甲苯-乙二醇两相界面反应合成CdS纳米粒子

以十八胺为表面修饰剂,硬脂酸镉和硫脲为前驱物,在甲苯-乙二醇两相界面处合成了CdS纳米粒子.研究了反应时间、前驱物浓度、前驱物和表面修饰剂摩尔比等因素对合成CdS纳米粒子的影响.采用紫外-可见吸收光谱、荧光光谱、透射电子显微镜(TEM)和广角X射线衍射(WAXD)等方法对CdS纳米粒子的光学性质、形貌及晶体结构进行了表...     

表面修饰纳米CdS制备中两个重要影响因素及结构表征

利用溶胶-凝胶法制备了PVP表面修饰的CdS纳米晶粒。考察了影响纳米CdS制备的两个重要因素Cd²⁺/S^2-和PVP,及其作用机理。确证表面过剩S^2-和PVP在反应体系中的作用是在较高浓度下制备纳米CdS的两个重要因素,进一步确定了PVP的最佳用量。通过TEM、ED、XRD、FT-IR等手段对合成的纳米粒子进行了结构表征,最小粒径为7～10nm,闪锌矿构型,粒子大小及形貌可通过改变Cd²⁺/S^2-及反应物浓度来控制。最后给出了CdS/PVP纳米晶粒的结构模型。     

PAMAM树形分子与Cd2＋的配位作用研究及CdS/PAMAM纳米复合材料的制备与表征

CdS半导体纳米簇具有独特的光、电性能, 如何制备均匀分散的、能够稳定存在的CdS纳米簇是目前的研究热点之一. 以聚酰胺-胺(PAMAM)树形分子为模板, 原位合成了CdS纳米簇. 首先用UV-Vis分光光度法研究了与树形分子的配位机理, 得出G4.5和G5.0的平均饱和配位数分别为16和34, 并发现在G4.5PAMAM树形分子中Cd^2＋主要与最外层叔胺基配位, 在G5.0PAMAM树形分子中Cd^2＋主要与最外层伯胺基配位. 酯端基的G4.5的模板作用要明显优于胺端基的G5.0. 通过改变Cd^2＋与G4.5树形分子的摩尔比可以得到不同粒径的CdS纳米簇. 溶液的pH值对CdS纳米簇影响很大, pH在7.0左右制备的CdS纳米簇粒径小而均匀, 且溶液稳定性高. 用UV-Vis分光光度计和TEM对CdS纳米簇的大小和形貌进行了表征. 结果表明TEM观测CdS纳米簇的粒径要大于用Brus公式的估算值.     

PAMAM树形分子与Cd2＋的配位作用研究及CdS/PAMAM纳米复合材料的制备与表征

CdS半导体纳米簇具有独特的光、电性能, 如何制备均匀分散的、能够稳定存在的CdS纳米簇是目前的研究热点之一. 以聚酰胺-胺(PAMAM)树形分子为模板, 原位合成了CdS纳米簇. 首先用UV-Vis分光光度法研究了与树形分子的配位机理, 得出G4.5和G5.0的平均饱和配位数分别为16和34, 并发现在G4.5PAMAM树形分子中Cd^2＋主要与最外层叔胺基配位, 在G5.0PAMAM树形分子中Cd^2＋主要与最外层伯胺基配位. 酯端基的G4.5的模板作用要明显优于胺端基的G5.0. 通过改变Cd^2＋与G4.5树形分子的摩尔比可以得到不同粒径的CdS纳米簇. 溶液的pH值对CdS纳米簇影响很大, pH在7.0左右制备的CdS纳米簇粒径小而均匀, 且溶液稳定性高. 用UV-Vis分光光度计和TEM对CdS纳米簇的大小和形貌进行了表征. 结果表明TEM观测CdS纳米簇的粒径要大于用Brus公式的估算值.     

硫脲表面修饰的ZnS∶Cd纳米晶的合成及表征

采用硫脲做为表面修饰剂,合成了硫脲表面修饰的掺杂Cd2 的ZnS纳米晶(ZnS∶Cd/SC(NH2)2),用X射线粉末衍射、透射电子显微镜、红外光谱以及荧光光谱等手段进行了表征.实验结果表明,Cd2 掺入了ZnS纳米晶中,硫脲分子中的S原子与该纳米晶表面的金属离子存在配位作用,ZnS∶Cd/SC(NH2)2纳米晶为分散性较好、平均粒径7 nm的球形粒子且具有良好的荧光性质.     

硫脲表面修饰的ZnS:Cd纳米晶的合成及表征

采用硫脲做为表面修饰剂，合成了硫脲表面修饰的掺杂Cd^2＋的ZnS纳米晶（ZnS：CA／SC（NH2）2），用X射线粉末衍射、透射电子显微镜、红外光谱以及荧光光谱等手段进行了表征．实验结果表明，CA抖掺入了ZnS纳米晶中，硫脲分子中的S原子与该纳米晶表面的金属离子存在配位作用，ZnS：CA／SC（NH2）2纳米晶为分散性较好、平均粒径7nm的球形粒子且具有良好的荧光性质．     

水溶性CdSe/CdS核壳纳米粒子制备的影响因素及其对CdSe/CdS光谱特性的影响

以半胱氨酸镉配合物为前体, 在水溶液中合成CdSe纳米粒子, 以CdS对其表面进行修饰, 得到具有核壳结构的CdSe/CdS 纳米粒子. 采用XRD, TEM表征其结构及形貌; 以荧光光谱研究了时间、pH值、壳量、壳前体加入方式、稳定剂用量等因素对CdSe/CdS光谱特性的影响.     

二氧化硅纳米粒子表面修饰及其表征

采用溶胶-凝胶法合成粒径在50—150nm范围内的二氧化硅（SiO2）纳米粒子。用甲基丙烯酸-3-（三甲氧基硅基）丙酯（MPS）对SiO2纳米粒子表面进行修饰，使其表面接枝能参与自由基聚合反应的碳碳双键基团。用元素分析、FTIR、^13C CP／MASNMR和^29Si CP／MASNMR等手段对修饰过的SiO2纳米粒子进行表征，以确证MPS接枝在SiO2纳米粒子上。分析修饰过的SiO2纳米粒子的^29Si CP／MASNMR和FTIR谱图，还可初步推断MPS接枝在SiO2纳米粒子表面的机理：MPS首先发生水解缩合反应形成低聚物，然后通过氢键作用吸附到SiO2纳米粒子表面，最后MPS低聚物中未缩合的硅羟基与SiO2纳米粒子表面的硅羟基发生缩合反应。     

四硫富瓦烯四硫醇盐对纳米硫化物表面的修饰

本文报道用四硫富瓦烯四硫醇盐(TTFS₄^4-，简写TTFS₄)修饰CdS、NiS的纳米微粒的方法，通过TEM、FT-IR等手段对修饰的纳米微粒进行了表征。实验发现CdS/TTFS₄的固体荧光强度随着修饰量的增加而逐渐减弱。表面修饰后的CdS和NiS的电导率比修饰前都有提高，后者更为明显。     

巯基修饰寡聚DNA包覆的CdS纳米粒子

用5'－端的1－C,2-C位之间磷酸根上修饰有巯基的寡聚胞嘧啶(oligoC10-SH)和矣鸟嘌呤(oligoG10-SH)作为包覆剂直接合成了CdS半导体纳米粒子。实验结果表明CdS的表面的寡聚DNA仍可进行正常的复性,并且复性后CdS的荧光发生了有利于DNA分子标识的显著增强。     

Effect of the method of production of TiO<Subscript>2</Subscript>/CdS nanohetero film structures on the effectiveness of photoinduced charge separation

The properties of TiO₂/CdS nanohetero structures produced by the chemical and photocatalytic deposition of CdS nanoparticles on the surface of nanocrystalline films of TiO₂ under the conditions of laser pulse photolysis were studied. It was shown that in the case of photocatalytically formed TiO₂/CdS nanocomposites the spatial separation of the photogenerated charges between the components of the hetero structure, leading to the formation of intermediates of the photochemical transformations (Ti^III centers in the TiO₂ nanoparticles and S^– radical-anions in the CdS nanoparticles), is an order of magnitude more effective.     

CdS-containing nano-assemblies of double hydrophilic block copolymers in water

Two samples of poly(sodium(sulfamate-carboxylate)isoprene)-block-poly(ethylene oxide) copolymer (SCIEO-1 and SCIEO-2) differing in molecular weight and relative length of polyelectrolyte blocks have been used as templates for the synthesis of cadmium sulfide (CdS) nanoparticles in aqueous media. The double-hydrophilic copolymer SCIEO has very high 1D charge density, and its polymer chain structure mimics that of polysaccharide heparin. It is soluble in aqueous media, but the addition of cadmium acetate (Cd(Ac)₂) to its aqueous solution causes the formation of micellar aggregates with Cd²⁺containing insoluble cores above the threshold Cd²⁺ concentration. The trapped Cd²⁺ ions can be chemically transformed to CdS nanoparticles. The stability of hybrid SCIEO/CdS micelles depends on the ratio of PEO-to-SCI lengths: it was found that the SCIEO-2 copolymer with sufficiently long PEO block behaves as an effective stabilizer for the synthesis of CdS nanoparticles embedded in micelles, while SCIEO-1 does not. The morphology of aggregates varies with the Cd-to-SCI ratios and ranges from spherical to mixture of spherical and necklace-like micellar aggregates. A number of experimental techniques including static and dynamic light scattering, fluorescence correlation spectroscopy, atomic force and transmission electron microscopy, UV-vis, and fluorescence spectroscopy were employed for the characterization of both CdS containing hybrid micelles and embedded CdS nanoparticles.     

Room temperature synthesis of CdS nanoparticle-decorated TiO2 nanotube arrays by electrodeposition with improved visible-light photoelectrochemical properties

Controllable CdS nanoparticles (NPs) decorated on TiO₂ nanotube arrays (NTAs) were prepared via electrodeposition in DMSO solution at room temperature, aiming to improve the photoelectrochemical properties of TiO₂ NTA electrode in visible-light region. By tuning the concentrations of sulfur and Cd^2 + as well as the deposition time, CdS NPs with different sizes can be controllably synthesized at room temperature. Excellent photocurrent response and incident photo to current conversion efficiency were achieved with smaller CdS NPs with optimal reactant concentrations and deposition time, which can be attributed to highly efficient charge separation and high dispersion of CdS NPs on both inner and outer surfaces of TiO₂ nanotubes.     

Mechanism of the formation of photosensitive nanostructured TiO<Subscript>2</Subscript> with low content of CdS nanoparticles

A method for synthesizing a CdS/TiO₂ composite material, active in the visible region, was described. The CdS/TiO₂ composite was obtained by the sol–gel synthesis of nanostructured TiO₂ in a medium of a stable colloidal solution of CdS nanoparticles. The TiO₂ matrix produced by the sol–gel process is amorphous and contains a nanocrystalline anatase phase, the content of which depends on the Ti(OBu)₄ hydrolysis rate. The content of CdS nanoparticles forming in the colloidal solution and participating in the TiO₂ matrix sensitization is determined by the initial CdS: Ti(OBu)₄ ratio. Although the content of CdS nanoparticles in the composite is low (no more than 3 wt %), the composite demonstrates catalytic activity in the visible region, thus proving the possibility of reducing the content of toxic CdS nanoparticles in the TiO₂ matrix without decreasing the photosensitivity of the CdS/TiO₂ composite.     

Fe3O4/PEI/Au@CdSe/CdS多功能复合材料的制备与表征

以共沉淀法制备出Fe₃O₄纳米粒子,通过聚乙烯亚胺(PEI)修饰Fe₃O₄纳米粒子,再原位复合上Au纳米粒子,制得Fe₃O₄/PEI/Au纳米颗粒微球。再将Fe₃O₄/PEI/Au纳米颗粒与巯基乙酸修饰的量子点CdSe/CdS连接,成功制备了Fe₃O₄/PEI/Au@CdSe/CdS多功能复合微球。经过傅里叶变换红外光谱仪(FTIR)、荧光分光光度计、荧光显微镜、X射线衍射(XRD)、透射电子显微镜(TEM)及振动样品磁强计(VSM)的表征。结果表明:多功能复合微球的粒径在40 nm左右,具有超顺磁性,剩磁,矫顽力近似等于零,饱和磁化强度为28.83 A·m²·kg^-1,同时兼有优越的荧光性能和金纳米粒子的特性。     

Fe3O4/PEI/Au@CdSe/CdS多功能复合材料的制备与表征

以共沉淀法制备出Fe₃O₄纳米粒子,通过聚乙烯亚胺(PEI)修饰Fe₃O₄纳米粒子,再原位复合上Au纳米粒子,制得Fe₃O₄/PEI/Au纳米颗粒微球。再将Fe₃O₄/PEI/Au纳米颗粒与巯基乙酸修饰的量子点CdSe/CdS连接,成功制备了Fe₃O₄/PEI/Au@CdSe/CdS多功能复合微球。经过傅里叶变换红外光谱仪(FTIR)、荧光分光光度计、荧光显微镜、X射线衍射(XRD)、透射电子显微镜(TEM)及振动样品磁强计(VSM)的表征。结果表明:多功能复合微球的粒径在40nm左右,具有超顺磁性,剩磁,矫顽力近似等于零,饱和磁化强度为28.83A·m₂·kg^-1,同时兼有优越的荧光性能和金纳米粒子的特性。     

Synthesis,characterization and stability of multicore-shell CdS-SiO<Subscript>2</Subscript> nanoparticles

Multicore-shell CdS-Si0₂ nanoparticles were synthesized in AOT/heptane/H₂O reverse micelles at room temperature. CdS-SiO₂ nanoparticles were characterized by UV-vis spectroscopy, TEM, and SEM methods. The results show that multicore-shell composites were formed. Fluorescence properties of composites were also investigated; the data imply that fluorescence properties of the silica-coated CdS nanoparticles were significantly improved when compared to those of the non-coated CdS nanoparticles. The stability of multicore-shell CdS-SiO₂ nanoparticles upon the UV irradiation was higher than that of non-coated CdS nanoparticles.     

Patterning porous matrices and planar substrates with quantum dots

Silica hydrogels and planar substrates were patterned with CdS nanoparticles using a photolithographic method based on the photo dissociation of thiols and cadmium-thiolate complexes. Silica hydrogels were prepared via a standard base-catalyzed route. The solvent was exchanged with an aqueous solution of CdSO₄ and 2-mercaptoethanol, and the samples were then exposed to a focused ultraviolet beam. Planar substrates were patterned by illuminating a precursor solution spin coated on the substrates. CdS nanoparticles formed in the illuminated spots, and had a diameter below about 2 nm. The diameter of the spots illuminated by the UV beam could be varied from a few hundred to a few μm, on both hydrogels and planar substrates. Samples were characterized with transmission electron microscopy, X-ray photoelectron spectroscopy, X-ray diffraction, and optical absorption, photoluminescence and Raman spectroscopies. All these techniques confirmed the chemical identity of the CdS nanoparticles. To investigate the mechanism of nanoparticle formation, we took absorption spectra of the precursor solution as a function of irradiation time. In unirradiated solutions, we noticed a maximum at 250 nm, characteristic of Cd-thiolate complexes. The absorption at 250 nm decreased with increasing irradiation time. A new band appeared at 265 nm for exposures around 5 min, and that band shifted to 290 nm in samples exposed for 10 min. A yellow precipitate formed after about 30 min. XRD showed that the precipitate was cubic CdS, with a mean particle size of 1.4 nm. We attribute formation of CdS to the photodissociation of the thiols and of the Cd-thiolates. UV irradiation of these precursors yields a series of species that can react with Cd²⁺, such as RS^·, S²⁻ and H₂S. Small CdS nanoparticles form in the initial stages of illumination, and present absorption bands in the 265–290 nm region. These CdS aggregates grow, coalesce and precipitate for longer irradiation times.     

Determination of Albumin Using CdS/SiO2 Core/shell Nanoparticles as Fluorescence Probes

CdS quantum dots (QD) were capped with SiO₂ via a microemulsion method for reducing the toxicity and imparting the biocompatibility of the CdS QD. The resulting CdS/SiO₂ core/shell nanoparticles (NP) showed an improved water‐solubility and stability even in pH 4.0 acidic medium. Their fluorescence could be effectively enhanced in the presence of bovine serum albumin (BSA), due to the passivation effect of BSA on the surface of the NP. Furthermore, the concentration dependence of the fluorescence intensity obeys the Langmuir‐type binding isotherm. Thus a novel fluorescence enhancement method for the determination of BSA has been developed using the less‐toxic CdS/SiO₂ core/shell NP as probes. Under optimal conditions, the linear range of calibration curve is 0.6–30 µg·mL^?1, and the detection limit is 0.18 µg·mL^?1. Compared with the water‐soluble CdS NP without SiO₂ shell, the CdS/SiO₂ core/shell NP exhibited slightly lower fluorescence response to BSA as well as other coexisting substances, such as heavy and transition metals, due to the inhibition of SiO₂ shell. The proposed method was applied to the quantification of BSA in synthetic and serum samples with satisfactory results.     

TiO2@CdS core–shell nanorods films: Fabrication and dramatically enhanced photoelectrochemical properties

In this paper, we prepared TiO₂@CdS core–shell nanorods films electrodes using a simple and low-cost chemical bath deposition method. The core–shell nanorods films electrodes were characterized by X-ray diffraction, scanning electron microscopy, transmission electron microscopy, and UV–vis spectrometry techniques. After applying these TiO₂@CdS core–shell nanorods electrodes in photovoltaic cells, we found that the photocurrent was dramatically enhanced, comparing with those of bare TiO₂ nanorods and CdS films electrodes. Moreover, TiO₂@CdS core–shell nanorods film electrode showed better cell performance than CdS nanoparticles deposited TiO₂ nanoparticles (P25) film electrode. A photocurrent of 1.31 mA/cm², a fill factor of 0.43, an open circuit photovoltage of 0.44 V, and a conversion efficiency of 0.8% were obtained under an illumination of 32 mW/cm², when the CdS nanoparticles deposited on TiO₂ nanorods film for about 20 min. The maximum quantum efficiency of 5.0% was obtained at an incident wavelength of 500 nm. We believe that TiO₂@CdS core–shell heterostructured nanorods are excellent candidates for studying some fundamental aspects on charge separation and transfer in the fields of photovoltaic cells and photocatalysis.