贵金属纳米粒子/硅纳米线复合纳米材料的制备及其催化性能研究

以十二烷基硫酸钠(SDS)作为保护剂, 利用贵金属阳离子(Mⁿ⁺)与HF处理后的硅纳米线(SiNWs)之间的氧化还原反应, 在SiNWs表面负载了贵金属纳米粒子. 通过调控SDS/Mⁿ⁺物质的量比、反应物浓度、反应温度等实验参数, 制备出了金属纳米粒子粒径均一且负载密集的AuNPs/SiNWs, PtNPs/SiNWs复合材料. 将AuNPs/SiNWs复合材料应用在亚甲基蓝的还原反应, 实验结果显示, 60 min内AuNPs/SiNWs可以将55%的亚甲基蓝还原, 表明AuNPs/SiNWs具有良好的催化活性. 这种复合材料易于从反应溶液中分离出来, 可以实现纳米催化剂的循环使用.     

环糊精作为纳米反应器催化的有机反应

环糊精是由六、七或八个D-吡喃葡萄糖单元通过a-1,4糖苷键连接成的环状低聚糖, 由于其特殊的结构使其在水溶液中可以复合包结系列底物. 这个特殊的性能使其在模拟酶及催化等许多领域有着广阔的应用, 特别适合作为一种纳米级的反应器来使用. 概述了近几年环糊精及其衍生物作为有机反应纳米反应器的功能特点.     

核壳结构纳米粒子

纳米粒子由于具有大量的潜在应用,近年来已引起人们极大的关注。通过表面改性(如制备核壳结构的纳米粒子)可以使其获得更多特殊的性质。本文就最近几年制备壳核结构纳米粒子的方法进行了总结,根据其核、壳的不同材料进行了分类,并对其中某些方法进行了比较。     

贵金属固体催化剂的纳米结构及催化性能

 综述了贵金属催化剂纳米结构的形成和制备方法,以及催化活性与纳米粒子尺寸的关系. 还以负载型双金属催化剂为例,介绍了催化剂中的短程有序结构.     

新型分子筛Ti-MMM-1的合成及其催化性能的研究

通过控制TEOS的水解，在不同时间添加与MCM-41和MFI相应的有机模板剂合成出了一种新型分子筛，Ti-MMM-1，采用XRD、FT-IR和低温N2吸附对其进行表征，并用H2O2氧化环己烷和环己醇对其催化活性进行评价．结果表明，Ti-MMM-1是一种具有MCM-41和MFI结构的两相混合的微孔／介孔材料，IR分析表明钛原子已进入分子筛骨架，并在环己烷和环己醇的氧化中表现出较好的催化活性和较高的选择性．     

有机官能化介孔硅基材料负载纳米金催化剂的制备及其催化性能

一步合成了桥键嵌入二硫醚官能化介孔硅基材料(PMO-SBA-15),利朋介孔硅基材料孔道内表面的二硫醚基团捕获纳米金(Au)粒子的作用,获得了负载型纳米Au催化剂(Au-PMO-SBA-15).小角X射线衍射和低温N2吸附-脱附的结果表明,PMO-SBA-15和Au-PMO-SBA-15均保持典型的介孔结构;高分辨透射电镜观察到纳米Au粒子在载体孔道内分散均匀,甲均粒径为(2.2±0.2)nm.以70%的叔丁基过氧化氧水溶液为氧化剂,考察了纳米Au催化剂Au-PMO-SBA-15在苯甲醇氧化反应中的催化性能.结果表明,当反应温度为353 K、反应时间为5 h时,苯甲醇的转化率为29.1%,苯甲醛的选择性为100%,且催化剂重复使用7次其催化活性和苯甲醛选择性基奉不变.     

基于介孔纳米粒子模板合成兼有荧光和近红外发光的稀土核-壳结构纳米材料

利用单分散性良好介孔SiO2纳米粒子为模板,选择Y2O3为基底,同时掺杂可见区红光中心Eu3+和近红外区Er3+(1.54 μm)发光中心,成功制备特殊结构的核壳多功能发光纳米材料. 光谱测试表明这种核壳材料同时具有可见区发光和近红外发光的双重性质. 表明Y2O3可作为红光Eu和近红外发光Er的良好基底材料. 该方法可以大大降低纳米发光材料中稀土元素的使用量,降低发光材料的成本,并且该核壳结构材料密度相对较低,易于分散在有机溶剂或者水中,在药物释放和多功能生物标记等方面有着潜在的应用价值.     

微结构的纳米设计膜反应器中的催化

For thermodynamically and kinetically controlled catalytic reactions,the influence of a membrane is discussed. For reactions operating near to the thermodynamic equilibrium,the conversion can be increased if one/all of the products is/are selectively removed in an extractor type membrane reactor. Examples are esterifications,dehydrogenations,and water dissociation using water,hydrogen,and oxygen selective membranes,respectively. For kinetically controlled reactions,i.e. reactions with a very negative free enthalpy,mainly the selectivity can be increased via the control of the partial pressure of the educts by dosing effects using distributor/contactor membrane reactors. Examples are partial oxidations and hydrogenations. In detail,the application of an oxygen transporting perovskite hollow fiber membrane with a nano-designed grain boundary structure in the hydrogen production by thermal water splitting and in the partial oxidation of hydrocarbons as case studies for thermodynamically and kinetically controlled reactions is discussed.     

介孔SiO2负载的纳米金及其催化应用

金（Au）的催化作用已成为催化领域的前沿研究课题。本文综述了近年来采用不同方法制备介孔二氧化硅(MCM-41, MCM-48, SBA-15)负载的纳米Au催化剂以及在CO低温氧化、环己烯加氢和环己烷氧化等反应中的催化作用。讨论了影响纳米Au催化剂活性的相关因素, 包括载体的种类、表面性质、Au纳米颗粒的尺寸、分散度以及稳定性等。最后对各种制备纳米Au的方法进行了总结。     

Synthesis of Chemically Asymmetric Silica Nanobottles and Their Application for Cargo Loading and as Nanoreactors and Nanomotors

We report the synthesis of chemically asymmetric silica nanobottles (NBs) with a hydrophobic exterior surface (capped with 3‐chloropropyl groups) and a hydrophilic interior surface for spatially selective cargo loading, and for application as nanoreactors and nanomotors. The silica NBs, which have a “flask bottle” shape with an average diameter of 350 nm and an opening of ca. 100 nm, are prepared by anisotropic sol–gel growth in a water/n‐pentanol emulsion. Due to their chemically asymmetric properties, nanoparticles (NPs) with hydrophilic or hydrophobic surface properties can be selectively loaded inside the NBs or on the outside of the NBs, respectively. A high‐performance nanomotor is constructed by selectively loading catalytically active hydrophilic Pt NPs inside the NBs. It is also demonstrated that these NBs can be used as vessels for various reactions, such as the in situ synthesis of Au NPs, and using Au NP‐loaded NBs as nanoreactors for catalytic reactions.     

Facile Fabrication of Well‐Dispersed Pt Nanoparticles in Mesoporous Silica with Large Open Spaces and Their Catalytic Applications

In this paper, a facile strategy is reported for the preparation of well‐dispersed Pt nanoparticles in ordered mesoporous silica (Pt@OMS) by using a hybrid mesoporous phenolic resin‐silica nanocomposite as the parent material. The phenolic resin polymer is proposed herein to be the key in preventing the aggregation of Pt nanoparticles during their formation process and making contributions both to enhance the surface area and enlarge the pore size of the support. The Pt@OMS proves to be a highly active and stable catalyst for both gas‐phase oxidation of CO and liquid‐phase hydrogenation of 4‐nitrophenol. This work might open new avenues for the preparation of noble metal nanoparticles in mesoporous silica with unique structures for catalytic applications.     

MnO_X-C@SiO_2核壳微球的制备及催化性能

为了制备高性能的Fenton反应催化剂以降解水中污染物,采用SiO_2包覆聚丙烯酸-二氧化锰复合胶团(PAA-Mn@SiO_2)然后碳化的方法,制备了以氧化锰-碳复合物为核,SiO_2为壳的核壳型纳米催化剂(MnO_X-C@SiO_2),该方法简单易行。通过X射线衍射(XRD)、X射线光电子能谱(XPS)、扫描电子显微镜(SEM)、透射电子显微镜(TEM)、比表面积等测试手段对产物进行了分析。结果表明,MnO_X-C@SiO_2中形成了对Fenton反应具有高催化活性的低价氧化锰(Mn_3O_4和MnO)。此外,SiO_2壳层能有效防止氧化锰在碳化过程中长大并阻止产物聚集,其内部的碳组分还能进一步稳定氧化锰纳米粒子并促进有机污染物的富集。MnO_X-C@SiO_2的比表面积为317.3 m~2/g,在水中具有良好的分散性,在Fenton反应催化降解亚甲基蓝(MB)溶液的过程中,仅经过40 min,降解率就可达到96.8%。     

一维CdTe@C@TiO2-Au异质结纳米线的制备及其光催化性能

先利用一步水热法制备了具有核壳结构的CdTe@C纳米线,然后以钛酸异丙酯（TIP）作为钛源对CdTe@C纳米线进行二氧化钛包覆,最后通过原位还原HAuCl4的方法将Au纳米粒子组装到CdTe@C@TiO₂表面形成CdTe@C@TiO₂-Au一维异质结纳米复合材料。用扫描电镜（SEM）,X射线能谱（EDX）,透射电镜（TEM）,X射线衍射（XRD）,X射线光电子能谱（XPS）和紫外-可见漫反射光谱（UV-Vis DRS）等对材料进行表征。探究了CdTe@C@TiO₂-Au催化剂在模拟可见光下降解罗丹明B（RhB）的光催化性能。实验结果表明：不同催化剂对RhB的光降解率不一样,其效果依次为CdTe@C@TiO₂-Au > CdTe@C@TiO₂ > pure TiO₂,其中CdTe@C@TiO₂-Au能在270 min的模拟太阳光下对RhB的光降解率达95.3%,这主要得益于CdTe、碳层、TiO₂和具有表面等离子效应的纳米Au的共同作用。     

有序多孔过渡金属氧化物及其负载贵金属催化剂对挥发性有机物氧化的催化性能

大部分的挥发性有机物(VOCs)污染环境,危害人身健康.目前,我国虽然已开展了治理 VOCs污染的工作,但还缺乏有效的、拥有自主知识产权的 VOCs治理技术,因此研发新型高效 VOCs处理技术迫在眉睫.催化氧化法是公认的最有效消除 VOCs的途径之一,而高性能催化剂的研发是实现该过程的关键.近年来,人们围绕消除 VOCs的高效且价廉的催化剂的研发开展了卓有成效的工作,许多过渡金属氧化物、混合或复合金属氧化物及其负载贵金属催化剂均被认为是有效的催化氧化材料.与体相材料相比,多孔材料具有发达的孔道结构和高的比表面积,一方面有利于反应物的扩散、吸附和脱附,因而具有更高的催化活性和选择性;另一方面有利于活性组分(如贵金属等)在多孔材料表面的高分散,抑制活性组分的烧结,因而具有更好的催化稳定性.本文简述了近年来多孔金属氧化物在环境污染物消除领域的研究进展,阐述了以有序介孔或大孔过渡金属氧化物、钙钛矿型氧化物和负载贵金属催化剂的制备及其对典型 VOCs(如苯系物、醇类、醛类及酮类等)氧化的催化性能,重点介绍了四类催化材料,包括有序介孔过渡金属氧化物或复合氧化物(Co3O4, MnO2, Fe2O3, Cr2O3和 LaFeO3等)催化剂,有序介孔金属氧化物负载贵金属(Au/Co3O4, Au/MnO2和 Pd/Co3O4等)催化剂,三维有序大孔过渡金属氧化物或复合氧化物(Fe2O3, LaMnO3, La0.6Sr0.4MnO3和 La2CuO4等)催化剂,以及三维有序大孔金属氧化物负载贵金属(Au/Co3O4, Au/LaCoO3, Au/La0.6Sr0.4MnO3和 AuPd/Co3O4等)催化剂的制备及其物化性质与对苯、甲苯、二甲苯、乙醇、丙酮、甲醛、甲烷或氯甲烷等 VOCs氧化的催化性能之间的相关性.借助二氧化硅或聚甲基丙烯酸甲酯微球等硬模板,采用纳米浇铸法可制备出二维或三维的有序单一或多级孔道结构的金属氧化物.研究表明,多孔金属氧化物的催化性能远优于其体相甚至纳米催化剂的.有序多孔材料的优异催化性能与其拥有大的比表面积、高的吸附氧物种浓度、优良的低温还原性、独特的孔道结构、活性组分的高分散以及贵金属与氧化物载体之间的强相互作用等有关.探明影响催化剂活性的因素有利于从原子水平上认识催化过程,为新型高效催化剂的设计与制备奠定基础.本文还指出了此类研究中存在的一些问题,例如利用硬模板法制备多孔材料的缺点是目标催化剂的收率低,硬模板浪费严重,大规模制备多孔催化剂势必增加制备成本,这些问题有待于妥善解决.与此同时,还展望了 VOCs消除技术的未来发展趋势,采用多种技术联用的方法有望最大程度地提高 VOCs的消除效率.     

Fabrication of Ruthenium Nanoparticles in Porous Organic Polymers: Towards Advanced Heterogeneous Catalytic Nanoreactors

A novel strategy has been adopted for the construction of a copolymer of benzene–benzylamine‐1 (BBA‐1), which is a porous organic polymer (POP) with a high BET surface area, through Friedel–Crafts alkylation of benzylamine and benzene by using formaldehyde dimethyl acetal as a cross‐linker and anhydrous FeCl₃ as a promoter. Ruthenium nanoparticles (Ru NPs) were successfully distributed in the interior cavities of polymers through NaBH₄, ethylene glycol, and hydrothermal reduction routes, which delivered Ru‐A, Ru‐B, and Ru‐C materials, respectively, and avoided aggregation of metal NPs. Homogeneous dispersion, the nanoconfinement effect of the polymer, and the oxidation state of Ru NPs were verified by employing TEM, energy‐dispersive X‐ray spectroscopy mapping, cross polarization magic‐angle spinning ¹³C NMR spectroscopy, and X‐ray photoelectron spectroscopy analytical tools. These three new Ru‐based POP materials exhibited excellent catalytic performance in the hydrogenation of nitroarenes at RT (with a reaction time of only ≈30 min), with high conversion, selectivity, stability, and recyclability for several catalytic cycles, compared with other traditional materials, such as Ru@C, Ru@SiO₂, and Ru@TiO₂, but no clear agglomeration or loss of catalytic activity was observed. The high catalytic performance of the ruthenium‐based POP materials is due to the synergetic effect of nanoconfinement and electron donation offered by the 3D POP network. DFT calculations showed that hydrogenation of nitrobenzene over the Ru (0001) catalyst surface through a direct reaction pathway is more favorable than that through an indirect reaction pathway.     

Step-by-step synthesis of copper(I) complex supported on platinum nanoparticle-decorated mesoporous silica hollow spheres and its remarkable catalytic performance in Sonogashira coupling reaction

In this study, a step-by-step method for the synthesis of platinum nanoparticles and copper(I) complex supported on mesoporous silica hollow spheres (Pt-MSHSs-Cu) is introduced. Scanning electron microscopy, transmission electron microscopy, powder X-ray diffraction, Fourier transform infrared spectroscopy, nitrogen adsorption–desorption, energy-dispersive X-ray spectrometry, X-ray photoelectron spectroscopy, and elemental and thermogravimetric analyses were applied for characterization of the surface, structure, size, phase composition, and morphology of the synthesized materials. The characterized material, Pt-MSHSs-Cu, was used as an efficient and heterogeneous catalyst in the Sonogashira coupling reaction under different reaction conditions. In comparison with MSHSs, Cu(I)-functionalized MSHSs (MSHSs-Cu), and Pt-MSHSs samples, the Pt-MSHSs-Cu catalyst exhibited significantly increased catalytic performance with 91.50% yield. Therefore, the results obtained suggested a synergistic effect derived from platinum nanoparticles, MSHSs substrate, and copper(I) complex, which enhanced the rate of the Sonogashira coupling reaction.     

苯基磺酸官能化中孔硅基材料催化环己酮Aldol缩合反应

2-(1环-己烯基)环己酮是一种植物防腐杀菌剂,作为制备柑桔类水果的保鲜剂、分散染料染色的载体物质邻苯基苯酚(Ortho-phenylphenol,OPP)的原料而备受重视。其与环己叉基环己酮互为同分异构体,均由环己酮A ldol缩合反应合成,该过程是包括醇醛缩合、脱水在内的亲核加成-消除反应,