铂-金交替修饰的铂核纳米颗粒的制备与表征

通过吸附在铂纳米颗粒表面的氢交替还原氯金酸和氯铂酸,得到了复合型纳米颗粒Pt@Au/Pt,用UV-Vis光谱、TEM和XRD对其进行了表征.     

星状多臂共聚物h-PCMS-g-PEMA-b-PMMA的合成

在CuCl/bpy催化体系下,通过对氯甲基苯乙烯（CMS）自引发制得球状超支化聚对氯甲基苯乙烯（h-PCMS）,再以h-PCMS作为大分子引发剂,通过两步原子转移自由基聚合（ATRP）成功在球状h-PCMS表面接枝二嵌段聚合物聚甲基丙烯酸乙酯-b-聚甲基丙烯酸甲酯（PEMA-b-PMMA）,合成了星状多臂共聚物h-PCMS₂₇₀₀-g-PEMA₄₁₀₀₀-b-PMMA₁₅₀₀₀（下标为分子量）,分子量分布为1.6,其结构和性能经¹H NMR、 IR、 GPC和DSC表征。通过¹H NMR定量分析表明,h-PCMS中的苄基氯具有活性,可进一步引发接枝反应,次苄基氯不能引发ATRP反应。在每一个h-PCMS表面有接近三分之一的苄基氯参与接枝反应,接枝臂数为6。     

Butacene合成方法的改进及性能研究

与以二茂铁,4-氯丁酰氯为原料的传统合成方法不同,直接以γ-二茂铁丁酸为原料,采用NaBH4-I2-THF体系代替有毒的锌汞齐作为还原剂,以SOCl2为氯代试剂,制备了4-氯丁基二茂铁,将其与镁粉反应制得格式试剂,再与二甲基氯硅烷反应合成4-二茂铁丁基二甲基硅烷,在高效可重复使用铂催化剂(二氧化硅负载壳聚糖络合氯铂酸SiO2-CS-Pt)催化下与端羟基聚丁二烯(HTPB)硅氢加成得到高收率的巴特辛(Butacene).采用1H-NMR和FTIR对其化学结构进行了表征,采用TGA分析了产物的热性能,并测定了接枝率和羟值.研究结果表明,所得产物与目标产物相符,初始热分解温度提前,热敏感度增加,热稳定性增加,具有良好的催化性能.     

氨功能化陶瓷膜支撑体担载钯纳米颗粒及其增强的催化性能(英文)

采用双氨基硅烷偶联剂N-β-(氨乙基)-γ-氨丙基三甲氧基硅烷(AAPTS)对陶瓷膜表面接枝功能化并负载钯纳米颗粒,制得一种有效的可重复使用的催化剂.利用X射线衍射、扫描电镜、电子能谱、感应耦合等离子体、X射线光电子能谱和高分辨透射电镜对催化剂进行了物性表征,并将其用于催化对硝基苯酚加氢制对氨基苯酚反应.和单氨基硅烷γ-氨丙基三乙氧基硅烷(3-APTS)功能化改性相比,担载在AAPTS功能化陶瓷膜上的钯纳米颗粒具有更高的催化活性和稳定性.相比于3-APTS,AAPTS分子中含有两个氨基,具有更强的供电子效应,因此钯纳米颗粒可更多更稳定地负载在AAPTS功能化陶瓷膜上,从而具有更高的催化活性和稳定性.     

高效组合型 Pd/C 催化剂用于 Suzuki 偶联反应

 采用有机金属 Pd2(dba)3 (dba 为二亚苄基丙酮) 还原分解法制得均匀分布的 Pd 纳米颗粒 (粒径为 3~6 nm) 混合液, 并用活性炭直接吸附得到了组合型 Pd/C 纳米催化剂. 采用透射电子显微镜、X 射线光电子能谱和 X 射线衍射等手段测定了催化剂表面 Pd 颗粒大小分布、晶型和化学态等. 将该催化剂用于 Suzuki 碳-碳偶联反应, 其催化活性比浸渍法制备的 Pd/C 催化剂高 2 倍以上. 以溴代芳烃为底物时, 在 80 oC 下 0.5 h 后偶联产物收率可达 98% 以上. 以邻氯硝基苯为底物时, 在 110 oC 下 1 h 后偶联产物收率可达 64%; 延长反应时间, 产物收率可达 90% 以上.     

用于质子交换膜燃料电池的碳载铂电催化剂

 以甲醛为还原剂，氯铂酸为原料，XC－72碳黑为载体，制备了不同铂含量的碳载铂电催化剂，并用BET，XRD，TEM和循环伏安法对催化剂进行了表征，用质子交换膜燃料电池单电池对催化剂性能进行了评价．结果表明，铂晶粒主要吸附在碳黑的表面和大孔中．当催化剂的铂载量由20％提高到40％时，由于铂颗粒占据部分碳黑表面，使催化剂的孔体积和比表面积都有所减小；当铂载量进一步提高到60％时，由于铂晶体颗粒形成的微孔开始占一定分率，使催化剂的总体积和比表面积的减小幅度下降．铂晶体颗粒大小在2～4nm范围内；随着铂载量的提高，表面铂有部分聚结，铂晶体的粒径增大，催化剂的电化学比表面积减小．铂载量为40％时，燃料电池阴极的性能最好．     

纳米二氧化硅的表面改性研究

以γ-缩水甘油醚丙基三甲氧基硅烷(GPTMS)对酸催化水解正硅酸乙酯(TEOS)聚合得到的纳米二氧化硅胶粒表面进行接枝改性,用激光粒径仪测定二氧化硅颗粒的粒径,并用透射电子显微镜(TEM)观察了改性前后二氧化硅胶粒的分散状况,采用傅立叶红外(FTIR)光谱法对改性前后的二氧化硅粉体进行了分析,通过热失重分析(TGA)法对GPTMS接枝改性二氧化硅胶粒表面的接枝度进行分析计算,同时对颗粒溶胶的ζ电位进行了测试,结果表明:改性后二氧化硅胶粒分散性大大提高,硅烷偶联剂浓度对接枝度有显著影响,当GPTMS的浓度为1mL/S iO2(g)时,接枝度达到最大,且颗粒表面的物理化学性能发生显著变化。     

接枝型三相转移催化剂的制备及其催化作用

将苯乙烯(St)接枝聚合在微米级硅胶表面,制备了接枝微粒PSt/SiO2;使用新型氯甲基化试剂1,4-二氯甲氧基丁烷,对接枝在硅胶表面的聚苯乙烯进行了氯甲基化(CM)反应,制得了氯甲基聚苯乙烯/硅胶(CMPS/SiO2)接枝微粒;使三乙胺与CMPS分子链上的苄氯基团发生季铵化反应,制得了固载有季铵盐(Quaternary salt)的接枝微粒QPSt/SiO2,即制得了接枝型三相相转移催化剂.将此相转移催化剂用于氯化苄与乙酸钠合成乙酸苄酯的相转移催化反应,考察了催化活性、各种因素对相转移催化反应的影响及催化剂的重复使用性能.实验结果表明,接枝型三相相转移催化剂QPSt/SiO2对乙酸苄酯的合成具有较高的催化活性,在液-固-液之间即可有效地实现反应物种乙酸根的转移,在60℃的较低温度下反应7 h,氯化苄的转化率可达66.1%;研究发现,固体催化剂QPSt/SiO2表面接枝聚合物PSt的季铵化程度对其催化活性有很大的影响,季铵化程度过大与过小催化活性都较低,当季铵化程度为20%左右时,催化剂的活性最高.     

氯磷灰石负载金属卤化物催化芳香化合物的Friedel-Crafts 苄基化反应研究

以氯磷灰石为载体,采用水热法制各了氯磷灰石负载金属卤化物固体酸催化剂,通过IR,XRD对载体和催化剂的结构进行了表征.研究了催化剂对芳香化合物与苄基氯、苄基溴和苄基醇的Friedel-Crafts烷基化反应.结果表明,溴化锌负载氯磷灰石催化剂的活性最高,而且催化剂易回收和重复使用,催化剂重复使用5次活性没有明显降低.     

Pt@Ag/Pt复合型纳米颗粒的合成与表征

通过吸附在铂纳米颗粒表面的氢交替还原硝酸银和氯铂酸,得到了复合型纳米颗粒Pt@Ag／Pt,用紫外-可见吸收光谱（UV-Vis）、透射电子显微镜（TEM）、X-射线衍射（XRD）对其进行了表征。通过氢化催化苯甲醛反应,由于Pt与Ag双金属间的协同效应,其催化活性较纯铂好。     

Composite Particles From Pickering‐Stabilized Radical Mediated Thiol‐Ene Suspension Polymerizations

Pickering stabilization is a facile method to create composite colloidal particles. Inorganic colloidal SiO₂ nanoparticles are often used as the stabilizer for particles instead of the more common amphiphilic surfactants. Here the use of this approach in radical‐mediated thiol‐ene suspension polymerizations using monomers 1,3,5‐triallyl‐1,3,5‐triazine‐2,4,6(1H,3H,5H)‐trione (TTT) and pentaerythritol tetrakis (3‐mercaptopropionate) (PETMP) is described. The resulting micron‐sized crosslinked poly(thioether) colloidal particles are coated with 80 nm silica nanoparticles. The addition of a small amount of various costabilizers is examined (hexadecane, cetyl alcohol and toluene), and while all yielded particles, cetyl alcohol provide more consistent results. Scanning electron microscopy and thermal analysis of the composite particles demonstrate morphologies that are consistent with a raspberry‐like structure. No significant changes to the glass transition temperature are observed, which is consistent with the silica nanoparticles being located at the surface of the polymer particles.     

Surface grafting of polymers onto inorganic ultrafine particles: Reaction of functional polymers with acid anhydride groups introduced onto inorganic ultrafine particles

The surface grafting onto inorganic ultrafine particles, such as silica, titanium oxide, and ferrite, by the reaction of acid anhydride groups on the surfaces with functional polymers having hydroxyl and amino groups was examined. The introduction of acid anhydride groups onto inorganic ultrafine particle was achieved by the reaction of hydroxyl groups on these surfaces with 4-trimethoxysilyltetrahydrophthalic anhydride in toluene. The amount of acid anhydride groups introduced onto the surface of ultrafine silica, titanium oxide, and ferrite was determined to be 0.96, 0.47, and 0.31 mmol/g, respectively, by elemental analysis. Functional polymers having terminal hydroxyl or amino groups, such as diol-type poly(propylene glycol) (PPG), and diamine-type polydimethylsiloxane (SDA), reacted with acid anhydride groups on these ultrafine particles to give polymer-grafted ultrafine particles: PPG and SDA were considered to be grafted onto these surfaces with ester and amide bond, respectively. The percentage of grafting increased with increasing acid anhydride group content of the surface: the percentage of grafting of SDA (M_n = 3.9 × 10³) onto silica, titanium oxide, and ferrite reaching 64.7, 33.7, and 24.1%, respectively. These polymer-grafted ultrafine particles gave a stable colloidal dispersion in organic solvents.     

Photografting of vinyl polymers onto ultrafine inorganic particles: Photopolymerization of vinyl monomers initiated by AZO groups introduced onto these surfaces

The photografting of polymers onto ultrafine inorganic particles, such as silica and titanium oxide, initiated by azo groups introduced onto these surfaces was investigated. The introduction of azo groups onto the particles was achieved by the reaction of 4,4′-azobis(4-cyanopentanoic acid) with surface isocyanate groups, which were introduced by the treatment with tolylene 2,4-diisocyanate. It was found that the photopolymerization of vinyl monomers, such as methyl methacrylate (MMA), styrene, and N-vinylcarbazole, is initiated by ultrafine particles having azo groups. The corresponding polymers were effectively grafted onto these surfaces through the propagation of the polymer from the surface radicals formed by the photodecomposition of the azo groups: e.g., the percentage of grafting of PMMA and polystyrene onto silica was reached to 112 and 176%, respectively. The percentage of grafting onto silica in the graft polymerization initiated by photodecomposition of surface azo groups was much larger than that initiated by thermal decomposition. Polymer-grafted ultrafine particles thus obtained gave a stable colloidal dispersion in good solvents for the grafted chain. © 1994 John Wiley & Sons, Inc.     

Organosilsesquioxane Particles Prepared by Controlled Sol-Gel Process or Heterocondensation with Colloidal Silica Particles: A Novel Route Towards Nanoporous Silica Particles by a Templating Effect

Hybrid organic-inorganic particles containing labile organic templates have been prepared by either controlled Sol-Gel processing or co-condensation of colloidal silica particles with organosilicon precursors. Chemical removal of the templating organic spacer led to monomodal, microstructured porous silica particles exhibiting up to 50% porosity. Particle size and distribution, and porosity varied depending upon the process and the chemistry used to remove the porogen organic groups.     

纳米金掺杂中空微胶囊的制备与表征

将表面含有双键的二氧化硅微粒分散在纳米金和聚乙烯吡咯烷酮溶液中.在此溶液中以聚乙烯吡咯烷酮为模板聚合物进行丙烯酸的模板聚合,得到二氧化硅为核、聚丙烯酸/聚乙烯吡咯烷酮/纳米金为壳层的核壳结构微粒.用氢氟酸将二氧化硅微粒去除后,得到了纳米金粒子掺杂的微胶囊.分别用扫描电子显微镜和激光共聚焦显微镜表征了微胶囊在干态和湿态下的形貌.通过电子衍射和透射电子显微镜确证了纳米金粒子在微囊壁上的存在和分布.     

Evaporation‐Driven Self‐Assembly of Colloidal Silica Dispersion: New Insights on Janus Particles

The evaporation driven self‐assembly of novel colloidal silica Janus particles was evaluated by scanning electron microscopy in comparison to unfunctionalized silica particles. The cyclodextrin‐ and azobenzene‐modified compound was obtained utilizing Pickering emulsion approach, in which the particles were immobilized on solidified wax droplets and subsequently functionalized. Silica particles were modified with 3‐aminopropyl trimethoxysilane and afterward reacted with tosyl‐β‐CD or phenylazo(benzoic acid), respectively. Mesoscopic structures of the colloidal dispersions, as dried films from aqueous solution, have been investigated by scanning electron microscopy and dynamic light scattering. Interestingly, it has been observed that the Janus particles show a significantly different evaporation‐induced assembly than the unmodified particles.     

Three-dimensional colloidal crystals with a well-defined architecture

Monodisperse silica spheres with diameters of 220-1100 nm were prepared by hydrolysis of tetraethyl orthosilicate (TEOS) in an alcoholic medium in the presence of water and ammonia. By grafting vinyl or amino groups onto silica surfaces using the coupling agents allyltrimethoxysilane and aminopropyltriethoxysilane, respectively, amphiphilic silica spheres were obtained and could be organized to form a stable Langmuir film at the air-water interface. The controlled transfer of this monolayer of particles onto a solid substrate gave us the ability to build three-dimensional regular crystals with a well-defined thickness and organization. These colloidal crystals diffract light in the UV, the visible, and the near-infrared (NIR) spectral regions, depending on the size of the silica spheres and according to Bragg's law. The depth of the photonic stop band can be tuned by varying the number of deposited layers of particles. By using successive depositions, we could prepare multilayered films with silica spheres of different sizes. The thickness of each slab in the binary crystals can be tuned at the layer level, while the crystalline order of each layer is well preserved.     

单分散聚丙烯酸丁酯-二氧化硅核壳粒子的制备

近年来,有机-无机核壳材料因其具有可调的光、电、磁等特性而备受关注．无机物外壳可以增强粒子的热力学稳定性、机械强度和抗拉性能．高分子乳胶粒内核具有弹性,且易成膜,外部包覆无机物的乳胶粒可结合两者特性并产生协同效应．     

Characterization of polymer-coated silica particles by microelectrophoresis

Electrophoretic mobility measurements have been used to characterize monodispersed colloidal particles of silica, silica coated with alumina (cores), of these cores incorporating a dye (pigments), and finally of pigments coated with polymers. The latter consisted of poly(divinylbenzene), of poly(vinylbenzyl chloride), and of their copolymers, synthesized directly on the core or pigment particles, with and without subsequent sulfonation.