超声波辅助制备单分散金属包覆聚苯乙烯导电微球

为了制备单分散聚合物基导电微球,以交联聚苯乙烯(PS)微球为基体,通过超声波辅助的化学镀方法制备了单分散Ni/PS导电微球,接着采用置换法在导电微球表面包覆一层导电性更好的Au层。采用FI-IR,SEM,EDS,XRD等测试方法分别对PS微球及导电微球的官能团变化、形貌、元素组成及晶型结构进行表征,结果表明:超声的引入可以改善导电微球的分散性;导电微球形貌规则,镀层连续均一且有纳米级"丘状"突起。经过金层包覆后导电微球的体电阻率可达到6.9×10-3Ω.cm,可以满足ACF中导电微球的使用要求。     

CdSe纳米晶／MEH—PPV复合型光电池研究

采用单前驱体热解法、高温微乳液法合成了高质量的CdSe纳米晶,将CdSe纳米晶按照一定比例与聚苯乙烯撑（MEH—PPV）共混制成光电池,利用TEM、XRD等研究了纳米晶的形貌结构特征,结果显示,所合成的半导体CdSe纳米晶为闪锌矿结构,直径在3-5nm之间,复合光电池最好的器件能量转化达到0．85％,     

SiO2空心球的制备与表面形貌调控

以聚苯乙烯(PS)微球为模板,通过水解正硅酸乙酯来包裹PS微球,制备了PS/SiO_2核壳结构微球,然后通过高温煅烧得到SiO_2空心球。利用纳米粒度仪、扫描电子显微镜、透射电子显微镜分析SiO_2空心球的粒径和表面形貌。采用控制变量法分别研究了PS微球表面电荷、pH、水和正硅酸乙酯的用量对SiO_2空心球表面形貌的影响。实验证明,以表面带正电荷的PS微球为模板,反应体系pH=11.0,正硅酸乙酯注入速度为100μL/min时,制备的SiO_2空心球表面最光滑。     

Ni/PS核壳结构纳米复合微球的制备及磁性能

采用乳液聚合法制备了纳米级聚苯乙烯微球,利用化学沉积法在微球表面镀镍,制备出了具有磁性的金属/高分子(Ni/PS)纳米复合微球。利用透射电子显微镜(TEM)、X射线衍射仪(XRD)和能量色散谱仪(EDS)分别对镀镍前后纳米微球的形貌结构、相组成、化学成分进行表征分析,用振动样品磁强计(VSM)测试了不同制备工艺条件下复合微球的磁学性能。结果表明,活化工艺、还原剂浓度、镀液pH值和温度对镀后复合微球的磁性能有显著影响。根据磁性能结果,优化工艺参数,制备了具有规则球形、单分散性好、粒径约为100nm、镀层完整、均匀的磁性Ni/PS核壳结构纳米复合微球,并获得最大的饱和磁化强度Ms=8.8764emu/g。     

交联PS微球负载纳米Ni颗粒的制备及表征

采用种子聚合法制备出交联聚苯乙烯(PS)微球,经预处理在微球表面引入官能团,采用化学镀法在微球表面负载纳米级Ni颗粒,利用FI-IR、SEM、XRD等测试手段对其进行表征,结果表明:PS微球粒径均匀,平均粒径约为4.3μm,表面光滑;微球负载的纳米Ni颗粒分散性良好、平均晶粒度为9.41nm.利用负载微球对高氯酸铵(AP)进行催化实验,表明负载微球可使AP高温分解峰降低94.2℃左右.研究表明:采用PS微球负载可提高纳米Ni颗粒的分散性,进而提高了Ni颗粒的催化性能.     

CdSe/SiO2复合微球的光电性及在安培型生物传感器中的应用

利用介孔材料纳米孔道作为微反应器,将带正电荷的Cd离子与介孔二氧化硅(SiO2)表面带有负电荷的-SiOH相互静电吸附生成Cd-O-Si,然后采用低温方法使其与SeSO32-反应,缓慢生长,形成CdSe纳米晶.XRD和高倍透射电镜说明介孔孔道中生成了CdSe纳米颗粒.利用CdSe/SiO在UV激发下产生光电流的特性,用得到的CdSe/SiO复合微球作载体固定辣根过氧化物酶HRP,在OTE涂上一层HRP/CdSe/SiO2膜,应用到H2O2生物传感器的检测.过氧化物酶-电极系统内,在紫外光(UV)365nm波长照射下,由CdSe/SiO2产生的光电子和电极提供的电子同时对H2O2进行还原,产生的空穴被CdSe和SiO2的界面捕获,提高了反应速度.     

单分散Eu~(3+)-PS荧光微球的制备及性能

采用分散聚合法研究了单分散纳米聚苯乙烯(PS)微球和宽稀土含量荧光PS微球的合成。在沸水排氧条件下,分别研究了单分散纳米PS微球、稀土配合物(Eu(MAA)3phen)与苯乙烯(St)共聚微球的合成和反应体系稳定性控制,成功制备出了粒径范围在120~260 nm的单分散PS微球及Eu~(3+)-PS共聚物荧光微球,拓宽了分散聚合制备PS微球的粒径范围。采用红外光谱、同步热分析、扫描电镜和透射电镜对产物的结构进行了表征,紫外光谱和荧光光谱对产物的光学性能进行了测试。结果表明产物的单分散性良好,具有Eu~(3+)离子的特征荧光发射。     

表面化学沉积法制备SiO2空心微球

研究了以聚苯乙烯(PS)微球为模板,采用表面化学沉积技术制备SiO2@PS微球的工艺.利用ξ电位及FT-IR吸收光谱分析了硅烷偶联剂(MPS)及引发剂(KPS)对PS微球表面电荷及表面官能目的影响,在PS微球表面官能化过程中加入KPS,促进PS微球与MPS聚合,增加了微球表面Si-OH的浓度,实现TEOS在PS微球表面的均匀包裹,制得了单分散的核壳结构的SiO2@PS微球.通过调整TEOS的加入量,可得到壁厚在20～55nm的SiO2空心球.     

不同形貌CdSe纳米晶的合成及其形成机理研究

采用水热反应法,通过调节反应时间制备得到了不同形貌的CdSe纳米晶材料,并用TEM、XRD、EDS、XPS等分析手段对其形貌结构进行表征。研究表明,在反应温度为180℃的条件下,所得产物均为六方晶相的CdSe纳米晶,形貌随着反应时间的改变而发生变化:当控制反应时间为2h、5h、10h时,得到的CdSe纳米晶的形貌分别为树枝状、由树枝状到棒状过渡的簇状及棒状。分析了CdSe纳米晶形成的化学反应原理,并运用结晶学原理和相关模型理论对CdSe纳米晶的形成机理及其形貌变化进行了探讨。     

无模板法可控合成多层次结构二氧化钛微球

以1,4-二氧六环为溶剂,采用溶剂热法成功实现无模板法可控合成二氧化钛多层次结构微球。通过系统改变反应体系中浓盐酸与四异丙醇钛(TTIP)相对物质的量比能够有效调控二氧化钛形貌。当浓盐酸与TTIP物质的量比控制在0(或0.7或0.9)、1.8、3.6与5.7时,所得产物分别为纳米颗粒构建二氧化钛微球、纳米棒修饰二氧化钛微球、纳米棒花菜结构以及纳米棒海胆结构。在成功进行形貌调控的基础上,进一步探讨了二氧化钛多种结构的形成机理,并对其光催化产氢性能进行了表征。研究发现,在这4种结构中,纳米棒修饰二氧化钛微球具有最佳的光催化性能,这可能是由于同时存在金红石和锐钛矿两种晶型而形成异质结结构所导致。     

Reduced photo-instability of luminescence spectrum of core-shell CdSe/CdS nanocrystals

Coated CdSe/CdS nanocrystals have been synthesized through a new reaction routine in micelle solution. High resolution transmission electron microscope image demonstrated the monodispersity and core-shell structure of CdSe/CdS nanocrystals. Photooxidation experiments shown that by coating with a wider bandgap material CdS, the surface states of CdSe cores could be decreased and the photo-instability of their luminescence spectrum could be reduced. This phenomena were temporary interpreted that lack of carriers at the outlayer surface reduced photooxidation degradation of CdSe/CdS nanocrystals.     

A mild phosphine-free synthesis of alkylamine-capped CdSe nanocrystals

A new phosphine-free approach has been developed to synthesize high-quality cadmium selenide (CdSe) nanocrystals with cubic zinc-blende structure, by using the highly reactive selenium (Se) precursor at milder temperature than that used in the traditional phosphine route. This Se precursor was obtained from the reduction of Se powder by sodium borohydride in N,N-dimetbylformamide, in the absence of phosphine. Without the addition of other long-chain coordinating substances in this approach, the alkylamines such as dodecylamine (DDA) and octylamine (OA) were used as reaction solvents, and they also acted as surface capping reagents to produce DDA-capped and OA-capped CdSe NCs, respectively. The rapid nucleation and slow growth were observed by ultraviolet-visible absorption spectrum. The resulting OA-capped CdSe NCs grew faster compared with DDA-capped CdSe NCs under the same other conditions. These as-synthesized CdSe nanocrystals showed relatively narrow size distribution and high photoluminescence quantum efficiency (up to 9.4% for OA-capped CdSe NCs). This mild approach is low cost, relatively low danger and high production yield (approximately 80%), indicating that it is very effective for the phosphine-free synthesis of alkylamine-capped CdSe nanocrystals.     

Layer-by-layer growth of CdSe-based nanocrystal light-emitting diodes

The partial exchange of surface-passivating trioctylphosphine oxide (TOPO) on CdSe and ZnS-clad CdSe (CdSe/ZnS) nanocrystals with primary amines was utilized to grow ultra-thin films of these nanocrystals under nonaqueous conditions. This growth was achieved using 1,12-diaminododecane in a layer-by-layer assembly format, where one of the amino groups binds with the nanocrystal surface and the other regenerates the interface for further binding of nanocrystals. The nature of the growth is dependent on the relative surface affinity between the TOPO and the primary amine toward the zinc or cadmium sites on the nanocrystals. Using this technique, high-quality luminescent films of these nanocrystals can be built with well-defined thicknesses. Electroluminescent devices have been fabricated using this methodology.     

Effect of surface capping molecules on the electronic structure of CdSe nanocrystal film

The optical band gap and the valence band of CdSe nanocrystals were investigated with respect to surface capping molecules by using photoluminescence and synchrotron photoemission spectroscopy. The optical band gap was shown to be mainly dependent on the size of the molecule controlling the inter-particle distance; the valence band, however, mainly depended on the chemical bonding nature of the molecule. UV in air and anneal under ultra high vacuum (UHV) were carried out to control the surface capping pyridine content on CdSe nanocrystal films. With UV treated film, a great reduction in the pyridine content was found, but extra oxygen was absorbed onto the naked CdSe surface. The surface absorbed oxygen exerted a strong influence on the electronic structure of CdSe nanocrystal films. This extra oxygen was successfully removed though UHV-anneal, and it was possible to distinguish the effect of oxygen from the effect of surface capping pyridine on the electronic structure of CdSe nanocrystal film. A quantitative relationship between the valence band maximum of CdSe nanocrystal films and the content of surface-absorbed oxygen could be given.     

魔力尺寸硒化镉纳米晶的压力稳定性研究

在极端条件下应用的耐压材料必须具有极高的结构和性能稳定性。魔力尺寸纳米晶体具有良好的结构、超小的粒子尺寸和精确的原子组成,逐渐成为研究的热点。采用胶体化学方法合成了硒化镉(CdSe)魔力尺寸纳米晶,其第一激子吸收峰位于463nm处,相应的光致发光光谱表现出窄的半高宽,仅为13nm。进一步利用金刚石对顶砧压机研究了所制备的CdSe魔力尺寸纳米晶在压力下的光学响应和稳定性。研究结果表明:随着压力的增大,CdSe魔力尺寸纳米晶的吸收和发光峰位保持不变,这种压力下的稳定行为与传统纳米材料在外界压力下所表现的敏感特性相反;压力卸下后,样品仍然保持CdSe魔力尺寸纳米晶的原始结构和形态。CdSe魔力尺寸纳米晶在加压过程中表现出的良好耐压性能,有助于极端压缩条件下的魔力尺寸纳米材料的研究。     

Effects of reaction temperature on size and optical properties of CdSe nanocrystals

We report experimental results on the reaction temperature dependence of luminescence properties in size-controlled CdSe nanocrystals. Such reaction temperature dependent property is also sizedependent. The diameter of the CdSe nanocrystals is tuned from 4–11.0 nm by varying the reaction temperatures. The growth process and characterization of CdSe nanocrystals are determined by photoluminescence (PL) spectroscopy, ultraviolet-visible (UV-Vis) spectroscopy, X-ray photoelectron spectrometry (XPS), X-ray powder diffraction (XRD), transmission electron microscopy (TEM) and high-resolution transmission electron microscopy (HRTEM). The influence of reaction conditions on the growth of CdSe nanocrystals demonstrates that low reaction temperature is favourable for the formation of high quality CdSe nanocrystals.     

Quantification of the morphological transition in cadmium selenide nanocrystals as a function of reaction temperature

Controlling the morphology of semiconductor nanocrystals has typically relied on controlling the concentration and species of surface ligands utilized in synthesis. Specific shapes, such as branched structures are of particular interest as the light harvesting and charge separating layer in a photovoltaic device. In this work we quantify how changes in the reaction temperature affect the resulting morphology of the nanocrystals. The narrowness of the temperature range over which the morphological transition occurred provides guidance to the tolerances necessary in the synthesis of CdSe utilized in commercial devices on a large scale.     

Detection of pathogens using luminescent CdSe/ZnS dendron nanocrystals and a porous membrane immunofilter

A biosensor system for detection of pathogens was developed by using CdSe/ZnS core/shell dendron nanocrystals with high efficiency and stability as fluorescence labels and a flowing chamber with a microporous immunofilter. The antibody-immobilized immunofilter captured the targeted pathogens, Escherichia coli O157:H7 as an example for bacteria and hepatitis B being a model system for viruses. The CdSe/ZnS core/shell dendron nanocrystals were conjugated with the corresponding antibodies and then passed through the microporous membrane where they attached to the membrane-antigen-antibody. The efficient and stable photoluminescence (PL) of the CdSe/ZnS nanocrystals on the formed "sandwich" structure complexes (membrane-antigen-antibody conjugated with the nanocrystals) was used as the detection means. The effects of the pore size of the membranes, buffer pH, and assay time on the detection of E. coli O157:H7 were investigated and optimized. The detectable level of this new system was as low as 2.3 CFU/mL for E. coli O157:H7 and 5 ng/mL for hepatitis B surface Ag (HBsAg). The assay time was shortened to 30 min without any enrichment and incubation.     

Shape control of cadmium hydroxides (Cd(OH)2) sensitive to pH quenching depth and massive production of CdSe nanocrystals by their chemical transformation

This study demonstrates that the structure of cadmium hydroxides (Cd(OH)(2)) precipitated from a basic cadmium nitrate solution can be finely controlled by adjusting the pH of the precursor solution. The synthesis process involves only pouring the saturated solution into pure water to quench the pH and the total process is finished within 30 s. At a shallow pH quenching, the unstable nanoparticles turned into microparticles via a ripening process. Cd(OH)(2) was precipitated in the form of one-dimensional nanowires and then two-dimensional plates as the pH quenching was increased. At a large pH quenching, porous aggregates of Cd(OH)(2) were obtained due to the too fast precipitation. The ultrafine Cd(OH)(2) nanowires were readily transformed into CdSe chain-like nanocrystals. The transformation was quick and gave 100% yield, facilitating massive production of CdSe nanocrystals in an aqueous condition. The Cd(OH)(2) nanowires were directly grown on Si nanowires and transformed into CdSe chain-like nanocrystals, decorating the surface of each Si nanowire.