatalytic' activity of multiwalled carbon nanotubes in the detection of the anaesthetic halothane: occluded copper nanoparticles

The electrocatalytic detection of the anaesthetic halothane on a multiwalled carbon nanotube modified glassy carbon electrode is reported with a low limit of detection of 4.6 microM. A thorough investigation of the underlying cause of this apparent catalytic effect is undertaken by comparing the response of various carbon electrodes including glassy carbon, basal- and edge-plane pyrolytic graphite electrodes (bppg and eppg respectively) to increasing additions of halothane. The reduction of halothane is shifted by 250-300 mV to more negative potentials at an eppg electrode than that observed at the GC-CNT electrode. Therefore the results of this investigation show that, surprisingly, the electrocatalysis is not solely due to the introduction of edge-plane-like defect sites on the carbon nanotubes as is commonly found for many other substrates showing favourable voltammetry at nanotube modified electrodes. Instead, we reveal that in this unusual case the electroactive sites for the reduction of halothane are due to the presence of copper nanoparticles occluded within the carbon nanotubes during their production, which are never completely removed by standard purification techniques such as acid washing. This is only the third known case where apparent electrocatalysis by carbon nanotube modified electrodes is due to occluded metal-related nanoparticles within the nanotube structure, rather than the active sites being the edge-plane-like defect sites on the nanotubes. Furthermore this is the first case where the active sites are nanoparticles of copper metal, rather than metal oxide nanoparticles (namely oxides of iron(II)/(III)) as was found to be the case in the previous examples.     

共价有机框架材料在多相催化领域的研究进展（英文）

共价有机框架(COFs)材料是近年来在拓扑学基础上发展起来的一类新型有机多孔聚合物,是有机单体通过可逆共价键连接而形成的晶型多孔材料,具有拓扑结构"可设计"、比表面积大、结构规整、孔道均一、孔径可调节以及易于修饰和功能化等优点.与金属有机框架材料(MOFs)相比,由于COFs是以共价键连接形成空间网络结构,具有较好的热稳定性和化学稳定性,又被称为"有机分子筛".COFs的构筑单体为有机小分子,有机小分子来源广泛而且种类繁多,使得构筑单体多样化,便于通过构筑单体来调控目标材料的结构和功能.自2005年首次报道以来,COFs以其独特的结构和优越的性能,吸引了广大科研工作者的极大兴趣,对其结构设计、可控合成、结构解析以及功能探索成为了研究热点,在气体吸附与分离、光电材料等领域展现出了广阔的应用前景.特别是在催化领域,由于COFs材料的多孔性、敞开的孔道结构、良好的稳定性以及易于修饰的特点,采用COFs作为催化剂以及催化剂载体受到了人们普遍的关注.作为催化剂,COFs可分为本征型催化剂和负载型催化剂.本征型催化剂的设计方法是基于"自下而上"策略将催化活性中心嵌入材料骨架之中;负载型催化剂的设计方法是以COFs为载体,通过后修饰方式负载金属颗粒或离子来构建多相催化剂.本征型COFs催化剂是在分子水平上引入催化活性中心,具有活性位点均匀分散、数量可控的特点,而且COFs规整均一的孔道结构有利于底物的传质,也为择形催化提供了可能;负载型催化剂通过后修饰方式引入催化活性中心,由于COFs以共价键连接,催化剂稳定性较高.COFs载体具有较大的比表面积,使得催化活性位点分散性好,也有利于底物与催化活性位点的结合.本文综述了COFs作为多相催化剂在催化领域的发展状况,按照COFs引入催化活性位点的类别,如单催化位点、双催化位点以及负载的金属纳米粒子进行了细致的阐述,重点讨论了COFs催化剂的设计理念、制备方式、功能化策略、材料的稳定性、催化活性以及选择性等内容.此外,对COFs作为光催化剂以及电催化剂方面的研究也进行了详细的介绍.最后,我们讨论了COFs在未来催化领域所面临的问题及挑战,并展望了COFs在超分子催化以及酶催化等方面的应用前景.     

金属有机骨架基催化剂在加氢反应中的应用

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.     

Recent Advances in the Support Layer,Interlayer and Active Layer of TFC and TFN Organic Solvent Nanofiltration (OSN) Membranes: A Review

Although separation of solutes from organic solutions is considered a challenging process, it is inevitable in various chemical, petrochemical and pharmaceutical industries. OSN membranes are the heart of OSN technology that are widely utilized to separate various solutes and contaminants from organic solvents, which is now considered an emerging field. Hence, numerous studies have been attracted to this field to manufacture novel membranes with outstanding properties. Thin-film composite (TFC) and nanocomposite (TFN) membranes are two different classes of membranes that have been recently utilized for this purpose. TFC and TFN membranes are made up of similar layers, and the difference is the use of various nanoparticles in TFN membranes, which are classified into two types of porous and nonporous ones, for enhancing the permeate flux. This study aims to review recent advances in TFC and TFN membranes fabricated for organic solvent nanofiltration (OSN) applications. Here, we will first study the materials used to fabricate the support layer, not only the membranes which are not stable in organic solvents and require to be cross-linked, but also those which are inherently stable in harsh media and do not need any cross-linking step, and all of their advantages and disadvantages. Then, we will study the effects of fabricating different interlayers on the performance of the membranes, and the mechanisms of introducing an interlayer in the regulation of the PA structure. At the final step, we will study the type of monomers utilized for the fabrication of the active layer, the effect of surfactants in reducing the tension between the monomers and the membrane surface, and the type of nanoparticles used in the active layer of TFN membranes and their effects in enhancing the membrane separation performance.     

Single‐Atom Catalyst of Platinum Supported on Titanium Nitride for Selective Electrochemical Reactions

As a catalyst, single‐atom platinum may provide an ideal structure for platinum minimization. Herein, a single‐atom catalyst of platinum supported on titanium nitride nanoparticles were successfully prepared with the aid of chlorine ligands. Unlike platinum nanoparticles, the single‐atom active sites predominantly produced hydrogen peroxide in the electrochemical oxygen reduction with the highest mass activity reported so far. The electrocatalytic oxidation of small organic molecules, such as formic acid and methanol, also exhibited unique selectivity on the single‐atom platinum catalyst. A lack of platinum ensemble sites changed the reaction pathway for the oxygen‐reduction reaction toward a two‐electron pathway and formic acid oxidation toward direct dehydrogenation, and also induced no activity for the methanol oxidation. This work demonstrates that single‐atom platinum can be an efficient electrocatalyst with high mass activity and unique selectivity.     

Atomic Layer Deposition Overcoating: Tuning Catalyst Selectivity for Biomass Conversion

The terraces, edges, and facets of nanoparticles are all active sites for heterogeneous catalysis. These different active sites may cause the formation of various products during the catalytic reaction. Here we report that the step sites of Pd nanoparticles (NPs) can be covered precisely by the atomic layer deposition (ALD) method, whereas the terrace sites remain as active component for the hydrogenation of furfural. Increasing the thickness of the ALD‐generated overcoats restricts the adsorption of furfural onto the step sites of Pd NPs and increases the selectivity to furan. Furan selectivities and furfural conversions are linearly correlated for samples with or without an overcoating, though the slopes differ. The ALD technique can tune the selectivity of furfural hydrogenation over Pd NPs and has improved our understanding of the reaction mechanism. The above conclusions are further supported by density functional theory (DFT) calculations.     

A Universal Strategy toward Ultrasmall Hollow Nanostructures with Remarkable Electrochemical Performance

A facile and versatile microwave‐assisted and shell‐confined Kirkendall diffusion strategy is used to fabricate ultrasmall hollow nanoparticles by modulating the growth and thermal conversion of metal–organic framework (MOF) nanocrystals on graphene. This method involves that the adsorption of microwave by graphene creates a high‐energy environment in a short time to decompose the in situ grown MOF nanocrystals into well‐dispersed uniform core–shell nanoparticles with ultrasmall size. Upon a shell‐confined Kirkendall diffusion process, hollow nanoparticles of multi‐metal oxides, phosphides, and sulfides with the diameter below 20 nm and shell thickness below 3 nm can be obtained for the first time. Ultrasmall hollow nanostructures such as Fe2O3 can promote much faster charge transport and expose more active sites as well as migrate the volume change stress more efficiently than the solid and large hollow counterparts, thus demonstrating remarkable lithium‐ion storage performance.     

Preparation of organic nanoparticles using microemulsions: their potential use in transdermal delivery

Organic nanoparticles of cholesterol and retinol have been synthesized in various AOT (Aerosol OT; sodium bis(2-ethylhexyl) sulfosuccinate)/heptane/water microemulsions by direct precipitation of the active principle in the aqueous cores. The nanoparticles are observed by transmission electron microscopy (TEM) using the adsorption of a contrasting agent, such as iodine vapor. The size of the nanoparticles can be influenced, in principle, by the concentration of the organic molecules and the diameter of the water cores, which is related to the ratio R=[H2O]/[surfactant]. The particles remain stable for several months. The average diameter of the cholesterol nanoparticles varies between 3.0 and 7.0 nm, while that of retinol varies between 4.0 and 10 nm. The average size of the cholesterol nanoparticles does not change much either as a function of the ratio R or as a function of the concentration of cholesterol. The constant size of the nanoparticles can be explained by the thermodynamic stabilization of a preferential size of the particles. Chloroform is used to carry the active principle into the aqueous cores. Retinol molecules form J-complexes composed of two or three molecules, as detected by UV-visible spectroscopy.     

Electrochemistry and electrogenerated chemiluminescence of organic nanoparticles

This review discusses briefly the preparation, electrochemistry, and electrogenerated chemiluminescence (ECL) as well as spectroscopic properties of organic nanoparticles. Organic nanoparticles, ranging from several tens of nanometers to hundreds of nanometers in diameter, were successfully prepared by various methods. Using a simple reprecipitation method, organic nanoparticles of a very small size can be prepared and show unique electrochemical and ECL characteristics. As with inorganic nanoparticles, organic nanoparticles suggest possible applications, like labels for the analysis of biological materials with ECL.     

Synthesis of Highly Accessible and Reactive Sites in Gold Nanoparticles Using Bound Bis(Diphenylphosphine) Ligands

While bound organic ligands provide steric protection against aggregation for metallic nanoparticles in solution, they can block a large fraction of the surface atoms which are needed for binding in catalysis and sensing applications. In this work, highly accessible Au nanoparticles ligated with bis(diphenylphosphine) molecules are synthesized and characterized in solution. Characterization is performed using high angle annular dark field-scanning transmission electron microscopy (HAADF-STEM), ultraviolet-visible (UV-Vis) spectroscopy, and fluorescence chemisorption experiments. These synthesized nanoparticles are accessible to a 2-napthalenethiol (2-NT) probe molecule in solution. The highest 2-NT accessibility is observed when using 1,1-bis(diphenylphosphino)methane (dppm) ligand where 61 % of the total gold atoms are accessible. It is hypothesized that increasing the rigidity of the bis(diphenylphosphine) ligand increases the number of binding sites on the Au nanoparticles. These nanoparticles are catalytically active for resazurin reduction, and the resazurin reduction rate scales with the number of binding sites.     

MOF-Mediated Synthesis of Supported Fe-Doped Pd Nanoparticles under Mild Conditions for Magnetically Recoverable Catalysis**

Metal–organic framework (MOF)-driven synthesis is considered as a promising alternative for the development of new catalytic materials with well-designed active sites. This synthetic approach is used here to gradually transform a new bimetallic MOF, with Pd and Fe as the metal components, by the in situ generation of aniline under mild conditions. This methodology results in a compositionally homogeneous nanocomposite formed by Fe-doped Pd nanoparticles that, in turn, are supported on iron oxide-doped carbon. The nanocomposite has been fully characterized by several techniques such as IR and Raman spectroscopy, TEM, XPS, and XAS. The performance of this nanocomposite as an heterogeneous catalyst for hydrogenation of nitroarenes and nitrobenzene coupling with benzaldehyde has been evaluated, proving it to be an efficient and reusable catalyst.     

Cobalt Single‐Atom Catalysts with High Stability for Selective Dehydrogenation of Formic Acid

Metal–organic framework (MOF)‐derived Co‐N‐C catalysts with isolated single cobalt atoms have been synthesized and compared with cobalt nanoparticles for formic acid dehydrogenation. The atomically dispersed Co‐N‐C catalyst achieves superior activity, better acid resistance, and improved long‐term stability compared with nanoparticles synthesized by a similar route. High‐angle annular dark‐field–scanning transmission electron microscopy, X‐ray photoelectron spectroscopy, electron paramagnetic resonance, and X‐ray absorption fine structure characterizations reveal the formation of Co^IIN_x centers as active sites. The optimal low‐cost catalyst is a promising candidate for liquid H₂ generation.     

Keggin ion mediated synthesis of hydrophobized Pd nanoparticles for multifunctional catalysis

Development of simple and reliable protocols for the synthesis of organically soluble catalytically active metal nanoparticles is an important aspect of research in nanomaterials. We demonstrate herein the formation of Pd nanoparticles by reduction of aqueous Pd(NO(3))(2) by photoexcited Keggin ions (phosphotungstate anions). This results in the formation of Pd nanoparticles capped with with Keggin ions that render the particles negatively charged. The Keggin ion capped Pd nanoparticles may then be phase transferred into nonpolar organic solvents such as toluene by electrostatic complexation with cationic surfactants such as octadecylamine at the liquid-liquid interface. This results in a new class of catalyst wherein both the Pd core and Keggin ion shell may be used in a range of catalytic reactions leading to a truly multifunctional catalyst dispersible in organic solvents.     

Electrochemistry and electrogenerated chemiluminescence of organic nanoparticles

This review discusses briefly the preparation, electrochemistry, and electrogenerated chemiluminescence (ECL) as well as spectroscopic properties of organic nanoparticles. Organic nanoparticles, ranging from several tens of nanometers to hundreds of nanometers in diameter, were successfully prepared by various methods. Using a simple reprecipitation method, organic nanoparticles of a very small size can be prepared and show unique electrochemical and ECL characteristics. As with inorganic nanoparticles, organic nanoparticles suggest possible applications, like labels for the analysis of biological materials with ECL.

     

纳米材料掺杂聚合物整体柱的构筑及在前处理领域的应用

聚合物整体柱是由单体、交联剂、引发剂和致孔剂在模具中通过原位聚合而成的棒状整体。与传统的填充式固相萃取柱相比,聚合物整体柱吸附剂凭借制备简单、柱压低、传质快及pH使用范围宽泛等优点已广泛应用于食品分析、生物医药和环境卫生等领域的前处理中。然而,通常由于聚合方式难以控制,聚合物整体柱在制备过程中容易产生颗粒堆积、孔道不均匀从而导致孔隙率低和比表面积有限等问题。近年来,将纳米材料掺杂至聚合物整体柱以获得有序结构分布、良好吸附效率以及优越选择性能的新型吸附剂成为研究热点。纳米材料种类繁多,尺寸小,利用其表面丰富的活性基团、作用位点和超大的比表面积等优势,通过简单掺杂、共聚合和原位修饰等方法合成纳米掺杂聚合物整体柱,不仅能够改善其微观结构、柱床机械强度和稳定性,同时可以显著提高掺杂聚合物整体柱吸附剂的萃取性能和选择性。该文综述了碳材料、金属和金属氧化物、金属有机骨架、共价有机骨架和无机纳米粒子等不同纳米材料掺杂的聚合物整体柱、常用的构筑方法以及该类吸附剂在固相萃取、固相微萃取、搅拌棒吸附萃取和在线固相萃取等样品前处理领域的应用,并展望这一研究的发展趋势和应用前景,以期为前处理领域的研究提供参考。