硫脲修饰法制备高发光性能CdTe量子点

通过巯基水解制备了具有优异荧光特性的碲化镉量子点. 详细研究前驱体镉离子与巯基丙酸(MPA)摩尔比、镉离子浓度等制备条件对大尺寸、高量子产率的亲水性碲化镉量子点光学性能的影响. 在不同的水热生长时间下, 可制备出荧光发射峰位于485-660 nm范围内的不同尺寸的碲化镉水溶性量子点, 荧光发射峰半高宽控制在40-75 nm之间, 量子点的最高量子产率(QY)达到了45%. 并利用硫脲缓慢水解和光解释放自由硫离子, 修饰碲化镉表面, 检测修饰后的量子点在12天内光学性能的变化情况. 通过考察硫脲用量对量子点修饰效果, 发现当n(CdTe)/n(thiourea)=1:4(量子点浓度以镉离子浓度计)时, 硫脲对发射峰为505 nm的碲化镉量子点修饰效果最为理想, 量子点荧光强度加强了5倍, 量子产率达到68.3%.     

Microwave-assisted Synthesis of CdTe Quantum Dots Using 3-Mercaptopropionic Acid as Both a Reducing Agent and a Stabilizer

In this paper, a facile synthetic approach to prepare CdTe quantum dots(QDs) with high luminescence via a one-pot microwave irradiation reaction route using 3-mercaptopropionic acid(MPA) as both a sodium tellurite reducer and a capping molecule was described, and the mechanism of the formation of CdTe QDs was elucidated. In this approach, CdTe QDs with six different emission wavelengths of 553, 567, 577, 595, 608 and 615 nm were obtained via changing the refluxing time and the quantum yields(QY) of these QDs were 40.6%, 55.3%, 63.6%, 43.4%, 37.4% and 29.7%, respectively. The characterization results of X-ray powder diffraction(XRD) and transmission electron microscopy(TEM) indicate that the obtained QDs have a pure cubic zinc blended structure with a spherical shape. No toxic gases were released during the preparation process, indicating that the method is relatively fast, cheap and environmentally friendly.     

Effect of CdS Interlayer on Properties of CdTe Based Quantum Dots

Highly luminescent thioglycolic acid-capped CdTe-based core/shell quantum dots (QDs) were synthesized through encapsulating CdTe QDs in various inorganic shells including CdS, ZnS and CdZnS. CdTe/CdS core/shell QDs exhibited a significant redshift of emission peaks (a maximum emission peak of 652 nm for the core/shell QDs and 575 nm for CdTe cores) with increasing shell thickness. In contrast, the redshift of photoluminescence (PL) peak wavelength of CdTe/ZnS QDs was less than 15 nm. The PL peak wavelengths of the core/shell QDs depended strongly on core size and shell thickness. The PL quantum yields (QYs) of the CdTe/CdS core/shell QDs are up to 67 % while that of CdTe/ZnS core/shell QDs is 45 %. A composite CdZnS shell made CdTe cores a high PL QY up to 51 % and broadly adjusted PL spectra (a maximum PL peak wavelength of 664 nm). The epitaxial growth of the shell was confirmed by X-ray powder diffraction analysis and luminescence decay experiments. Because of high PL QYs, tunable PL spectra, and low toxicity from a ZnS surface layer, CdTe/CdZnS core/shell QDs will be great potential for bioapplications.     

CdTe/CdSe核壳量子点的合成及其在指纹显现中的应用

以CdCl2和Te粉为原料,在水相中合成了CdTe量子点核;通过外延生长在CdTe量子点核上包覆一层CdSe量子点,得到具有良好荧光性能的CdTe/CdSe核壳量子点;采用X射线衍射仪、透射电镜、高分辨透射电镜分析了不同反应条件下合成的CdTe/CdSe核壳量子点的晶体结构和微观结构,并对其进行了荧光光谱等测试和指纹显现分析.结果表明,合成的CdTe和CdTe/CdSe量子点粒径在3～5nm之间,粒径分布窄,水分散性良好;可以通过控制反应时间和Te/Se比等得到在500～700nm显示荧光发射峰的CdTe/CdSe核壳量子点.此外,核壳CdTe/CdSe量子点可以有效地和指纹物质结合,可应用于对铝合金油潜指纹的鉴别.     

颜色可调的高荧光CdTe量子点的水相合成

以亚碲酸钠为碲源,硼氢化钠为还原剂,一步合成了巯基丁二酸(MSA)稳定的CdTe量子点.研究了反应液pH值、镉与碲的摩尔比及镉与巯基丁二酸的摩尔比等实验条件对CdTe量子点体系荧光量子产率的影响,并用荧光光谱、X射线粉末衍射及透射电子显微镜等对其进行了表征.结果表明,CdTe量子点具有闪锌矿结构,形貌呈球状;在pH=1...     

表面修饰CdTe量子点的合成及其光学特性

在水相中合成高发光性能的CdTe量子点,研究以巯基乙酸(TGA)为稳定剂对CdTe表面进行修饰,制备在水中分散性良好的纳米晶,通过对CdTe量子点合成反应条件的摸索,掌握了其合成的反应规律.同时用紫外分光光度计、荧光分光光度计和透射电子显微镜对其进行了表征.结果表明,回流时间、n(Cd²⁺):n(HTe^-)、反应物浓度、TGA用量、反应体系pH值,对纳米晶的光学性质具有显著影响.回流2 h制得的CdTe纳米粒子直径约为5 nm,其发射峰窄且对称,表现出良好稳定的光学性质.     

Ultrafast synthesis of near-infrared-emitting aqueous CdTe/CdS quantum dots with high fluorescence

The traditional aqueous route to synthesis CdTe/CdS Core/shell (c/s) quantum dots (QDs) via decomposition of Cd-thiol complexes is usually time consuming. Herein, an ultrafast and facile aqueous synthetic approach under atmospheric pressure for CdTe/CdS c/s QDs with emission from the green to the near-infrared window (535–820 nm) is reported. With purified CdTe core QDs diluted in solution of Cd-3-mercaptopropionic acid (MPA) complexes, CdTe/CdS c/s QDs with emission wavelengths at 700 and 800 nm can be obtained within 20- and 45-min refluxing under the optimized experimental conditions, respectively. This is the most rapid way to prepare CdTe/CdS c/s QDs in aqueous phase, and the obtained QDs were highly luminescent without postsynthesis treatment. The influences of various experimental factors, including Cd²⁺ concentration, MPA-to-Cd ratio, pH value, and dilution ratio on the growth rate and luminescent properties of the obtained CdTe/CdS c/s QDs, have been taken into consideration. The three processes “purification-dilution-addition” ensure the synthesis environment with high pH value and low core concentration and have a marked impact on the rapid synthesis rate and the resulting high fluorescence of CdTe/CdS c/s QDs.     

Biotin-modified glutathione as a functionalized coating for bioconjugation of CdTe-based quantum dots

In this study, biotin-conjugated glutathione was synthesized using peptide bonding of the biotin carboxy group and amino group of the γ-glutamic acid to prepare an alternative coating for CdTe quantum dots (QDs). This type of coating combines the functionality of the biotin with the fluorescent properties of the QDs to create a specific, high-affinity fluorescent probe able to react with avidin, streptavidin and/or neutravidin. Biotin-functionalized glutathione-coated CdTe QDs were prepared by a simple one-step method using Na? TeO? and CdCl?. Obtained QDs were separated from the excess of the biotin-conjugated glutathione by CE employing 300?mM borate buffer with pH 7.8 as a background electrolyte. The detection of sample components was performed by the photometric detection at 214?nm and LIF employing Ar? ion laser (488?nm).     

基于L-半胱氨酸/CdTe量子点修饰电极的电化学传感器的制备及其对Pb~(2+)的检测

成功制备了由L-半胱氨酸和CdTe量子点作为修饰材料的电化学传感器并用于水体中Pb~(2+)的检测。巯基丙酸修饰的CdTe量子点通过水相合成,表面含有大量羧基,与L-半胱氨酸表面的氨基形成酰胺键,修饰于金电极表面。通过荧光分光光度计、透射电子显微镜、红外光谱、X射线衍射对L-Cys/CdTe QDs复合材料进行表征。采用循环伏安法(CV)研究了L-Cys/CdTe QDs修饰成分在金电极上的电化学性能及CdTe量子点的最佳自组装时间。采用差分脉冲溶出伏安法(DPSV)研究了铅离子在修饰电极上的电化学行为。在优化实验条件下,Pb~(2+)浓度在1.0×10~(-6)~1.0×10~(-2) mol/L范围内与其峰电流呈良好的线性关系,相关系数(r2)为0.993 8,检出限(3σ,n=5)为4.0×10~(-7) mol/L。该传感器具有良好的重现性和稳定性,有望用于实际水样中铅离子的检测。     

一锅合成绿色到近红外发射的CdTe量子点

以3-巯基丙酸(MPA)为稳定剂,采用水相合成法制备了从绿色到近红外发射的CdTe量子点。系统研究了反应液pH值、镉和碲的物质的量之比及镉和3-巯基丙酸的物质的量之比等实验条件对CdTe量子点体系的发射波长和荧光量子产率的影响。在pH值为10.5,且nCd2+∶nTe2-∶nMPA=1∶0.05∶1.1的条件下,回流0.5 h,CdTe量子点体系在569 nm波长处的荧光量子产率达到30.8%;在7 h的回流时间内,制备的量子点的波长覆盖范围为525～730 nm。分别用X射线粉末衍射、透射电镜和红外光谱对CdTe量子点的晶体结构、形貌及表面基团进行表征。     

水溶性的高荧光CdTe/CdSeⅡ型核壳量子点的合成与表征

用L-半胱氨酸(L-cysteine)作为稳定剂,以制备的CdTe量子点为核模板,水相合成了具有近红外发光的Ⅱ型核壳CdTe/CdSe半导体量子点。实验考察了合成温度,核模板的尺寸和组分比等因素对合成高质量的CdTe/CdSe量子点的影响。用紫外-可见吸收和荧光光谱研究了合成的量子点的光学性质。在优化的合成条件下,荧光发射光谱在586～753nm范围连续可调,荧光量子产率高达68%;通过X-射线衍射(XRD),X射线光电子能谱(XPS)和透射电镜(TEM)对合成的Ⅱ型核壳CdTe/CdSe量子点进行了结构和形貌表征。     

水相合成CdX (X＝Te, Te/CdS, Te/ZnS)红色量子点及毒性效应

分别以巯基乙酸(Mercaptoacetic Acid, MA)、还原型谷胱甘肽(Glutathione, GSH)为稳定剂在水相中直接合成了巯基乙酸CdTe (CdTe-MA)、红色巯基乙酸CdTe/CdS (CdTe/CdS-MA)、巯基乙酸CdTe/ZnS (CdTe/ZnS-MA)及谷胱甘肽CdTe (CdTe-GSH)量子点. 其中, CdTe-GSH量子点的量子产率可达47.3%. 体外溶血实验证实CdTe/ZnS-MA和CdTe-GSH量子点的溶血率较CdTe-MA和CdTe/CdS-MA低, 浓度为0.05 mmol/L的量子点溶血率＜5%, 达到了生物医用材料的要求. 活体实验证实: 通过尾静脉方式把量子点注入小鼠体内后, 荧光显微镜观察发现高剂量的量子点(0.4 mmol/10 g)在体内主要在心、肝、脾、肾组织中分布较多, 且引起不同程度的组织病变.     

A potential visual fluorescence probe for ultratrace arsenic (III) detection by using glutathione-capped CdTe quantum dots

The interaction between mercaptoacetic acid (MA)-capped CdTe QDs, MA-capped CdTe/ZnS QDs or glutathione (GSH)-capped CdTe QDs with As(III) was studied using fluorescence spectrometry. As (III) has a high-affinity to reduced-GSH to form As(SG)₃, and the emission of the GSH-capped CdTe QDs (λ_em. = 612 nm) is quenched effectively. Thus, a novel fluorescence spectrometric method was developed for As (III) determination by using GSH-CdTe QDs. Under optimal conditions, the quenched fluorescence intensity (F₀/F) increased linearly with the concentration of As (III) ranging from 5.0 × 10⁻⁶ to 25 × 10⁻⁵ mol L⁻¹. The limit of detection (3σ) for As (III) was found to be 2 × 10⁻⁸ mol L⁻¹. This method is potentially useful in visual detection of As (III) under irradiation of the ultraviolet light.     

Highly luminescent SiO(2) beads with multiple QDs: Preparation conditions and size distributions

Multiple CdTe quantum dots (QDs) were incorporated in SiO(2) beads using a reverse micelle route (i.e., a water-in-oil emulsion) and a precursor solution of SiO(2)-coated CdTe QDs as the water phase. The QDs in the beads retained their initial photoluminescence efficiency (56%) because they had a thin SiO(2) shell that prevented removal of the ligands from their surface during incorporation. Because of the SiO(2) sol in the precursor solution, the size of the water pools in water-in-oil emulsion increased to 700±320nm compared to 25±5nm when an aqueous CdTe QD solution was used. The size of the beads prepared in the water pools depended strongly on the preparation parameters (water phase injection speed, tetraethyl orthosilicate concentration, reaction time). The beads were easily separated into three size ranges (60±23, 160±40, and 650±200nm) by filtering for further application.     

Sized dependence and microstructural defects on highly photocatalytic activity based on multisized CdTe quantum dots sensitized TiO2

A series of sensitized TiO₂ NPs with enhanced photocatalytic activity were prepared by different sized CdTe QDs with bifunctional ligand interlinking. The microstructures and morphologies of four different sizes of CdTe QDs and CdTe QDs sensitized TiO₂ NPs were characterized systematically by fluorescence spectroscopy, UV-Vis diffuse reflectance spectroscopy, FT-IR, XRD, XPS, FE-SEM, HRTEM, BET, and positron annihilation lifetime spectroscopy (PALS). The photocatalytic performance of CdTe QDs sensitized TiO₂ NPs was investigated by degrading MO and MB in aqueous solution under visible light irradiation. The process of degradation complied with the first-order reaction kinetics. Four different sized CdTe QDs sensitized TiO₂ exhibited higher photocatalytic activities than TiO₂. Particularly, yellow emitting CdTe QDs (3.28 nm) sensitized TiO₂ (CT_1.5) showed the best photocatalytic performance, which may be attributed to the optimal NP size, and has a moderate light absorption and electron injection. The effect of microstructural defects on CdTe QDs sensitized TiO₂ has been confirmed effectively by positron lifetime measurements.     

Enhanced chemiluminescence from reactions between CdTe/CdS/ZnS quantum dots and periodate

A novel chemiluminescence (CL) performance of CdTe/CdS/ZnS quantum dots (QDs) with periodate (KIO₄) was studied. Effects of concentration and pH on the CL system were investigated. Electron spin resonance (ESR) and the effects of radical scavenger analysis were employed for identification of intermediate species. The CL spectra for this system showed only one maximum emission peak centered around 620 nm, which was similar with photoluminescence (PL) spectra of CdTe/CdS/ZnS QDs. The CL of CdTe/CdS/ZnS QDs was induced by direct chemical oxidation and the possible mechanism could be explained by radiative recombination of injected holes and electrons. This investigation not only provided new sight into the optical characteristics of CdTe/CdS/ZnS QDs, but also broadened their potential optical utilizations.     

Aqueous synthesis of type-II core/shell CdTe/CdSe quantum dots for near-infrared fluorescent sensing of copper(II)

Type-II core/shell CdTe/CdSe quantum dots (QDs) were synthesized in aqueous medium by employing thiol-capped CdTe QDs as core template and CdCl(2) and Na(2)SeSO(3) as shell precursors, respectively. Compared with the original CdTe cores, the core/shell CdTe/CdSe QDs showed an obvious red-shifted emission with the color-tune capability to the near-infrared (NIR) wavelength, because of the formation of an indirect excitation. The prepared QDs exhibited high stability and moderate fluorescence quantum yields (10-20%), and their core/shell heterostructure was characterized by UV-vis absorption, steady-state and time-resolved fluorescence spectra, X-ray powder diffraction, X-ray photoelectron spectroscopy and high-resolution transmission electron microscopy. The fluorescence of the core/shell QDs could be markedly quenched by Cu(II), and approximate concentrations of other physiologically important cations, such as Zn(II), Ca(II), Na(I) and K(I) etc., had no effect on the fluorescence. Based on this, a simple and rapid method for Cu(II) determination was proposed using the NIR CdTe/CdSe QDs as fluorescent probes. Under optimal conditions, the response was linearly proportional to the concentration of Cu(II) between 0.05 to 50.0 x 10(-6) mol L(-1), the limit of detection was 2.0 x 10(-8) mol L(-1). The developed method was successfully applied to the detection of trace Cu(II) in real samples.     

Fe_3O_4/CdTe/聚氨酯纳米复合物的制备及其性能研究

由共沉淀法和Stober法制备了伯胺基功能化SiO2稳定的Fe3O4磁性纳米粒子Fe3O4@SiO2-NH2;Fe3O4@SiO2-NH2与二异氰酸酯及咪唑阳离子二醇、聚乙二醇的反应使其表面形成阳离子型聚氨酯稳定层;通过阳离子型聚氨酯与CdTe量子点表面修饰的巯基乙酸间的电荷相互作用,制备得到了Fe3O4/CdTe/聚氨酯纳米复合物.用X射线衍射(XRD)、红外吸收光谱(FTIR)、热重分析(TGA)、透射电子显微镜(TEM)、磁强计(VSM)、紫外吸收光谱(UV)、荧光发射光谱(PL)表征了该纳米复合物的结构与性能.结果表明,CdTe量子点均匀地分散在Fe3O4@SiO2磁性纳米粒子周围,所得纳米复合物在溶剂中分散均匀,不团聚,且具有超顺磁性,并保持了CdTe量子点的荧光性能.     

水溶性CdTe量子点的合成及影响因素研究

本文以巯基乙酸(TGA)为稳定剂,在水相中合成了高荧光CdTe量子点.其荧光发射波长在507 ～ 628nm范围内可调,最窄半峰宽37 nm,粒径约3.4nm,量子产率达42.1％.本实验在固定前躯体配比不变的情况下,考察了前躯体中镉离子的浓度、pH及回流时间对CdTe生长的影响.并用透射电子显微镜(TEM),荧光分光光度计(FS),X射线衍射仪(XRD)等手段对制备的量子点进行了表征.结果表明:CdTe量子点的尺寸随回流时间而增长;反应的pH对量子点的荧光强度有显著影响;镉离子的浓度越大,量子点的生长速度越快,荧光强度却随之降低.     

镍配合物分子印迹光电流型传感器的研究

制作了一种基于光电流检测的分子印迹传感器,并应用于Ni2+测定。此传感器以CdTe量子点为光电材料,将量子点覆盖在导电玻璃表面,并在此层上以光聚合法制作镍-1-(2-吡啶偶氮)-2-萘酚( PAN)分子印迹膜。365 nm紫外光作为激发光源,量子点在光照下生成电子-空穴对,电子与电子受体-抗坏血酸作用形成的光电流作为检测信号,根据“门效应”进行Ni2+检测。实验中对配合物进行了红外表征,对量子点进行了紫外和荧光表征,对洗脱吸附时间和底液中抗坏血酸浓度的用量进行了优化。实验表明Ni2+浓度在5×10-11~5×10-8 mol/L的范围内与光电流大小呈线性关系,检出限达8.3×10-12 mol/L。此传感器具有较好的选择性,已用于水样分析。