One‐step green synthesis by organic molten salt method and optical properties of CdS nanosheets

Cadmium sulfide (CdS) nanosheets were synthesized by an environment friendly, “green” organic molten salt (OMS) method at 220 °C. The as‐synthesized products were characterized by X‐ray diffraction (XRD), scanning electron microscopy (SEM), Transmission electron microscopy (TEM) and energy dispersive spectroscopy (EDS), respectively. The XRD results reveal that the as‐synthesized CdS nanosheets are of the hexagonal wurtzite structure and the CdS nanosheets grow along the c‐axis. The SEM results indicate that the diameters and thickness of the CdS nanosheets are about 20–40 nm and 5–10 nm, respectively. The optical properties of the CdS nanosheets were investigated by ultraviolet–visible (UV‐Vis) spectroscopy and photoluminescence (PL) spectroscopy. The ultraviolet–visible spectrum exhibits two excitonic peaks with a step‐like absorption and the photoluminescence spectrum shows a green emission peak centered at around 524 nm. A possible growth mechanism of CdS nanosheets was discussed.     

Preparation of PbS nano‐microcrystals with different morphologies and their optical properties

PbS nano‐microcrystals were prepared from Pb(OAc)₂·3H₂O and sulfur in a solution without any surfactant using the solvothermal process. Different morphologies, mainly including polyhedron microcrystals and sphere‐like assemblies, were characterized using a scanning electron microscope (SEM) and a transmission electron microscope (TEM). PbS nano‐microcrystals with cubic crystal structure were detected using X‐ray diffraction (XRD), electron diffraction (ED) and high resolution transmission electron micrograph (HRTEM) techniques. The optical properties were investigated by ultraviolet‐visible (UV‐vis) spectroscopy, and photoluminescence spectroscopy (PL). The UV‐vis absorption peaks of PbS exhibited a large blue‐shift and the PL spectra had a strong and broad emission bands centered at 408 nm. The crystal growth mechanism of PbS was also discussed.     

Synthesis and characterization of semiconductor metal sulfide nanocrystals using microemulsion technique

The semiconductor nanocrystals ZnS, PbS, CdS and CuS were synthesized via microemulsion technique involving metal acetate, reducing agent (Na₂S) and Triton X‐100 as surfactant. Nanocrystals were characterized by X‐ray diffraction (XRD), transmission electron microscopy (TEM) and dynamic light scattering (DLS). The average size of ZnS, PbS, CdS and CuS nanocrystals were found to be 5.6 nm, 13.3 nm, 11.4 nm and 6.2 nm, respectively. Different parameters like surfactant (Triton X‐100) concentration, water‐to‐surfactant ratio (ω), precursor concentration [zinc acetate, (Zn(AC)₂], reducing agent concentration [sodium sulphide, (Na₂S)] were optimized to synthesize ZnS quantum dots.     

Synthesis and photoluminescence properties of bundle‐like CdS nanostructures assembled by high‐quality nanorods

Bundle‐like cadmium sulfide (CdS) nanostructures assembled by high‐quality nanorods have been successfully synthesized on a large scale via a facile solvothermal route in a mixed solvent of ethylenediamine and dodecanethiol. The typical lengths of bundle‐like CdS nanostructures are several tens of micrometers, and the diameters and lengths of CdS nanorods are about 50–70 nm and several micrometers, respectively. The influence of the concentration of dodecanethiol on the morphologies of CdS nanostructures has been investigated carefully. Photoluminescence spectra (PL) of CdS nanostructures reveal that the bundle‐like CdS nanostructures exhibited two fluorescence emission peaks centered at 495nm (2.51 eV) and 522 nm (2.38 eV) as the excitation wavelength is 405 nm. (© 2011 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

宽吸收带MEH-PPV/PbS量子点复合材料的制备

制备出粒径在3~8nm之间的宽吸收带聚合物MEH-PPV/PbS量子点复合材料。该材料在400~1100nm波长区域内表现出强吸收,能覆盖太阳光谱的大部分。准原位吸收光谱分析表明,MEH-PPV的加入不是获得宽吸收带纳米颗粒的主要因素。     

PbS crystals with clover‐like structure: Preparation,characterization, optical properties and influencing factors

A new and simple route to synthesize Lead sulfide (PbS) crystals with the clover‐like structure was described in the current paper. PbS was prepared in a simple aqueous solution employing (CH₃COO)₂Pb and thiourea as the initial materials under 130 W microwave irradiation. No any surfactant or template including organic polyamines with N‐chelation property was needed. The phase and composition of the product were identified by X‐ray powder diffraction (XRD) and X‐ray photoelectron spectra (XPS). TEM observation showed that the product with the six‐petal flower‐shaped structures was obtained, but SEM observation confirmed the clover‐like structure of the product; and the six‐petal flowers were formed via the overlap of two clovers revolved 60° around the center of the flower. Some factors affected the shape of the final product were studied and the optical properties of PbS crystals with the clover‐like structure were measured. (© 2004 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Microwave‐assistant route to hybrid semiconductor nanocrystals with quasi solution‐solid‐solid mechanism

A facile microwave‐assistant route was developed for the synthesis of hybrid nanocrystals. Colloidal hybrid nanocrystals, Ag₂S‐CdS, were prepared by using Ag₂S nanocrystals and cadmium diethyldithiocarbamate as raw materials under microwave irradiation. The fast ion conductor, Ag₂S nanocrystal, catalyzes the growth of CdS nano‐building blocks through a quasi solution‐solid‐solid mechanism. The ultraviolet‐visible absorption and photoluminescence spectra of the Ag₂S‐CdS hybrid nanocrystals were investigated. One of the main advantages for this synthesis is the efficiency of dramatically reducing overall processing time. This report provides a new route for the growth of semiconductor hybrid nanocrystals based on Ag₂S and may be extended to the preparation of other hybrid colloidal nanostructures.     

Morphology‐controllable synthesis of ZnO nano‐/micro‐ structures by a solvothermal process in ethanol solution

Flower‐like ZnO nanostructures assembled by nanorods with bimodal size distribution have been synthesized by a solvothermal process in NaOH‐Et system. Various effects of the solvothermal parameters and assistant additives on the morphologies of ZnO nanostructures have been investigated. The directing effect of chloride ions have been observed in the formation of highly symmetrical 3D ZnO nanostructures. A possible mechanism has been proposed to explain the formation of ZnO nanoflowers in NaOH‐Et system. A strong near‐UV emission band centered at around 396 nm is observed in the photoluminescence spectrum of flower‐like ZnO nanostructures, indicating of their high crystal quality.     

Effect of ferric ions on the morphology and size of magnetite nanocrystals synthesized by ultrasonic irradiation

Two‐dimensional plate‐like Fe₃O₄ nanocrystals and nanoparticles could be synthesized by a simple one‐step sonochemical method through ultrasonic irradiation in reverse co‐precipitation solution at low temperature. This technique provided a facile and rapid way to prepare Fe₃O₄nanocrystals with different morphology and size. Magnetite nanoplates were synthesized with only ferrous salt adding into alkali solution, and adding ferric ions with low molar ratio in the metal salts solution would lead to the formation of very small magnetite nanoparticles (∼10 nm). The size of as‐prepared magnetite nanoparticles increased with increasing reaction temperature and showed narrow size distribution, the standard deviation less than 2 nm. This investigation indicated that ferric ions had significant influence on the morphology of Fe₃O₄ nanocrystals. (© 2011 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Optical properties of novel PbS and PbSe quantum-dot-doped alumino-alkali-silicate glasses

Lead sulfide PbS and lead selenide PbSe quantum dots (QDs) were synthesized in novel alumino-alkali-silicate glass. The synthesis of the nanocrystals was stabilized by introduction of two alkaline components. The presence of crystalline phase was confirmed by X-ray diffraction analysis, transmission electron microscopy and optical spectroscopy. For PbS (PbSe) QD-doped glass, the position of the 1S–1S excitonic absorption peak can be managed in the spectral range of 1.5–2.1 μm (for PbS) or 1.8–2.2 μm (for PbSe) by appropriate heat‐treatment mode. The corresponding QD average diameter was found to be 5.8–9.7 nm (for PbS) and 7.5–9.5 nm (for PbSe). The influence of the secondary heat-treatment at the temperatures of 490–525 °C on the PbS QD growth in the glass matrix initially treated at 480 °C was studied in details. The photoluminescence of the PbS-QD-doped glass was observed, it was referred to the radiative recombination of the excitons from the 1S–1S state. The possibility to obtaining narrow 1S–1S absorption lines at the wavelengths longer than 2 μm is discussed.     

Synthesis and characterization of starch-stabilized Ag nanostructures for sensors applications

Silver nanostructures were successfully synthesized through a simple and ‘green’ route using starch as a capping agent. High resolution electron microscopy (HREM), X-ray diffraction (XRD), UV–Vis absorption suggested that Ag nanocrystals, having a size lower than 10 nm, were obtained, in addition a self-assembly into ribbon-like structures was been also observed. The silver nanostructures were electrodeposited onto suitable substrates with gold interdigital electrodes realizing amperometric sensors that showed a high sensitivity to hydrogen peroxide.     

表面活性剂溶液中硫化铅纳米结构的可控生长

应用软模板法成功制备了半导体硫化铅树枝状纳米结构。此反应是在非离子表面活性剂Triton X-100存在下进行的,具有条件温和,操作简单等优点。对反应过程中硫化铅各向异性生长的影响因素进行系统的阐述,通过简单地控制反应时间及表面活性剂的加入量就可得到纳米棒、纳米分枝结构以及立方结构。考虑到形貌对半导体性能有重要影响,这一实验结果的取得应具有很高的实际应用价值。     

Synthesis by organic molten salt method and characterization of chalcopyrite AgInS2 nanorods

In this paper, chalcopyrite AgInS₂ nanorods were synthesized for the first time by a one‐step, ambient pressure, environment friendly organic molten salt (OMS) method at 200 °C. The as‐synthesized products were characterized by X‐ray diffraction (XRD), scanning electron microscopy (SEM) and energy dispersive spectroscopy (EDS), respectively. The XRD results reveal that the as‐synthesized products at 120–160 °C under ambient pressure contain AgIn₅S₈ which will decrease with the increase of growth temperature. A sample containing only the chalcopyrite AgInS₂ phase is successfully obtained at 200 °C. Furthermore, the elemental compositions are found to become increasingly stoichiometric with increasing temperature. UV‐Vis and photoluminescence (PL) spectra are utilized to investigate the optical properties of AgInS₂ nanorods. By testing on UV‐Vis spectra, it is concluded that the limiting wavelength of the AgInS₂ nanorods is 661 nm and the band gap is 1.88 eV. A broad red emission band peak centered at about 1.874 eV (662 nm) is clearly observed at room temperature, and the intensity of the emission increases with excitation wavelength. In addition, the photoluminescence quantum yield (PLQY) of the nanocrystals at the excitation wavelength of 250 nm was determined to be 13.2%. A possible growth mechanism of AgInS₂ nanorods was discussed. (© 2010 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Studies on fabrication of urchin‐like WO3·H2O hollow spheres and their photocatalytic properties

Urchin‐like tungsten oxide hydrate (WO₃ · H₂O) hollow spheres were successfully synthesized via a self‐sacrifice template method at low temperature. The effects of reaction parameters on the preparation were studied in solution. The growth mechanism was also proposed on the basis of experimental results. In addition, the acid amount and temperature have important effects on size control of the as‐obtained samples. The achieved nanoarchitectures have typical diameters of 4–6 μm with nanoflakes of several nanometers at surface. Crystal structure, morphology, and composition of final nanostructures were characterized by X–ray diffraction (XRD) and scanning electron microscopy (SEM). Degradation experiments of organic contaminant were also performed on samples of hollow spheres and walnut‐like structures under visible‐light illumination. Hollow sphere sample exhibited better photocatalytic capability than walnut‐like sample. Possible mechanism was studied for WO₃ · H₂O assisted photocatalytic degradation of organic contaminant under visible light.     

Band gap energy of PbS quantum dots in oxide glasses as a function of concentration

PbS nanocrystals embedded in glass matrix (SiO₂–Na₂CO₃–Al₂O₃–B₂O₃) were synthesized by means of the fusion method using four different PbS concentrations (0.05, 0.1, 1.5, and 2.0 wt%). Thermal treatment was performed at 550 °C with annealing time of 6 h. Measurements of optical absorption and photoluminescence were carried out as a function of PbS concentration. It is argued that, with the same thermal treatment and annealing time, the formation of large nanocrystals becomes easier as the PbS concentration increases. Optical absorption spectra showed that the band-gap energy increases as the PbS concentration decreases, making this relationship important in the obtainment of a desired band-gap in PbS-doped glasses.     

热注法合成CuInSe2纳米晶的性能研究

以氯化亚铜(CuCl)、氯化铟(InCl3·4H2O)作为金属源,溶解在三辛基膦(TOP)中的Se粉作硒源,利用油胺(OLA)作为配体、十八烯作为溶剂,采用热注入法合成出了CuInSe2纳米晶(NCs),研究了反应温度对产物的影响.采用X射线衍射仪(XRD)、透射电子显微镜(TEM)、能谱仪(EDS)和紫外-可见分光光度计(UV-Vis)等测试手段对CuInSe2纳米晶的晶体结构、形貌、化学组分和光学性能进行了表征.实验结果表明:通过调控反应温度合成了具有不同形貌的黄铜矿结构的CuInSe2纳米晶,纳米晶的形貌由三角形或四边形向球形演化,其晶粒平均尺寸为3.71~13.65 nm,其光学带隙Eg在1.75~1.50 eV之间变化.所得到的产物在有机溶剂甲苯中分散性良好,这样的"墨水"溶液在后期制备薄膜太阳能电池更有利.     

Ethylenediamine inducing growth of {100} facets exposed PbS nanosheets

A simple ethylenediamine‐assisted hydrothermal method was developed for the synthesis of sheet‐like PbS nanostructures. Studies show that ethylenediamine not only provides a weakly basic environment for the reaction system, but also acts as a capping reagent to control the growth habit of cubic PbS. A reasonable growth mechanism for the PbS nanosheet structure has been proposed on the basis of the experimental studies. The structure, morphology, and composition of the nanosheets have been characterized by X‐ray powder diffraction, field‐emission scanning electron microscopy, energy‐dispersive X‐ray spectroscopy, and transmission electron microscopy.     

Template‐free synthesis of hierarchical zinc oxide with improved photocatalytic properties

Novel hierarchical nano materials possess tremendous latent force in many applications. In this paper, hierarchical flower‐like, spherical and bowl‐like zinc oxide was successfully synthesized by altering solvent ratio (absolute ethanol and diethylene glycol) via a simple and template‐free solvothermal synthetic route. The solvent ratio also plays a vital role in deciding the structure, crystalline, band gap energy and specific surface area of the as‐synthesized samples. The preparation mechanism of ZnO in mixed alcohols was discussed. The obtained samples were characterized by energy dispersive spectroscopy(EDS), X‐ray diffraction (XRD), field emission scanning electron microscope (FESEM), transmission electron microscopy (TEM), N2 adsorption‐desorption, UV–vis diffuse reflectance spectroscopy (DRS). Photocatalytic activity of the as‐prepared ZnO nanocrystals was evaluated by the degradation of MB under UV irradiation. Among, the most effective photocatalyst was synthesized when the diethylene glycol was 10 ml.     

Morphology‐photocatalytic properties‐growth mechanism for ZnO nanostructures via microwave‐assisted hydrothermal synthesis

ZnO nanostructures with various morphologies including rod‐like, sheet‐like, needle‐like and flower‐like structures were successfully synthesized via a fast and facile microwave‐assisted hydrothermal process. Reaction temperature, reaction time and the addition of NaOH were adjusted to obtain ZnO with different morphologies. Scanning electron microscopy(SEM), transmission electron microscope(TEM), X‐ray diffraction (XRD) and ultraviolet spectrophotometer (UV) were used to observe the morphology, crystal structure, ultraviolet absorption and photocatalytic activity of the obtained ZnO. The results indicated that growth rate of ZnO nanostructure along [001] direction was more sensitive to temperature compared with those along [101] and [100] directions. The competition between anionic surfactant and OH⁻ played an important role in the formation of ZnO with various morphologies. Flower‐like ZnO had better ultraviolet absorption property and excellent photocatalytic activity than ZnO in the other morphologies. On the basis of the above results, a possible growth mechanism for the formation of ZnO nanostructures with different morphologies was described.     

Controlled growth of ZnO torch‐like nanostructure arrays

Single‐crystal ZnO torch‐like nanostructure arrays were synthesized using a simple two‐step pressure controlled thermal evaporation method without any catalyst. The nanostructures had a hierarchical morphology, with well‐hexagonal faceted holders and needle‐like flames on them. The diameter of each single flame was about 20–40nm at the base and 10nm at the tip. Both the holders and flames were found to grow along the [0001] direction. The morphology of the structures could be effectively controlled by varying the growth temperature and vacuum pressure. The experimental results and analysis provided easy strategies to control the morphology of nanostructures and also enhanced the understanding of the growth mechanism. (© 2008 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)