L-半胱氨酸修饰的水溶性ZnS:Mn量子点的合成及其荧光性质

以L-半胱氨酸(L-Cys)为修饰剂,采用共沉淀法在水溶液中合成了水溶性L-Cys修饰的ZnS:Mn量子点(1),其结构经IR和XRD表征。利用UV和荧光发射光谱研究了1的光学性质,结果表明:1为立方闪锌矿结构;与体相ZnS的吸收相比(340 nm),1的吸收蓝移;1具有独特的荧光性质,ZnS的特征发射峰为390 nm,Mn2+的特征发射峰为581 nm。     

反胶束法制备SiO2包裹的ZnS:Mn/ZnS量子点

采用反胶束法制备了SiO2包裹的ZnS∶Mn/ZnS量子点(1)。1的UV吸收峰在295 nm附近,低于体相ZnS(约340 nm);1中Mn2+含量升高,ZnS基质的缺陷荧光发射峰减弱,595 nm处的Mn2+特征荧光发射峰增强;但Mn2+含量过高时产生荧光淬灭。光学显微镜和透射电镜分析表明,1分散性较好,内核呈结晶态;Mn2+含量为2.2%时,1的内核直径和SiO2壳层厚度分别为6 nm和5 nm左右。     

单分散ZnS纳米球与纳米梭之间的形貌转换及光学性能研究

利用平平加作为表面活性剂, 正戊醇作为助表面活性剂, 环己烷作为油相, 以硫化钠(Na₂S)和醋酸锌(Zn(Ac)₂)作为反应物, 通过控制反应条件在反相胶束体系中合成出单分散的ZnS纳米球与纳米梭. 采用XRD和TEM对产物的结构和形貌进行表征, 结果表明产物均为六方相ZnS, 晶胞参数为a＝0.3823 nm, c＝56.2 nm, 纳米球直径约为50 nm, 纳米梭直径约为60 nm, 长度约为110 nm. 采用UV-Vis(紫外可见吸收光谱)和PL(荧光光谱)研究了产物的光学性能. 纳米球的紫外可见光谱的吸收峰出现在288 nm处, 而纳米梭在305 nm处有强吸收峰, 与块体材料相比, 分别有约60和50 nm的蓝移. 当激发波长为270 nm时, 纳米球和纳米梭产物分别能够发出波长为408和303 nm的紫外光.     

Mn2+掺杂对低温生长ZnS的形貌及光致发光性能的影响

以Zn粉和S粉为原料,Au纳米颗粒为催化剂,采用低温(450℃)化学气相沉积法(CVD),在Si(100)衬底上制备了未掺杂和Mn2+掺杂的ZnS微纳米结构.利用X射线衍射仪(XRD)、能量弥散X射线谱(EDS)、场发射扫描电子显微镜(SEM)和光致发光光谱(PL)等测试手段对样品的结构、成分、形貌和发光性能进行了分析.结果表明,所得ZnS样品均为六方纤锌矿结构,未掺杂的ZnS为微纳米球,在波长为450和463 nm处有2个发光强度较大的蓝光峰;Mn2+掺杂ZnS为纳米线,在波长479和587 nm处分别有1个微弱的蓝光峰和1个强度相对较大的红光峰.此外,还对ZnS微纳米结构的形成过程进行了探讨,并提出了可能的形成机理.     

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.     

聚甲基丙烯酸甲酯在纳米氧化铝表面的吸附和氢键作用

研究了聚甲基丙烯酸甲酯(PMMA)在纳米氧化铝表面的吸附行为, 采用透射红外光谱研究了吸附的PMMA中的羰基和纳米氧化铝表面羟基之间的氢键作用. 结果表明, PMMA在纳米氧化铝表面的吸附曲线为典型的Langmuir曲线, 饱和吸附值为1.2 mg/m2, 受氢键作用影响, 键合羰基在红外光谱中的吸收峰向低波数方向移动. 根据计算, 羰基的最大键合值(即含键合羰基的甲基丙烯酸甲酯单元的总质量)为0.36 mg/m2, 其余为自由羰基. 随着吸附量的增加, 羰基的键合比例逐渐降低. 吸附达到饱和时, 羰基键合比例为0.30, 说明PMMA主要以平铺的方式覆盖在纳米氧化铝的表面.     

低温合成广谱发光CuInS_2/ZnS量子点

以二乙基二硫代氨基甲酸锌(ZDC)为ZnS的前驱体材料、三辛基膦(TOP)为主要配体,在温度不高于200℃的条件下合成了广谱发光的核壳结构CuInS2/ZnS(CIS/ZnS)量子点.研究了ZDC用量、壳层包裹温度和配体对CIS/ZnS光学特性及荧光量子产率的影响.结果表明,使用ZDC可在相对较低的温度下实现ZnS的包裹过程,并且随着包裹温度的提高,ZnS的包裹速度明显加快.吸收光谱、荧光光谱及X射线衍射分析结果表明,使用TOP为配体合成的CIS/ZnS量子点的明显吸收峰为其激发吸收峰.使用荧光分光光度计、高分辨透射电子显微镜、X射线光电子能谱仪和傅里叶变换红外光谱仪对使用不同配体进行壳层包裹得到的样品进行了表征.结果表明,在ZnS的包裹过程中,配体TOP和十二硫醇作为有机层包覆在颗粒表面也会影响量子点的光学性能和晶体生长速度.使用TOP能够加速ZnS的包裹速度,形成的颗粒尺寸均一,其荧光波长可蓝移至550nm.     

ZnS纳米球的水热法制备及其光催化性能研究

在表面活性剂十六烷基三甲基溴化铵(CTAB)的辅助下,以乙酸锌为锌源,硫脲(NH₂)₂CS为硫源,使用水热法通过改变反应时间,成功制备了不同粒径的ZnS球状颗粒.利用X射线衍射(XRD)、扫描电子显微镜(SEM)、X射线能谱,高分辨透射电子显微镜(HRTEM))、紫外可见分光光谱和光致发光谱(PL)等测试手段对样品的晶体结构、形貌、光学性质进行了分析.通过对不同粒径的ZnS纳米颗粒对亚甲基蓝的光催化降解的催化活性进行了评估.实验结果表明:在表面活性剂CTAB的作用下,随着反应时间的增加,生成的ZnS晶核生长成纳米颗粒,然后ZnS纳米颗粒将进一步发生团聚从而形成平均粒径超过500nm的ZnS纳米球,但制备的ZnS产物的晶体结构均为立方纤锌矿结构.随着ZnS粒径的增加,样品的紫外吸收峰从418nm逐渐蓝移到362nm,而PL发射峰位的峰强随着粒径的增大而增强.光催化结果显示,反应12h制备的ZnS纳米球的光催化性能最佳.     

表面修饰CdS和(CdS)ZnS纳米晶的性能研究

在水相中合成了CdS纳米微粒,以ZnS对其进行表面修饰,得到具有核壳结构的(CdS)ZnS水溶性纳米晶。采用红外光谱、X射线衍射(XRD)、透射电镜(TEM)表征其粒度和形貌,紫外-可见吸收光谱(UV)、荧光光谱表征其光学特性。制得的CdS近似呈球形,直径为8nm;CdS纳米颗粒表面经ZnS修饰后,其荧光发射峰强度显著增强,表面态发射减弱。     

ZnS纳米球的水热法制备及其光催化性能研究

在表面活性剂十六烷基三甲基溴化铵(CTAB)的辅助下,以乙酸锌为锌源,硫脲(NH2)2CS为硫源,使用水热法通过改变反应时间,成功制备了不同粒径的ZnS球状颗粒。利用X射线衍射(XRD)、扫描电子显微镜(SEM)、X-射线能谱,高分辨透射电子显微镜(HRTEM))、紫外可见分光光谱和光致发光谱(PL)等测试手段对样品的晶体结构、形貌、光学性质进行了分析。通过对不同粒径的ZnS纳米颗粒对亚甲基蓝的光催化降解的催化活性进行了评估。实验结果表明:在表面活性剂CTAB的作用下,随着反应时间的增加,生成的ZnS晶核生长成纳米颗粒,然后ZnS纳米颗粒将进一步发生团聚从而形成平均粒径超过500nm的ZnS纳米球,但制备的ZnS产物的晶体结构均为立方纤锌矿结构。随着ZnS粒径的增加,样品的紫外吸收峰从418nm逐渐蓝移到362nm,而PL发射峰位的峰强随着粒径的增大而增强。光催化结果显示,反应12h制备的ZnS纳米球的光催化性能最佳。     

Controllable synthesis of ZnS/PMMA nanocomposite hybrids generated from functionalized ZnS quantum dots nanocrystals

We reported controllable synthesis of ZnS nanocrystal-polymer transparent hybrids by using polymethylmethacrylate (PMMA) as a polymer matrix. In a typical run, the appropriate amounts of zinc chloride (ZnCl₂) and sodium sulfide (Na₂S) in the presence of 2-mercaptoethanol (ME) as the organic ligand were well dispersed in H₂O/dimethylformamide solution without any aggregation. In addition, the Mn-doped ZnS nanocrystals (NCs) were synthesized with similar method. Then, ZnS-PMMA hybrids were obtained via free radical polymerization in situ by using ZnS NCs functionalized with methacryloxypropyltrimethoxysilane (MPS). FT-IR characterization indicates the formation of robust bonding between ZnS NCs and the organic ligand. The TEM images show that ZnS NCs are well dispersed in PMMA matrix, and particle size of as-prepared ZnS NCs is about 2.6 nm, in agreement with the computing results of Brus’s model and Debye–Scherrer formula. The photoluminescence measurements present that ZnS NCs, Mn-doped ZnS NCs, and ZnS/PMMA hybrid show good optical properties.     

核壳结构CdS/ZnS纳米微粒的制备与光学特性

CdS and CdS/ZnS core-shell structure nano particles were synthesized in micro emulsion, and characterized by X-ray diffraction(XRD), transmission electron microscopy (TEM), UV absorption spectra and PL. The average diameter of CdS was about 3.3 nm, and CdS/ZnS core-shell structure was confirmed by XRD and UV. Considering the optical properties of CdS/ZnS core-shell structure nanoparticles which have different ZnS shell thickness, the UV absorption edge of CdS/ZnS becomes as lightred-shift with the thickness of ZnS layer increasing, and the absorption of shortwave band is strongly enhanced at the same time. The PL spectra indicate that ZnS shell layer can greatly eliminate surface defects of CdS nanoparticles and make its band-edge directed recombination increased, and the luminous efficiency of CdS is improved greatly when it has appropriate shell thickness.     

水溶性的CdSe/ZnS纳米微粒的合成及表征

用L-半胱氨酸(Cys)作为稳定剂，合成了水溶性的CdSe/ZnS核壳结构的半导体纳米微粒。吸收光谱和荧光光谱表明，CdSe/ZnS纳米微粒比单一的CdSe纳米粒子具有更优异的发光特性。透射电子显微镜（TEM）、ED和XPS表征了CdSe/ZnS纳米微粒的结构、分散性及形貌。红外光谱证实半胱氨酸分子中的硫原子和氧原子参加了与纳米粒子表面的金属离子的配位作用。     

Synthesis and Optical Properties of Mn2+-Doped ZnS Nanoparticles in Solutions and Coatings

Mn2+-doped ZnS nanoparticles with different Mn-doping concentrations stabilized by hydroxypropyl cellulose (HPC) have been synthesized in ethanolic solutions and coatings. Their optical and structural properties have been characterized by means of UV-vis spectroscopy, luminescence spectroscopy, high resolution transmission electron microscopy (HRTEM) and small angle X-ray scattering (SAXS). Solutions and coatings exhibit a strong luminescence at 590 nm when excited with UV light showing that Mn2+ is incorporated into the ZnS nanoparticles. The highest luminescence intensity is obtained with an Mn2+ concentration of 2 mol%. HRTEM and SAXS investigations show that the particles are crystalline and are 3 ± 0.5 nm in size. Irradiation of the coatings with UV light leads to a photochemical oxidation of the particles, as shown by the decreasing absorption of the coating with irradiation time and a blue shift of the absorption maximum. Furthermore, the luminescence intensity first strongly increases and then decreases completely with UV-irradiation time. Both phenomena can be explained by the photochemical oxidation of the particles.     

Sol-Gel Synthesis of Hybrid Organic-Inorganic Monoliths Doped with Colloidal CdSe/ZnS Core-Shell Nanocrystals

Colloidal CdSe/ZnS core-shell nanocrystals, with a narrow size distribution, were dispersed in a hybrid sol resulting from the hydrolysis of tetraethylorthosilicate and 3-glycidoxypropyltrimethoxysilane (GLYMO). In order to reduce the gelation time and the exposure of the nanoparticles to air, several catalysts of the GLYMO epoxy ring opening were employed for the sol preparation, such as imidazole, methyl-imidazole, pyridine, benzylamine, propylamine. The role of the various catalysts was monitored by optical absorption measurements in the near infrared region, by observing the evolution of the epoxy bands. Imidazole was found to provide the fastest gelation and the best results in terms of bubble disappearance from the gel structure. The variation in the optical properties of the semiconductor nanoparticles embedded in the matrix was monitored as a function of the gelation time and was compared to the optical absorption and photoluminescence spectra of the nanoparticles dissolved in a chloroform solution. A decrease in the gelation-time results in a closer resemblance between the optical properties of the CdSe/ZnS doped monoliths and those of the particles dissolved in the solvent, before incorporation in the matrix. The photoluminescence of the CdSe/ZnS nanocrystals is not bleached after they are trapped in the glassy matrix.     

ZnS纳米粒子的固相合成及其光学性能

将不同的添加剂引入到低温固相反应中，快速合成了不同尺寸的ZnS纳米粒子。利用TEM表征了产物形貌，利用XRD研究了不同的添加剂、同一添加剂下不同的反应温度、不同反应时间对纳米粒子尺寸的影响。结果表明，不同的添加剂对粒子的尺寸影响较大，其中，十二烷基胺以其特殊的反应方式在较高温度下获得了较小的纳米粒子。另外，在PEG400存在条件下，反应温度和反应时间对粒子尺寸均有一定的影响。同时，对不同条件下所得产物的紫外-可见光吸收性能也进行了测试。     

Influence of cobalt concentration on structural and optical properties of ZnS quantum dots

ZnS and Co-doped ZnS nanoparticles have been prepared by simple chemical precipitation method. Zinc acetate, sodium sulfide, and cobalt nitrate have been used as precursors for the preparation of Co-doped ZnS quantum dots. The X-ray diffraction results revealed that the undoped and Co-doped ZnS quantum dots exhibit hexagonal structure. The average grain size of quantum dot was found to lie in the range of 2.6–3.8 nm. The surface morphology has been studied using scanning electron microscope. The compositional analysis results confirm the presence of Co, Zn and S in the sample. The optical properties of undoped and Co-doped ZnS quantum dots have been studied using absorption spectra. TEM results show that undoped and Co-doped ZnS nanoparticles exhibit a uniform size distribution with average size of 2.5–3.4 nm.     

Far-infrared characteristics of ZnS nanoparticles measured by terahertz time-domain spectroscopy

The optical and dielectric properties of ZnS nanoparticles are studied by use of terahertz time-domain spectroscopy (THz-TDS) over the frequency range from 0.3 to 3.0 THz. The effective medium approach combined with the pseudo-harmonic model of the dielectric response, where nanoparticles are embedded in the host medium, provides a good fit on the experimental results. The extrapolation of the measured data indicates that the absorption is dominated by the transverse optical mode localized at 11.6+/-0.2 THz. Meanwhile, the low-frequency phonon resonance of ZnS nanoparticles is compared with the single-crystal ZnS. The THz-TDS clearly reveals the remarkable distinction in the low-frequency phonon resonances between ZnS nanoparticles and single-crystal ZnS. The results demonstrate that the acoustic phonons become confined in small-size nanoparticles.     

纳米ZnS在KGM-AE高分子模板中的可控制备与光限幅性能研究

设计了一种新的乙酸酐改性魔芋葡苷聚糖(KGM-AE)作为高分子模板，通过调节模板剂的改性度、模板剂溶液浓度以及Zn²⁺离子浓度，探讨了ZnS纳米粒子形成的机理，制备出了大小及形貌可控的纳米ZnS。利用IR、ICP-AES、XRD、TEM等对ZnS结构进行了表征，并测定了纳米ZnS光限幅性能，结果显示纳米ZnS溶液均呈现出明显的光限幅性能。     

A new solid-phase nanoparticle FRET assays based on GO/CS/ZnS nanocomposite film and developed in sensing for bromonium ion

Composite thin films consisting of nano-sized ZnS particles dispersed in chitosan/GO films have been prepared by in-situ method. The films obtained were characterized by FTIR and UV–Vis spectroscopy. The ZnS nanoparticles with 90 nm in diameter were dispersed uniformly in the film matrix. Optical absorption peak due to the size of ZnS particles was observed around 350 nm. The fluorescence emission at 430 nm of the GO/CS/ZnS nanocomposite films is very sensitive to the presence of bromonium ion from aqueous solutions. New solid-phase nanoparticles FRET assays are firstly immobilized on the substrate and then interacted with functionalized acceptor molecules in the solution to trigger the FRET effect to detect Br^–.