One-pot synthesis of gold nanorods via autocatalytic growth of sonochemically formed gold seeds: The effect of irradiation time on the formation of seeds and nanorods

A one-pot synthesis for gold nanorods was developed using sonochemical reduction of gold ions in an aqueous solution in the presence of cetyltrimethylammonium bromide, silver nitrate, and ascorbic acid, where we focused on the autocatalytic growth of gold seeds formed by ultrasonic irradiation for short times. In growth experiments with these sonochemically formed gold seeds, sigmoidal shape growth curves were observed, and the induction period before growth began was longer for shorter irradiation times. This result indicated that the number of sonochemically formed gold seeds increased with increasing irradiation time. The average aspect ratio of the gold nanorods produced changed from 2.0 at an irradiation time of 0.5 min to 3.6 at 15 min. The gold nanorods produced were longer and wider when the irradiation time was shorter.     

Efficient seed-mediated method for the large-scale synthesis of Au nanorods

Seed-mediated methods are widely followed for the synthesis of Au nanorods (NRs). However, mostly dilute concentrations of the Au precursor (HAuCl₄) are used in the growth solution, which leads to a low final concentration of NRs. Attempts of increasing the concentration of NRs by simply increasing the concentration of HAuCl₄, other reagents in the growth solution and seeds lead to a faster growth kinetics which is not favourable for NR growth. Herein, we demonstrate that the increase in growth kinetics for high concentrations of reagents in growth solution can be neutralised by decreasing the pH of the solution. The synthesis of the NRs can be scaled up by using higher concentrations of reagents and adding an optimum concentration of HCl in the growth solution. The concentration of HAuCl₄ in the growth solution can be increased up to 5 mM, and 10–20 times more NRs can be synthesised for the same reaction volume compared to that of the conventional seed-mediated method. We have also noticed that a cetyltrimethylammonium bromide (CTAB)-to-HAuCl₄ molar ratio of 50 is sufficient for obtaining high yield of NRs.     

Synthesis and properties of Au/ZnO nanorods as a plasmonic photocatalyst

It is of great interest to develop plasmonic photocatalysts with high activity and stability recently. In this paper, Au/ZnO nanorods were synthesized via a facile hydrothermal method and used as photocatalysts for methyl orange dye degradation. The results revealed an interesting phenomenon that photocorrosion cracks were produced specially along the c-axis of pure ZnO nanorods for five cycles photodegradation experiments under UV–vis. light irradiation, while Au nanoparticles surface modification can effectively inhibit the occurrence of photocorrosion and improve its photocatalytic activity. The formation of photocorrossion cracks along the c-axis of pure ZnO nanorods verifies the photogenerated charges may follow the route that electrons migrate to Zn-terminated (0001) plane and holes to O-terminated $(000\stackrel{-}{1})$ plane. SPR effect of Au nanoparticles enhances the light absorption ability and the electrons capture ability of Au/ZnO nanorods. Moreover, the surface adsorbed hydroxyl groups content is also increased due to Au nanoparticles modification. As Au nanoparticles can capture photogenerated electrons and hydroxyl groups are the favorable holes scavenger, the charges generation and separation in photocatalysis are strengthened. Especially, the charges separation path in Au/ZnO nanorods have changed, thus inhibiting the occurrence of photocorrosion along the c-axis of ZnO nanorods and improving the photocatalytic activity.     

Optimization of accurate controlled formation of Au MNPs via non-thermal microplasma continuous glow discharge within aqueous electrochemical (GDE) method

In this work, micro plasma-induced non-equilibrium liquid chemistry was utilized to synthesize and controlled formation of gold metallic nanoparticles (Au MNPs) by governing the concentration of (HAuCl₄). These new approaches based on both plasma and liquid electrolytes contain charged species, and the interactions between the two phases represent a unique combination of physics, chemistry, and materials science. Continuous and stable DC glow discharge was done in home–made cavity to synthesize the definite sizes of (Au MNPs) by means of (3 kV) discharge voltage and (2 mA) discharge current for a period of (7 min) in aqueous solution of HAuCl₄ with four different concentrations of about 1 mM, 5 mM, 10 mM and 20 mM at room temperature. The atmospheric pressure plasma discharge between stainless steel capillary tube cathode electrode over the (HAuCl₄) solution and platinum plate as an anode dipped in solution for rapid formation of colloidal Au MNPs. Morphology aspects of the synthesized Au MNPs layer were studied by examining the (FE-SEM), HR-TEM images and X-ray difraction (XRD) pattern. Optical features of (Au MNPs) were considered via a UV–Vis beam spectrophotometer. These measurements showed that Au MNPs were organized by governing the concentration of HAuCl₄, and uniform Au MNPs with specific exclusive sizes were acquired. Grain size, specific surface area and optical stability of Au MNPs strongly be affected by the HAuCl₄ concentrations.     

Highly sensitive and selective trimethylamine sensors based on WO3 nanorods decorated with Au nanoparticles

One-dimensional tungsten oxide (WO₃) gas sensing materials have been widely used for the detection of trimethylamine (TMA) gas. Furthermore, it is believed that an effective method to improve the gas sensing performance is to introduce noble metals into sensing materials. In this work, a novel gas sensing material was prepared by decorating Au nanoparticles on WO₃ nanorods. Based on field emission scanning electron microscopy (FESEM/EDS), X-ray diffraction (XRD), and transmission electron microscopy (TEM), the morphology and microstructure of as-prepared samples were characterized. Results show that Au nanoparticles with diameter of 13–15 nm are loaded on the surface of WO₃ nanorods with length of about 1–2 µm and width of 50–80 nm. Gas sensing tests reveal that the Au@WO₃ sensor has remarkably enhanced response to TMA gas compared with pure WO₃ nanorods. In addition, and the gas sensing mechanism has been investigated based on the experimental results. The superior sensing features indicate the present Au@WO₃ nanocomposites are promising for gas sensors, which can be used in the detection of the trimethylamine gas and this work provides insights and strategies for the fabrication of sensing materials.     

Mechanism for sonochemical reduction of Au(III) in aqueous butanol solution under Ar based on the analysis of gaseous and water-soluble products

When an aqueous Au(III) solution containing 1-butanol was sonicated under Ar, Au(III) was reduced to Au(0) to form Au particles. This is because various reducing species are formed during sonication, but the reactivity of these species has not yet been evaluated in detail. Therefore, in this study, we analyzed the effects of Au(III) on the rates of the formation of gaseous and water-soluble compounds (CH₄, C₂H₆, C₂H₄, C₂H₂, CO, CO₂, H₂, H₂O₂, and aldehydes), and the rate of Au(III) reduction as a function of 1-butanol concentration. The following facts were recognized: 1) for Au(III) reduction, the contribution of the radicals formed by the pyrolysis of 1-butanol was higher than that of the secondary radicals formed by the abstraction reactions of 1-butanol with ·OH, 2) ·CH₃ and CO acted as reductants, 3) the contribution of ·H to Au(III) reduction was small in the presence of 1-butanol, 4) aldehydes and H₂ did not act as reductants, and 5) the types of species that reduced Au(III) changed with 1-butanol concentration.     

介孔SiO2纳米棒的制备及其表面锚接金纳米粒子

 以正硅酸乙酯为硅源,十六烷基三甲基溴化铵为模板剂,聚乙二醇为分散剂,采用溶胶-凝胶法制备出SiO₂纳米粒子,应用透射电镜、扫描电镜、X射线衍射仪、红外光谱仪和X射线能谱仪研究了粒子的性能。结果表明：所得产物是具有周期性规则介孔的棒状粒子,长径比随着硅源、模板剂和分散剂浓度的降低而减小;向反应体系中引入乙醇,随着乙醇与水的体积比例的增加,粒子由棒状向球状转变,进而形成不规则絮状凝聚体。用硅烷化技术对SiO₂纳米棒表面进行修饰后吸附平均粒径3.7 nm的金种子,再用多轮生长法使种子长大,经过30轮生长,种子平均粒径增大至59 nm,得到了SiO₂-Au复合纳米体系。透射电镜和紫外-可见分光光度计分析结果表明：金纳米粒子锚接在SiO₂纳米棒表面的某些点位,呈分散分布;复合体系表现出强烈的金的表面等离子体共振吸收峰,该峰随着金粒子的粒径增大,在500~700 nm波段内红移。     

DFT calculations for Au adsorption onto a reduced TiO2 (110) surface with the coexistence of Cl

Residual chlorines, which originate from HAuCl₄, enhance the aggregation of gold (Au) nanoparticles and clusters, preventing the generation of highly active supported Au catalysts. However, the detailed mechanism of residual-chlorine-promoted aggregation of Au is unknown. Herein to investigate this mechanism, density functional theory (DFT) calculations of Au and Cl adsorption onto a reduced rutile TiO₂ (110) surface were performed using a generalised gradient approximation Perdew, Burke, and Ernzerhof formula (GGA–PBE) functional and plane-wave basis. Although both Au and Cl atoms prefer to mono-absorb onto oxygen defect sites, Cl atoms have a stronger absorption onto a reduced TiO₂ (110) surface, abbreviated as rTiO₂ (110) in the following, than Au atoms. Additionally, co-adsorption of a Cl atom and a Au atom or Au nanorod onto a rTiO₂ surface was investigated; Cl adsorption onto an oxygen defect site weakens the interaction between a Au atom or Au nanorod and rTiO₂ (110) surface. The calculation results suggest that the depletion of interaction between Au and rTiO₂ surface is due to strong interaction between Cl atoms at oxygen defect sites and neighbouring bridging oxygen (O^B) atoms.     

Facile synthesis and visible-light photocatalytic activity of bismuth titanate nanorods

Highly crystalline bismuth titanate (Bi₁₂TiO₂₀, BiT) nanorods, as visible-light photocatalysts were prepared by a template-free hydrothermal process. The as-prepared BiT nanorods fabricated in high yields by simply manipulating pH values in the absence of any capping agent, were characterized by a number of techniques, such as XRD, SEM, TEM, HRTEM, BET, and UV–Vis spectrum. In this case, hydroxide ions seem to play a pivotal role in controlling the formation of seeds and the growth of the BiT nanorods. Based on the structural analysis of nanocrystals obtained at different pH values, we proposed a plausible mechanism to account for the formation of the tunable morphologies. Most importantly, the BiT nanorods with good stability exhibited higher photocatalytic activities in the degradation of Rhodamine B under visible light irradiation (λ ≥ 420 nm) than the commercial P25 TiO₂ and bulk BiT powders, demonstrating that Bi₁₂TiO₂₀ is a promising candidate as a visible-light photocatalyst.     

Preparation and optical properties of HgWO<Subscript>4</Subscript> nanorods by hydrothermal method coupled with ultrasonic technique

For the first time, a newly luminescent nanomaterial, monoclinic wolframite-type HgWO₄ nanorods (diameter: ∼200 nm; length: ~2000 nm) are prepared by hydrothermal method together with ultrasonic technique. Fluorescent (FL) and UV–Vis results both show that for HgWO₄, ultrasonic irradiation procedure will change its optical behaviors greatly. When the crystals become into nanorods, the fluorescent emitting peaks (365 and 495 nm) shift to central region, and finally form a wider one at 435 nm. Similar results of UV–visible absorption peaks are observed for these two products. FTIR spectra further characterize their structure. All above unique optical performances might result from both small sizes caused by ultrasonic irradiation procedure and involvement of incompact d¹⁰ electrons. Moreover, possible synthesis mechanisms of HgWO₄ nanorods are also investigated.     

Au cluster growth on ZnO thin films by pulsed laser deposition

Nanostructures formed by Au nanoparticles on ZnO thin film surface are of interest for applications which include medical implants, gas-sensors, and catalytic systems. A frequency tripled Nd:YAG laser (λ = 355 nm, τ_FWHM ∼ 10 ns) was used for the successive irradiation of the Zn and Au targets. The ZnO films were synthesized in 20 Pa oxygen pressure while the subsequent Au coverage was grown in vacuum. The obtained structures surface morphology, crystalline quality, and chemical composition depth profile were investigated by acoustic (dynamic) mode atomic force microscopy, X-ray diffraction, and wavelength dispersive X-ray spectroscopy. The surface is characterized by a granular morphology, with average grain diameters of a few tens of nanometers. The surface roughness decreases with the increase of the number of laser pulses applied for the irradiation of the Au target. The Au coverage reveals a predominant (1 1 1) texture, whereas the underlying ZnO films are c-axis oriented. A linear dependence was established between the thickness of the Au coverage and the number of laser pulses applied for the irradiation of the Au target.     

Deposition of Au/TiO2 film by pulsed laser

Au nanoparticles, which were photoreduced by a Nd:YAG laser in HAuCl₄ solution containing TiO₂ colloid and accompanied by the TiO₂ particles, were deposited on the substrate surface. The film consisting of Au/TiO₂ particles was characterized by the absorption spectra, scanning electron microscopy (SEM) and X-ray diffraction (XRD) analysis. The adhesion between the film and substrate was evaluated by using adhesive tape test. It was found that the presence of TiO₂ dramatically enhanced the adhesion strength between the film and the substrate, as well as the deposition rate of film. The mechanism for the deposition of Au/TiO₂ film was also discussed.     

Nanospherical Surface‐Supported Seeded Growth of Au Nanowires: Investigation on a New Growth Mechanism and High‐Performance Hydrogen Peroxide Sensors

In this paper, a novel strategy with a new growth mechanism for fast and large‐scale growth of Au long nanowires on high‐curvature SiO₂ nanospherical surfaces has been developed. The synthesis includes three steps, i.e., amino modification of SiO₂ nanospheres, Au seed loading on aminated SiO₂ nanospheres and subsequently, Au seed‐mediated nanowire growth on SiO₂ nanospheres. The prepared Au nanowires (Au NWs) (exhibit long length, high aspect ratio, and good flexibility, and can naturally form the dense nanowire film, which is promising as a stable conductive electrode. In addition, the effect of synthetic conditions such as reactant feeding order, Au seeds and SiO₂@Au seeds on the morphology of Au nanostructures (nanowires, nanoteeth, and nanoflowers) has been investigated. It is found that Au seeds and high‐curvature SiO₂ nanospherical surfaces are necessary conditions for the successful preparation of Au NWs and nanowire films. The different growth mechanisms for Au NWs and nanoteeth have been proposed and discussed. Moreover, the novel nonenzymatic H₂O₂ sensor based on Au NWs exhibits much enhanced performance such as higher sensitivity, stability, and selectivity, wider linear range and lower detection limit, compared with that of Au nanoparticles‐based H₂O₂ sensor.     

Shape and size transformation of gold nanorods (GNRs) via oxidation process: A reverse growth mechanism

The anisotropic shape transformation of gold nanorods (GNRs) with H₂O₂ was observed in the presence of “cethyl trimethylammonium bromide” (CTAB). The adequate oxidative dissolution of GNR is provided by the following autocatalytic scheme with H₂O₂: Au⁰ → Au⁺, Au⁰ + Auⁿ⁺ → 2Au³⁺, n = 1 and 3. The shape transformation of the GNRs was investigated by UV-vis spectroscopy and transmission electron microscopy (TEM). As-synthesised GNRs exhibit transverse plasmon band (TPB) at 523 nm and longitudinal plasmon band (LPB) at 731 nm. Upon H₂O₂ oxidation, the LPB showed a systematic hypsochromic (blue) shift, while TPB stays at ca. 523 nm. In addition, a new emerging peak observed at ca. 390 nm due to Au(III)-CTAB complex formation during the oxidation. TEM analysis of as-synthesised GNRs with H₂O₂ confirmed the shape transformation to spherical particles with 10 nm size in 2 h, whereas centrifuged nanorod solution showed no changes in the aspect ratio under the same condition. Au³⁺ ions produced from oxidation, complex with excess free CTAB and approach the nanorods preferentially at the end, leading to spatially directed oxidation. This work provides some information to the crystal stability and the growth mechanism of GNRs, as both growth and shortening reactions occur preferentially at the edge of single-crystalline GNRs, all directed by Br⁻ ions.     

Synthesis of iron oxide nanorods via chemical scavenging and phase transformations of intermediates at ambient conditions

Chemically induced shape transformations of isotropic seeds, comprised of iron oxyhydroxides and iron oxide borate into nanorods, is reported. Transient growth studies show that the nanorods are formed via phase transformation and aggregation of various metastable species. Addition of tetra-methyl-ammonium hydroxide (TMAH) to the in situ synthesized seeds ensures a typical reaction pathway that favors formation of magnetite (Fe ₃ O ₄) via the steps of chemical etching, phase transformation of intermediates, and crystal consolidation. Whereas, with addition of sodium hydroxide (NaOH), either magnetite (Fe ₃ O ₄) or a mixture of (γ-Fe ₂ O ₃ + α-FeOOH) is obtained. The shape with both the additives is always that of nanorods. When the seeds treated with TMAH were aged in an ultrasonication bath, rods with almost twice the length and diameter (length = 2800 nm, diameter = 345 nm) are obtained as compared to the sample aged without ultrasonication (length = 1535 nm, diameter = 172 nm). The morphology of nanostructures depending upon other experimental conditions such as, aging the sample at 60 ^°C, seeds synthesized under ultrasonication/ stirring or externally added are also examined and discussed in detail. All the samples show high coercivity and strong ferromagnetic behavior at room temperature and should be promising candidates as ferro-fluids for various applications.     

Ion-beam induced mixing of Cu/Au bilayer thin film (kinematics and formation of solid solutions)

Ion-beam induced atomic mixing of Cu/Au bilayer thin film is studied using combined electrical resistivity measurements and Rutherford Backscattering Spectrometry (RBS). 400 keV Kr⁺ ion irradiation with fluences ranging from 3.3×10¹⁵ to 7.6×10¹⁶ ions/cm² at room temperature have been used. Ion beam mixing lead to a uniformly mixed metal alloy. The formation of Cu/Au solid solutions depends on the initial composition and on the fluence of irradiating ions. For an initial composition of Cu₄₂Au₅₈, a Cu-rich solid solution of composition Cu₇₂Au₂₈ is formed after irradiation with 7.6×10¹⁶ ions/cm². The kinematics of the intermixing process is also studied by in situ electrical resistivity measurements which confirmed the formation of the Cu/Au solid solutions.     

Synthesis of SERS active Au nanowires in different noncoordinating solvents

Au nanowires with length up to micrometers were synthesized through a simple and one-pot solution growth method. HAuCl₄ was reduced in a micellar structure formed by 1-octadecylamine and oleic acid in hexane, heptane, toluene and chloroform, respectively. As the non-polarity of noncoordinating solvents can affect the nucleation and growth rates of Au nanostructures, Au nanowires with different diameters could be obtained by changing the noncoordinating solvents in the synthetic process. The influences of the solvents on the morphology of Au nanowires were systematically studied. When using hexane as reaction solvent, the product turned to be high portion of Au nanowires with more uniform size than the others. Furthermore, surface-enhanced Raman scattering (SERS) spectrum of 2-thionaphthol was obtained on the Au nanowire-modified substrate, indicating that the as-synthesized Au nanowires have potential for highly sensitive optical detection application.     

具有双共振吸收峰的Au纳米粒子制备及其拉曼表征

表面增强拉曼散射(SERS)很大程度的弥补了拉曼散射强度弱的缺点,迅速成为科研工作者们的研究热点,在食品安全、环境污染、毒品以及爆炸物检测等领域应用广泛。纳米技术的发展使得目前对于SERS的研究主要集中于金属纳米颗粒基底的制备,金属纳米粒子的种类、尺寸及形貌对SERS增强和吸收峰峰位均有影响,要获得好的增强效果,需要对金属纳米结构进行工艺优化。特别是,需要结合金属纳米粒子的结构和激励光波长,以期获得更好的增强效果。为了研究SERS增强和吸收峰之间的关系,开展了具有双共振吸收峰的金属纳米粒子的研究。首先利用FDTD Solutions仿真建模,主要针对金纳米颗粒直径、金纳米棒长径比及分布状态对共振吸收峰进行仿真,得到金纳米球理论直径在50 nm左右,金纳米棒理论长径比在3.5~4.5左右时,吸收峰分别分布在532及785 nm附近,符合多波段激励光拉曼增强条件;对于激励光偏振方向,其沿金纳米棒长轴方向偏振时吸收峰位于785 nm附近,沿金纳米球短轴方向偏振时吸收峰位于532 nm附近。然后采用种子生长法,制备了可用于多种波长激励光的双吸收峰表面增强拉曼散射基底。通过改变硝酸银用量(5,10,20,30和40 μL)、盐酸用量(0.1和0.2 mL)以及其生长时间(15,17,21和23 h)等多种工艺参数来控制金纳米棒含量,得到了同时含有金纳米球及金纳米棒的双吸收共振峰金纳米粒子。最后用该样品作为基底,罗丹明6G(R6G)作为探针分子,分别测试其在532,633和785 nm激励光入射时的SERS表征,对分析物R6G最低检测浓度均达到了10-7 mol·L-1,增强因子达到了~105,满足了多波段SERS检测的需要。     

Controlled synthesis of gold nanospheres and single crystals in hydrogel

Narrow-dispersed gold nanospheres, regular single-crystal nanoplates and nanobulks were prepared, respectively, by reducing HAuCl₄ within a hydrogel system under UV irradiation. The formation of gold products with different geometric shape and size was found to depend on both the microenvironment of the gel matrix and the initial concentration of HAuCl₄. The resultant gold particles were investigated by UV–vis spectroscopy, X-ray diffraction, transmission electron microscopy, scanning electron microscopy, and energy-dispersion X-ray spectroscopy. Electronic Supplementary Material The online version of this article at (doi: ) contains supplementary material, which is available to authorised users.     

Effect of ultrasonic treatment before and after hydrothermal process on the morphologies and formation mechanism of ZnO nanorods

ZnO nanorods were fabricated by ultrasonic treatment before and after a hydrothermal process. The morphology and structure of the nanorods were individually characterized by scanning electron microscopy and X-ray diffraction. The results show that before the hydrothermal process, fore-ultrasonic treatment can directly gain ZnO nanorods which mainly experienced four conversion stages from initial bulk Zn(OH)₂, a coexisting phase of bulk Zn(OH)₂ with ZnO nanoslices, ZnO nanoslices with flower-like ZnO nanorods and finally to purely flower-like ZnO nanorods. After the hydrothermal process, the post-ultrasonic treatment mainly influences the aggregation degree of the ZnO nanorods. The formation mechanism of ultrasonic treatment on ZnO nanorods is also discussed.