Solvothermal synthesis and luminescence properties of CdS:Mn nanorods

CdS:Mn nanorods have been produced via a solvothermal approach in the nonaqueous solvent of ethylenediamine. An absolutely dominant single Mn²⁺ emission originating from the d-d (⁴T₁-⁶A₁) transition was obtained in CdS:Mn nanocrystals at room temperature. The effects of varying reaction temperature, molar ratio of S/Cd, and reaction time on the crystallinity and luminescence of CdS:Mn nanocrystals were systematically investigated. 1% Mn²⁺-doped CdS nanorods without any other additives were synthesized at 130°C for 10 h with an S/Cd molar ratio of 2:1. They show a rod-like shape, and their luminescence intensity around 593 nm is almost the strongest of all the nanorod samples investigated. CdS:Mn nanorods promise potential applications in nanoscale electronic and photonic devices.     

Synthesis of high aspect ratio quantum-size CdS nanorods and their surface-dependent photoluminescence

Colloidal CdS nanorods with diameters near 4 nm and narrow size distributions ( approximately +/-10%) were synthesized up to 300 nm long by a sequential reactant injection technique that utilizes phosophonic acids as capping ligands. The phosphonic acid strongly passivates the nonpolar CdS surfaces and sequential reactant injection provides controlled CdS formation kinetics to enable heterogeneous and facet-selective CdS deposition on the more reactive {002} surfaces. With this process, the nanorod length can be systematically increased by increasing reactant addition to extend nanorod growth. The phosphonic acid concentration, however, is quite important, as "low" concentrations allow radial deposition and branching to occur. These high aspect ratio (>100) CdS nanorods luminesce with relatively high efficiencies of 10.8% quantum yield at room temperature. The luminescence, however, mostly arises from trap-related recombination, and the emission is significantly red-shifted from the absorption edge. Various surface passivation treatments were explored to eliminate trap emission and increase the luminescence quantum yield. Thiol and amine passivation both significantly reduced trap emission and enhanced band-edge emission, but the total luminescence quantum yields dropped significantly, with a maximum measured value of 1.5% for the amine-passivated CdS nanorods.     

Sonochemical fabrication and characterization of stibnite nanorods

Regular stibnite (Sb(2)S(3)) nanorods with diameters of 20-40 nm and lengths of 220-350 nm have been successfully synthesized by a sonochemical method under ambient air from an ethanolic solution containing antimony trichloride and thioacetamide. The as-prepared Sb(2)S(3) nanorods are characterized by employing techniques including X-ray powder diffraction, X-ray photoelectron spectroscopy, scanning electron microscopy, energy-dispersive X-ray analysis, transmission electron microscopy, selected area electron diffraction, high-resolution transmission electron microscopy, and optical diffuse reflection spectroscopy. Microstructural analysis reveals that the Sb(2)S(3) nanorods crystallize in an orthorhombic structure and predominantly grow along the (001) crystalline plane. High-intensity ultrasound irradiation plays an important role in the formation of these Sb(2)S(3) nanorods. The experimental results show that the sonochemical formation of stibnite nanorods can be divided into four steps in sequence: (1) ultrasound-induced decomposition of the precursor, which leads to the formation of amorphous Sb(2)S(3) nanospheres; (2) ultrasound-induced crystallization of these amorphous nanospheres and generation of nanocrystalline irregular short rods; (3) a crystal growth process, giving rise to the formation of regular needle-shaped nanowhiskers; (4) surface corrosion and fragmentation of the nanowhiskers by ultrasound irradiation, resulting in the formation of regular nanorods. The optical properties of the Sb(2)S(3) amorphous nanospheres, irregular short nanorods, needle-shaped nanowhiskers, and regular nanorods are investigated by diffuse reflection spectroscopic measurements, and the band gaps are measured to be 2.45, 1.99, 1.85, and 1.94 eV, respectively.     

Use of ionic liquids in the synthesis of nanocrystals and nanorods of semiconducting metal chalcogenides

We have synthesized nanoparticles of hexagonal CdS in the diameter range 3-13 nm by the reaction of cadmium acetate dihydrate with thioacetamide in imidazolium [BMIM]-based ionic liquids. We have obtained three different particle sizes of CdS by changing the anion of the ionic liquid. Addition of trioctylphosphine oxide (TOPO) to the reaction mixture causes greater monodispersity as well as smaller particle size, while addition of ethylenediamine produces nanorods of 7 nm average diameter. Hexagonal ZnS and cubic PbS nanoparticles with average diameters of 3 and 10 nm, respectively, have been prepared by the reaction of the metal acetates with thioacetamide in [BMIM][BF4]. Hexagonal CdSe nanoparticles with an average diameter 12 nm were obtained by the reaction of cadmium acetate dihydrate with dimethylselenourea in [BMIM][BF4]. In this case also we observe the same effect of the addition of TOPO as in the case of CdS. Addition of ethylenediamine to the reaction mixture gives rise to nanorods. ZnSe nanowires with a cubic structures, possible diameters in the range 70-100 nm by the reaction of zinc acetate dihydrate with dimethylselenourea in [BMIM][MeSO4]. The nanostructures obtained are single crystalline in all the cases. Most of the nanostructures show characteristic UV/Vis absorption and photoluminescence emission spectra. The thermodynamically most stable structures are generally produced in the synthesis carried out in ionic liquids.     

CeO2 nanorods and gold nanocrystals supported on CeO2 nanorods as catalyst

The formation mechanism of uniform CeO2 structure at the nanometer scale via a wet-chemical reaction is of great interest in fundamental study as well as a variety of applications. In this work, large-scale well-crystallized CeO2 nanorods with uniform diameters in the range of 20-30 nm and lengths up to tens of micrometers are first synthesized through a hydrothermal synthetic route in 5 M KOH solution at 180 degrees C for 45 h without any templates and surfactants. The nanorod formation involves dehydration of CeO2 nanoparticles and orientation growth along the 110 direction in KOH solution. Subsequently, gold nanoparticles with crystallite sizes between 10 and 20 nm are loaded on the surface of CeO2 nanorods using HAuCl4 solution as the gold source and NaBH4 solution as a reducing agent. The synthesized Au/CeO2 nanorods demonstrate a higher catalytic activity in CO oxidation than the pure CeO2 nanorods.     

Fabrication of CdS Nanorods in PVP Fiber Matrices by Electrospinning

Summary: A controlled fabrication of rod‐like nanostructures of cadmium sulfide (CdS) incorporated into polymer fiber matrices has been developed by an electrospinning method. Here, poly(vinyl pyrrolidone) (PVP) was used as a polymer capping reagent, utilizing the interactions of cadmium ions with the carbonyl groups in the PVP molecules. The formation of CdS nanorods inside the PVP was carried out via the reaction of Cd²⁺ with H₂S. SEM images showed that the electrospun films of PVP/CdS are composed of fibers with a diameter between 100 and 900 nm. TEM proved that most of the CdS nanorods are incorporated in the PVP fibrous film. The diameter of the rod is about 50 nm and the length is from 100 to 300 nm.

TEM image of the CdS nanorods formed in the PVP fibrous film.     

Synthesis and formation mechanism of nanoneedles and nanorods of manganese oxide octahedral molecular sieve using an ionic liquid

Single-crystalline cryptomelane-type manganese oxide octahedral molecular sieve (OMS-2) nanoneedles and nanorods were prepared by a solution-phase approach in the presence of an ionic liquid 1-n-butyl-3-methylimidazolium tetrafluoroborate ([BMIM]BF4). [BMIM]BF4 can act as a cosolvent, structure-directing agent, and reducing reagent in the reaction system. Based on the redox reaction of MnCl2 and KMnO4 in the mixed solvents of water and [BMIM]BF4, the formation of OMS-2 nanoneedles followed the rolling mechanism with lamellae as an intermediate. However, the direct reaction of KMnO4 with [BMIM]BF4 resulted in the formation of OMS-2 nanorods with diameters as small as 3-6 nm. The formation mechanism of OMS-2 nanostructures was discussed.     

Synthesis of ZnO nanorods and their application in quantum dot sensitized solar cells

ZnO nanorod thin films of different thicknesses and CdS quantum dots have been prepared by chemical method. X-ray diffraction pattern reveals that the CdS quantum dot and ZnO nanorods are of hexagonal structure. Field emission scanning electron microscope images show that the diameter of hexagonal shaped ZnO nanorods ranges from 110 to 200 nm and the length of the nanorod vary from 1.3 to 4.7 μm. CdS quantum dots with average size of 4 nm have been deposited onto ZnO nanorod surface using successive ionic layer adsorption and reaction method and the assembly of CdS quantum dot with ZnO nanorod has been used as photo-electrode in quantum dot sensitized solar cells. The efficiency of the fabricated CdS quantum dot-sensitized ZnO nanorod-based solar cell is 1.10 % and is the best efficiency reported so far for this type of solar cells.     

Synthesis of CeO2 nanorods via ultrasonication assisted by polyethylene glycol

Polycrystalline CeO2 nanorods 5-10 nm in diameter and 50-150 nm in length were synthesized via ultrasonication using polyethylene glycol (PEG) as a structure-directing agent at room temperature. The properties of the CeO2 nanorods were characterized by TEM, EDS, XRD, XPS, FT-IR, TG, BET, and UV-vis spectroscopy. Various reaction parameters, such as the content of PEG, the molecular weight of PEG, the concentration of KOH, the pH value, and the sonication time, were investigated by a series of control experiments. The content of PEG, the molecular weight of PEG, and the sonication time were confirmed to be the crucial factors determining the formation of one-dimensional CeO2 nanorods. A possible ultrasonic formation mechanism has been suggested to explain the formation of CeO2 nanorods.     

Simultaneous phase- and size-controlled synthesis of TiO(2) nanorods via non-hydrolytic sol-gel reaction of syringe pump delivered precursors

The simultaneous phase- and size-controlled synthesis of TiO(2) nanorods was achieved via the non-hydrolytic sol-gel reaction of continuously delivered two titanium precursors using two separate syringe pumps. As the injection rate was decreased, the length of the TiO(2) nanorods was increased and their crystalline phase was simultaneously transformed from anatase to rutile. When the reaction was performed by injecting titanium precursors contained in two separate syringes into a hot oleylamine surfactant solution with an injection rate of 30 mL/h, anatase TiO(2) nanorods with dimensions of 6 nm (thickness) x 50 nm (length) were produced. When the injection rate was decreased to 2.5 mL/h, star-shaped rutile TiO(2) nanorods with dimensions of 25 nm x 200 nm and a small fraction of rod-shaped anatase TiO(2) nanorods with dimensions of 9 nm x 100 nm were synthesized. Pure star-shaped rutile TiO(2) nanorods with dimensions of 25 nm x 450 nm were synthesized when the injection rate was further decreased to 1.25 mL/h. The simultaneous phase transformation and length elongation of the TiO(2) nanorods were achieved. Under optimized reaction conditions, as much as 3.5 g of TiO(2) nanorods were produced. The TiO(2) nanorods were used to produce dye-sensitized solar cells, and the photoconversion efficiency of the mixture composed of star-shaped rutile TiO(2) nanorods and a small fraction of anatase nanorods were comparable to that of Degussa P-25.     

Synthesis of single-crystalline platinum nanorods within a soft crystalline surfactant-Pt(II) complex.

Single-crystalline platinum nanorods, monodisperse in diameter, are synthesized through a simple process at room temperature, in cetyltrimethyl ammonium bromide (CTAB) solution. The complexation of the CTA+ surfactant ion with tetrachloroplatinate in the presence of hexanol leads to the formation of a precipitate with a lamellar crystalline structure. The reduction of Pt(II) metal ions to Pt(0) is carried out using gamma radiolysis. Transmission electron microscopy (TEM) observations of the nanoparticles extracted from the solution, three weeks after radiolysis, revealed single-crystalline Pt nanorods, monodisperse in diameter (3-4 nm) and 20-60 nm long. By following the shape of the nanorods at various stages of the growth, it was found that the single-crystalline nanorods grow by coalescence of spherical seeds 3-4 nm in diameter. This suggests an aggregative mechanism similar to that recently observed for silver particles in solution.     

Photocatalytic Dye Methyl Orange Decomposition on Ternary Sulfide （CdIn2S4） under Visible-light

A novel and efficient photocatalyst, CdIn2S4, was simply prepared by a programmed temperature hydrothermal method. The product had a nanometer size （10-15 nm） and strong absorption in the range of 200 to 580 nm, and it exhibited visible-light photocatalytic activity to decompose dye methyl orange in aqueous system.     

Design of liquid-crystalline aqueous suspensions of rutile nanorods: evidence of anisotropic photocatalytic properties

TiO2 rutile nanorods of average length L = 160 +/- 40 nm and average diameter D = 15 +/- 5 nm have been synthesized through a seed-mediated growth process by TiCl4 hydrolysis in concentrated acidic solution. These nanorods were dispersed in water to yield stable (aggregation-free) colloidal aqueous suspensions. At volume fractions phi > 3%, the suspensions spontaneously display a phase separation into an isotropic liquid phase and a liquid-crystalline phase identified as nematic by X-ray scattering. At phi > 12%, the suspensions form a nematic single phase, with large order parameter, S = 0.75 +/- 0.05. Very well aligned rutile films on glass substrate were produced by spin-coating, and their photocatalytic properties were examined by monitoring the decomposition of methylene blue under UV light. We found that UV-light polarized along the quadratic axis of the rutile nanorods was most efficient for this photocatalytic reaction.     

Solventless synthesis of copper sulfide nanorods by thermolysis of a single source thiolate-derived precursor

Organic monolayer protected Cu2S nanorods, 4 nm in diameter and 12 nm long, were synthesized using a novel solventless synthetic approach. Thermolytic degradation of a copper thiolate precursor at temperatures ranging from 140 to 200 degrees C produces Cu2S nanorods. Higher temperatures promote isotropic growth of spherical nanocrystals. X-ray diffraction and high-resolution TEM reveal that the nanorods exhibit a hexagonal Cu2S crystal structure, which in the bulk is ferroelectric. The appropriate reaction conditions produce nanorods that are size and shape monodisperse and organize into smectic superlattices. The extent of superlattice ordering and the appearance of extended strands of nanorods provide evidence for strong dipole-dipole coupling between Cu2S nanorods.     

利用牛血清蛋白合成CdS纳米棒和网状纳米线

采用简单易控、对环境友好的矿化方法, 利用牛血清蛋白(BSA)做模板, 通过Cd2+与硫代乙酰胺(TAA)反应制备了形貌均一的CdS纳米棒和网状纳米线. 分别采用透射电子显微镜(TEM)、X射线能谱(EDS)、X射线衍射(XRD)、荧光(PL)发射谱和导电原子力显微镜(C-AFM)等方法对不同实验温度下制备的CdS样品的结构形貌、成分组成和光学性质及微区电子传输行为进行了表征. 结果表明: 在实验反应温度为20 ℃时, 得到的产物为单分散性好的CdS 纳米棒, 长度为250 nm, 直径为30 nm; 在50 ℃时, 得到网状CdS纳米线, 其长度为2-3 μm; CdS纳米棒和网状纳米线均为立方相闪锌矿结构. 荧光性质的测试表明, CdS纳米棒和网状纳米线具有优良的荧光性能, 电流-电压(I-V)特性的表征表明CdS纳米线具有很好的电导特性.     

纳米硫化镉的合成及其电化学催化性能测试

采用CS2-SDS-正辛醇-水微乳体系制备了硫化镉纳米棒。利用XRD、SEM、TEM对产物进行表征，测试了其对多硫化物电极还原反应的催化性能，并与常规方法合成的大粒度CdS晶体进行对比．结果表明，纳米棒为六方型CdS晶体，直径约12nm．常规法合成的CdS为立方型晶体，平均粒度约为1μm．CdS纳米棒电极对硫化钠／多硫化钠电极反应的电催化活性明显高于大粒度CdS晶体电极．     

CdS nanocrystallites sensitized ZnO nanorods with plasmon enhanced photoelectrochemical performance

A novel architecture of CdS/ZnO nanorods with plasmonic silver (Ag) nanoparticles deposited at the interface of ZnO nanorods and CdS nanocrystallites, was designed as a photoanode for solar hydrogen generation, with photocurrent density achieving 4.7 mA/cm² at 1.6 V (vs. RHE), which is 8 and 1.7 times as high as those of pure ZnO and CdS/ZnO nanorod films, respectively. Additionally, with optical absorption onset extended to ～660 nm, CdS/Ag/ZnO nanorod film exhibits significantly increased incident photo-to-current efficiency (IPCE) in the whole optical absorption region, reaching 23.1% and 9.8% at 400 nm and 500 nm, respectively. The PEC enhancement can be attributed to the one-dimensional ZnO nanorod structure maintained for superior charge transfer, and the extended visible-light absorption of CdS nanocrystallites. Moreover, the incorporated plasmonic Ag nanoparticles could further promote the interfacial charge carrier transfer process and enhance the optical absorption ability, due to its excellent plasmon resonance effect.     

溶剂热法合成CdS纳米晶及其光学性质研究

以硫脲和醋酸镉为原料,采用溶剂热法在不同的反应介质和温度下合成了CdS纳米晶,比较了单胺与双胺对合成CdS纳米晶形貌的影响。采用透射电镜(TEM)、X射线粉末衍射仪(XRD)和荧光分光光度计(PL)对合成的CdS纳米晶结构和光学性能进行表征。结果表明:反应温度和反应介质对其形貌有影响,在双胺的条件下,60℃时合成了纯相的六方相CdS纳米棒;双胺条件下更易生成纳米棒,且高温下晶体的结晶性更好。PL分析表明,水(溶剂)热法制备的CdS的荧光光谱图与大多数CdS类似,均在440~480 nm和550 nm处存在发射峰,但较宽的发射峰蓝移说明材料的光学性质受到材料形貌和制备方法的影响。     

CdS nanocrystallites sensitized ZnO nanorods with plasmon enhanced photoelectrochemical performance

A sandwiched structure of CdS/Ag/ZnO nanorod photoanode exhibits greatly enhanced photoelectrochemical activity for solar hydrogen generation, due to synergistic effect of CdS nanocrystallites and plasmonic Ag nanoparticles for the enhanced optical absorption and the promoted charge carrier separation.     

Liquid-crystalline polymer composites with CdS nanorods: structure and optical properties

We report on the structure, uniaxial orientation, and photoluminescent properties of CdS nanorods that form stable nanocomposites with smectic C hydrogen-bonded polymers from the family of poly(4-(n-acryloyloxyalkoxy)benzoic acids. TEM analysis of microtomed films of nanocomposites reveals that CdS nanorods form small domains that are homogeneously distributed in the LC polymer matrix. They undergo long-range orientation with the formation of one-dimensional aggregates of rods when the composite films are uniaxially deformed. The Stokes photoluminescence was observed from CdS NRs/LC polymer composites with emission peak located almost at the same wavelength as that of NRs solution in heptane. An anti-Stokes photoluminescence (ASPL) in polymer nanocomposites was found under the excitation below the nanoparticles ground state. The mechanism of ASPL was interpreted in terms of thermally populated states that are involved in the excitation process. These nanocomposites represent an unusual material in which the optical properties of anisotropic semiconductor nanostructures can be controlled by mechanical deformation of liquid-crystalline matrix.