Synthesis and optical properties of small Au nanorods using a seedless growth technique

Gold nanoparticles have shown potential in photothermal cancer therapy and optoelectronic technology. In both applications, a call for small size nanorods is warranted. In the present work, a one-pot seedless synthetic technique has been developed to prepare relatively small monodisperse gold nanorods with average dimensions (length × width) of 18 × 4.5 nm, 25 × 5 nm, 15 × 4.5 nm, and 10 × 2.5 nm. In this method, the pH was found to play a crucial role in the monodispersity of the nanorods when the NaBH(4) concentration of the growth solution was adjusted to control the reduction rate of the gold ions. At the optimized pH and NaBH(4) concentrations, smaller gold nanorods were produced by adjusting the CTAB concentration in the growth solution. In addition, the concentration of silver ions in the growth solution was found to be pivotal in controlling the aspect ratio of the nanorods. The extinction coefficient values for the small gold nanorods synthesized with three different aspect ratios were estimated using the absorption spectra, size distributions, and the atomic spectroscopic analysis data. The previously accepted relationships between the extinction coefficient or the longitudinal band wavelength values and the nanorods' aspect ratios found for the large nanorods do not extend to the small size domain reported in the present work. The failure of extending these relationships over larger sizes is a result of the interaction of light with the large rods giving an extinction band which results mostly from scattering processes while the extinction of the small nanorods results from absorption processes.     

Spontaneous self-assembly of cerium oxide nanoparticles to nanorods through supraaggregate formation

Self-assembly of cerium oxide nanoparticles to nanorods is reported. Such nanorods have an aspect ratio of 6 with a diameter of approximately 40 nm. The formation of cylindrical supraaggregates and their subsequent growth by preferential assembling of ceria nanocrystallites along the longitudinal direction was proposed to be the probable mechanism of spontaneous self-assembly of nanorods. The supraaggregate formation was facilitated by influencing the local curvature of the micelle surface in the presence of nitrate ions as a precursor solution. The nanorods were characterized using high-resolution transmission electron microscopy with energy dispersive spectroscopy and selected area electron diffraction for their morphology, chemistry, and crystal structure.     

Quantitation of metal content in the silver-assisted growth of gold nanorods

The seed-mediated approach to making gold nanorods in aqueous surfactant solutions has become tremendously popular in recent years. Unlike the use of strong chemical reductants to make spherical gold nanoparticles, the growth of gold nanorods requires weak reducing conditions, leading to an unknown degree of gold reduction. The metal content of gold nanorods, made in high yield in the presence of silver ion, is determined by inductively coupled plasma atomic emission spectroscopy. Through the use of the known gold concentration in nanorods, molar extinction coefficients are calculated for nanorods of varying aspect ratios from 2.0 to 4.5. The extinction coefficients at the longitudinal plasmon band peak maxima for these nanorods vary from 2.5x10(9) to 5.5x10(9) M-1 cm-1, respectively, on a per-particle basis. Many of the gold ions present in the growth solution remain unreacted; insights into the growth mechanism of gold nanorods are discussed.     

Short gold nanorod growth revisited: the critical role of the bromide counterion

A one-step, surfactant-assisted, seed-mediated method has been utilized for the growth of short gold nanorods with reasonable yield by modifying an established synthesis protocol. Among the various parameters that influence nanorod growth, the impact of the bromide counterion has been closely scrutinized. During this study it has been shown that, irrespective of its origin, the bromide counterion [cetyltrimethylammonium bromide (CTAB) or NaBr] plays a crucial role in the formation of nanorods in the sense that there is a critical [Br(-)]/[Au(3+)] ratio (around 200) to achieve nanorods with a maximum aspect ratio. Beyond this value, bromide can be considered as a poisoning agent unless shorter nanorods are required. The use of AgNO(3) helps in symmetry breaking for gold nanorod growth, whereas the bromide counterion controls the growth kinetics by selective adsorption on the facets of the growth direction. Thus, a proper balance between bromide ions and gold cations is also one of the necessary parameters for controlling the size of the gold nanorods; this has been discussed thoroughly. The results have been discussed based on their absorption spectra and finally shape evolution has been confirmed by TEM. Due to their efficient absorption in the near-IR region, these short nanorods were used in photothermal imaging of living COS-7 cells with improved signal-to-background ratios.     

Computational modeling of nanorod growth

In this computational study, we used molecular dynamics and the embedded atom method to successfully reproduce the growth of gold nanorod morphologies from starting spherical seeds in the presence of model surfactants. The surfactant model was developed through extensive systematic attempts aimed at inducing nonisotropic nanoparticle growth in strictly isotropic computational growth environments. The aim of this study was to identify key properties of the surfactants which were most important for the successful anisotropic growth of nanorods. The observed surface and collective dynamics of surfactants shed light on the likely growth phenomena of real nanoprods. These phenomena include the initial thermodynamically driven selective adsorption, segregation, and orientation of the surfactant groups on specific crystallographic surfaces of spherical nanoparticle seeds and the kinetic elongation of unstable surfaces due to growth inhibiting surfactants on those surfaces. Interestingly, the model not only reproduced the growth of nearly all known nanorod morphologies when starting from an initial fcc or fivefold seed but also reproduced the experimentally observed failure of nanorod growth when starting from spherical nanoparticles such as the I(h) morphology or morphologies containing a single twinning plane. Nanorod morphologies observed in this work included fivefold nanorods, fcc crystalline nanorods in the [100] direction and [112] directions and the more exotic "dumbell-like" nanorods. Non-nanorod morphologies observed included the I(h) and the nanoprism morphology. Some of the key properties of the most successful surfactants seemed to be suggestive of the important but little understood role played by silver ions in the growth process of real nanorods.     

Synthesis and shape-tailoring of copper sulfide/indium sulfide-based nanocrystals

Heterostructured Cu2S-In2S3 nanocrystals with various shapes and compositions were synthesized by a high-temperature precursor-injection method using the semiconductor nanocrystal Cu1.94S as a catalyst. The intrinsic cationic deficiencies formed at high temperature by Cu ions made the Cu1.94S nanocrystal a good candidate for catalyzing the nucleation and subsequent growth of In 2S3 nanocrystals, eventually leading to the formation of heterostructured Cu2S-In2S3 nanocrystals. Gelification of the reaction systems, which were composed of different types of nanocrystal precursors and solvent, was found to be a very effective measure for controlling the growth kinetics of the heterostructured particles. Consequently, matchsticklike Cu2S3-In2S3 heterostructured nanorods, teardroplike quasi-core/shell Cu2S@In2S3 nanocrystals, and pencil-like In2S3 nanorods were successfully obtained by manipulating the gelification of the reaction system; this formed a solid experimental basis for further discussion of the growth mechanisms for differently shaped and structured nanocrystals. By reaction with 1,10-phenanthroline, a reagent that strongly and selectively binds to Cu(+), a compositional transformation from binary matchsticklike Cu2S-In2S3 nanorods to pure In2S3 nanorods was successfully achieved.     

熔盐法制备氧化锆纳米棒

采用非水解溶胶-凝胶工艺合成氧化锆干凝胶粉,然后将干凝胶粉与熔盐混合制备氧化锆纳米棒。借助DTA-TG、XRD、FE-SEM、TEM等测试手段研究了氧化锆的物相转变过程,探讨了熔盐种类与用量、氟化物的添加等工艺参数对制备氧化锆纳米棒的影响。结果表明:以Na VO3为熔盐,用量为1∶1(熔盐与干凝胶的质量比),并且在添加氟化钠的条件下能够制备产率高,且沿[010]方向择优生长的单斜氧化锆纳米棒;氟离子一方面加速了熔盐中Zr4+离子的传质,促使氧化锆干凝胶粉的溶解,另一方面吸附在氧化锆的高能晶面上抑制该晶面的生长,两者的共同作用促进了大量氧化锆纳米棒的形成。     

熔盐法制备氧化锆纳米棒

采用非水解溶胶-凝胶工艺合成氧化锆干凝胶粉,然后将干凝胶粉与熔盐混合制备氧化锆纳米棒。借助DTA-TG、XRD、FE-SEM、TEM等测试手段研究了氧化锆的物相转变过程,探讨了熔盐种类与用量、氟化物的添加等工艺参数对制备氧化锆纳米棒的影响。结果表明：以NaVO₃为熔盐,用量为1：1（熔盐与干凝胶的质量比）,并且在添加氟化钠的条件下能够制备产率高,且沿[010] 方向择优生长的单斜氧化锆纳米棒;氟离子一方面加速了熔盐中Zr⁴⁺离子的传质,促使氧化锆干凝胶粉的溶解,另一方面吸附在氧化锆的高能晶面上抑制该晶面的生长,两者的共同作用促进了大量氧化锆纳米棒的形成。     

Influences of Co doping on the structural,optical and magnetic properties of ZnO nanorods synthesized by hydrothermal route

Pure and Co-doped ZnO nanorods have been synthesized by a hydrothermal process. The structure, morphology and properties of as-prepared samples have been studied using X-ray diffraction (XRD), transmission electron microscopy (TEM), energy dispersive spectroscopy (EDS), X-ray photoelectron spectroscopy (XPS), photoluminescence (PL) spectrometer as well as by superconducting quantum interference device (SQUID). The structure and morphology analyses show that Co doping can slightly impede the ZnO crystallinity, influence the nanorods morphology, but cannot change the preferred growth orientation of ZnO nanorods. The amount of Co doping contents is about 3.0 at% in ZnO nanorods and dopant Co²⁺ ions substitute Zn²⁺ ions sites in ZnO nanocrystal without forming any secondary phase. The optical measurements show that the Co doping can effectively tune energy band structure and enrich surface states in both UV and VL regions, which lead to novel PL properties of ZnO nanorods. In addition, ferromagnetic ordering of the as-synthesized Zn_1?xCo_xO nanorod arrays has been observed at room temperature, which should be ascribed to sp–d and d–d carrier exchange interactions and presence of abundant defects and oxygen vacancies.     

Near-Infrared Fluorimetric Determination of Copper(Ⅱ) Ions Using CdHgTe Nanorods as Probe

Stable water‐soluble CdHgTe nanorods with an emission wavelength at 722 nm, obtained by doping Hg²⁺ into CdTe nanorods, has been used as a near‐infrared region (NIR) probe to investigate their interaction with copper(II) ions. A new fluorimetric method for the determination of copper(II) ions has been developed based on the quenching effect of copper(II) ions on the emission of CdHgTe nanorods. The mechanism studies show that an effective electron transfer from nanorods to the copper(II) ions occurred based on the coordination reaction between copper(II) ions and the carboxyl groups on the nanorods surface, which could be responsible for the emission quenching of CdHgTe nanorods. Under optimum conditions, the linear range of the calibration curve for the determination of Cu²⁺ is from 8.0×10^?9 to 1.0×10^?6 mol/L and the detection limit is 2.0×10^?9 mol/L. Owing to low background interference of NIR measurement, the proposed method displays relative high sensitivity and selectivity. Especially, some physiologically important cations almost do not interfere with the determination of Cu²⁺. The proposed method was also applied to the determination of trace Cu²⁺ in real aqueous samples with satisfactory results.     

Self-construction of core-shell and hollow zeolite analcime icositetrahedra: a reversed crystal growth process via oriented aggregation of nanocrystallites and recrystallization from surface to core

Zeolite analcime with a core-shell and hollow icositetrahedron architecture was prepared by a one-pot hydrothermal route in the presence of ethylamine and Raney Ni. Detailed investigations on samples at different preparation stages revealed that the growth of the complex single crystalline geometrical structure did not follow the classic crystal growth route, i.e., a crystal with a highly symmetric morphology (such as polyhedra) is normally developed by attachment of atoms or ions to a nucleus. A reversed crystal growth process through oriented aggregation of nanocrystallites and surface recrystallization was observed. The whole process can be described by the following four successive steps. (1) Primary analcime nanoplatelets undergo oriented aggregation to yield discus-shaped particles. (2) These disci further assemble into polycrystalline microspheres. (3) The relatively large platelets grow into nanorods by consuming the smaller ones, and meanwhile, the surface of the microspheres recrystallizes into a thin single crystalline icositetrahedral shell via Ostwald ripening. (4) Recrystallization continues from the surface to the core at the expense of the nanorods, and the thickness of the monocrystalline shell keeps on increasing until all the nanorods are consumed, leading to hollow single crystalline analcime icositetrahedra. The present work adds new useful information for the understanding of the principles of zeolite growth.     

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.     

Preparation and characterization of LiFe0.975Rh0.025PO4 nanorods using the hydrothermal method

An effective method for the synthesis of LiFe(0.975)Rh(0.025)PO(4) nanorods to serve as a cathode material for lithium-ion batteries is described. During their preparation, L-lysine was used as the growth director of nanorods. The contribution from chloride ions to the formation of the unique nanorods was also investigated. The samples were characterized using X-ray diffraction, X-ray photoelectron spectroscopy, M?ssbauer measurements, scanning electron microscopy, electronic conductivity measurements, and transmission electron microscopy. The pH of the solution played a key role in controlling the particle size of the samples. The sample prepared at a pH of 9.5 exhibited excellent electrochemical performance. It delivered an initial discharge capacity of 143.1 mA h g(-1), and a capacity fade of only 7.7% was observed after 200 cycles at 2.5 C over a voltage range of 2.0-4.2 V. Furthermore, its discharge capacity remained stable for values as high as 20 C. The excellent electrochemical performance of LiFe(0.975)Rh(0.025)PO(4) nanorods can be attributed their unique nanorod structure, which limits the distance of lithium ion diffusion in the electrode material to the radius of the nanorods and decreases the surface-film resistance for the charge-transfer process.     

One-step synthesis of silver nanoparticles, nanorods, and nanowires on the surface of DNA network

Here, we describe a one-step synthesis of silver nanoparticles, nanorods, and nanowires on DNA network surface in the absence of surfactant. Silver ions were first adsorbed onto the DNA network and then reduced in sodium borohydride solution. Silver nanoparticles, nanorods, and nanowires were formed by controlling the size of pores of the DNA network. The diameter of the silver nanoparticles and the aspect ratio of the silver nanorods and nanowires can be controlled by adjusting the DNA concentration and reduction time.     

Fabrication and Visible Light Photocatalytic Activity of Co-doped ZnO Nanorods

Co-doped ZnO nanorods were prepared by electrochemical deposition method in aqueous solution. lb study the as-grown samples, several characterizations were carried out. The scanning electron microscopy（SEM） images show that the samples present a rod-like shape with hexagonal cross sections and roughened surthce. There is a slight shift for （002） diffraction peak of Co-doped ZnO nanorods in XRD because Co2~ ions entered into the ZnO lattice. Energy-dispersive X-ray spectroscopy（EDS） and X-ray photoelectron spectroscopy（XPS） results also show the exist of Co in the sample. Photoluminescence（PL） spectra of the samples were observed at room tempera- ture, the UV emission of Co-doped ZnO shows a slight red shift compared with that of undoped ZnO. Thus, we can reach the conclusion that Zn2＋ ions have been substituted by Co2. ions in the ZnO samples. In addition, photocatalysis property of Co-doped ZnO nanorods was investigated under the irradiation of visible light. It was found that the degradation rate of methyl orange is increased greatly nanorods. by Co-doped ZnO nanorods in comparison to undoped ZnO     

Roles of anionic and cationic template components in biomineralization of CdS nanorods using self-assembled DNA-membrane complexes

Complexes of anionic DNA and cationic liposomes self-assemble into a multilamellar structure where two-dimensional lipid sheets confine a periodic one-dimensional lattice of parallel DNA chains, between which Cd(2+) ions can condense, and be subsequently reacted with H(2)S to form CdS nanorods. In this work, we identify the synergistic roles of the anionic and cationic components within the DNA-membrane template; DNA is highly anionic and condenses the Cd(2+) ions, while the cationic membrane modulates the concentration of condensed Cd(2+) ions to control the final CdS nanorod dimensions. Due to the strong electrostatic interactions between the DNA sugar-phosphate backbone and the Cd(2+) ions, crystallographic control of CdS nanostructures is possible using these simple DNA-membrane templates, which we demonstrate using nanobeam electron diffraction experiments on individual templated CdS nanorods.     

Synthesis and characterization of colloidal ternary ZnCdSe semiconductor nanorods

For the synthesis of colloidal ternary ZnCdSe nanorods, CdSe nanorods were first prepared under a mixture of tetradecylphosphonic acid/trioctylphosphine oxide surfactants at 250 degrees C, and then ZnSe shell layer was grown onto CdSe nanorods at 180 degrees C, forming CdSeZnSe core/shell nanorods. Green-yellow emitting ternary ZnCdSe nanorods were obtained by a subsequent alloying process at 270 degrees C for 1-3 h through the diffusion of Zn ions into CdSe nanorods. The photoluminescence quantum yield (QY) of ZnCdSe nanorods was 5%-10%, which is higher than that from pristine CdSe nanorods (0.6%). The QY of these alloy nanorods depends on the alloying time and is discussed in terms of compositional disorders and defects produced by the alloying process. The Raman and time resolved photoluminescence spectroscopies were used to understand the detailed alloying process from CdSeZnSe core/shell to ZnCdSe alloy nanorods.     

Size-controlled synthesis and growth mechanism of monodisperse tellurium nanorods by a surfactant-assisted method

This article describes a surfactant-assisted approach to the size-controlled synthesis of uniform nanorods of trigonal tellurium (t-Te). These nanorods were grown from a colloidal dispersion of amorphous Te (a-Te) and t-Te nanoparticles at room temperature, which was first formed through the reduction of (NH4)2TeS4 by Na2SO3 in aqueous solution at 80 degrees C. Nuclei formed in the reduction process had a strong tendency to grow along the [001] direction due to the inherently anisotropic structure of t-Te. The formation of Te nanorods could be ascribed to the confined growth through the surfactant adsorbing on the surfaces of the growing Te particles. By employing various surfactants in the synthesis system, Te nanorods with well-controlled diameters and lengths could be reproducibly produced by this method. Both the diameters and lengths of nanorods decreased with the increase of the alkyl length and the polarity of the surfactants. Te nanorods could also be obtained in mixed surfactants, where the different surfactants were used to selectively control the growth rates of different crystal planes. We also observed that the as-synthesized nanorods with uniform size could be self-assembled into large-area smecticlike arrays.     

Some Aspects of Seedless Synthesis of Gold Nanorods

Seedless synthesis of gold nanorods with the use of sodium borohydride and hydroquinone as reductants of metal ions has been systematically studied. The effect of reaction system composition on the morphology and optical characteristics of the formed particles has been determined. It has been found that the position of the band of the longitudinal surface plasmon resonance of the nanorods varies nonmonotonically with variations in the concentration of hydroquinone or silver nitrate. The seedless synthesis has been shown to yield high-quality gold nanorods, with the tunable position of their longitudinal surface plasmon resonance in a wide spectral range (from 700 to ~1050 nm). Therewith, the conversion of metal ions is no lower than 78 wt %.     

Fast and slow deposition of silver nanorods on planar surfaces: application to metal-enhanced fluorescence

Two methods have been considered for the deposition of silver nanorods onto conventional glass substrates. In the first method, silver nanorods were deposited onto 3-(aminopropyl)triethoxysilane-coated glass substrates simply by immersing the substrates into the silver nanorod solution. In the second method, spherical silver seeds that were chemically attached to the surface were subsequently converted and grown into silver nanorods in the presence of a cationic surfactant and silver ions. The size of the silver nanorods was controlled by sequential immersion of silver seed-coated glass substrates into a growth solution and by the duration of immersion, ranging from tens of nanometers to a few micrometers. Atomic force microscopy and optical density measurements were used to characterize the silver nanorods deposited onto the surface of the glass substrates. The application of these new surfaces is for metal-enhanced fluorescence (MEF), whereby the close proximity of silver nanostructures can alter the radiative decay rate of fluorophores, producing enhanced signal intensities and an increased fluorophore photostability. In this paper, it is indeed shown that irregularly shaped silver nanorod-coated surfaces are much better MEF surfaces as compared to traditional silver island or colloid films. Subsequently, these new silver nanorod preparation procedures are likely to find a common place in MEF, as they are a quicker and much cheaper alternative as compared to surfaces fabricated by traditional nanolithographic techniques.