Silver,gold and the corresponding core shell nanoparticles: synthesis and characterization

Simple strategies for producing silver and gold nanoparticles (AgNP and AuNP) along with the corresponding core shell nanoparticles (Au–Ag and Ag–Au) by reduction of the metal salts AgBF₄ and HAuCl₄ by NaBH₄ in water will be presented. The morphologies of the obtained nanoparticles are determined by the order of addition of reactants. The obtained NPs, with sizes in the range 3–40 nm, are characterized by transmission electronic microscopy (TEM) and UV–Vis absorption spectroscopy, so as to evaluate their qualities. Moreover, a direct electrochemical detection protocol based on a cyclic voltammetry in water solution that involves the use of glassy carbon electrode is also applied to characterize the prepared NPs. The developed NPs and the related electroanalytical method seem to be with interest for future sensing and biosensing applications including DNA sensors and immunosensors.     

Adjustable surface plasmon resonance with Au,Ag, and Ag@Au core-shell nanoparticles

We report an experimental study on the synthesis of metal nanoparticles （NPs） with adjustable optical density based on surface plasmon resonance （SPR）. Metal NPs prepared by laser ablation in liquid method and the effect of laser parameters on the size, distribution, wavelength of SPR of Ag, Au, and mixture of Ag-Au, and Ag core/Au shell NPs are investigated. Our results show that the adjustable SPR band can be achieved in each class of NPs which is suitable for adjustable optical window applications.     

Design of Enhanced Catalysts by Coupling of Noble Metals (Au,Ag) with Semiconductor SnO2 for Catalytic Reduction of 4‐Nitrophenol

The reduction of 4‐nitrophenol (Nip) into 4‐aminophenol (Amp) by NaBH₄, which is catalyzed by both binary and ternary yolk–shell noble‐metal/SnO₂ heterostructures, is reported. The binary heterostructures contain individual Au or Ag nanoparticles (NPs) and the ternary heterostructures contain both Au and Ag NPs. The Au@SnO₂ yolk–shell NPs are synthesized via a silica seeds‐mediated hydrothermal method. Subsequently, the Au@SnO₂@Ag and Au@SnO₂@Au yolk–shell–shell (YSS) NPs are synthesized, whereby SnO₂ is located between the Au and Ag NPs. The morphology, composition, and optical properties of the as‐prepared samples are analyzed. For the binary heterostructures, the rate of the reduction reaction increases with decreasing particle size. The catalytic results demonstrate the synergistic effect of Au and Ag in the ternary metal–semiconductor heterostructures, which is beneficial to the catalytic reduction of Nip into Amp. Both the binary and ternary heterostructures exhibit significantly better catalytic performances than the corresponding bare Au and Ag NPs. It is envisaged that the current synthesized strategy will promote further interest in the field of bimetal NP‐based catalysis.     

Solution-processed Au@rGO/GaN nanorods hybrid-structure for self-powered UV,visible photodetector and CO gas sensors

Although metal nanoparticles (NPs) have been widely reported, Au NPs functionalized reduced graphene oxide (rGO)/GaN nanorods (NRs) for multi-functional applications are rarely discussed. The rGO is a well known transparent electrode and has been considering an alternative electrode to ITO in the current optoelectronic community. In this work, Au NPs functionalized rGO (Au@rGO)/GaN NRs hybrid structure probed for photodetector and CO gas sensing applications. The hybrid structure was characterized by scanning electron microscopy, transmission electron microscope, current-voltage characteristics, photo conductivity, and gas sensor measurements. The Au@rGO/GaN NRs showed higher photoresponsivity (λ = 382 nm, 516 nm) compared to rGO/GaN NRs at room temperature. The rising and falling times of Au@rGO/GaN NRs are faster than that of rGO/GaN NRs. The hybrid structure Au@rGO/GaN NRs exhibited high CO gas response compared to rGO/GaN NRs at room temperature (∼38% to the 20 ppm). Au NPs played an important role in terms of electronic and chemical changes in the hybrid structure for improving both photodetectors the CO gas response. Such a multi-functional hybrid device is an interest of various room temperature applications.     

1-Hexadecylamine as both reducing agent and stabilizer to synthesize Au and Ag nanoparticles and their SERS application

1-Hexadecylamine (HDA)-capped Au and Ag nanoparticles (NPs) have been successfully prepared by a one-pot solution growth method. The HDA is used as both reducing agent and stabilizer in the synthetic process is favorable for investigating the capping mechanism of Au and Ag NPs’ surface. The growth process and characterization of Au and Ag NPs are determined by Ultraviolet–visible (UV–vis) spectroscopy, transmission electron microscopy (TEM), and X-ray diffraction (XRD). Experimental results demonstrate that the HDA-capped Au and Ag NPs are highly crystalline and have good optical properties. Furthermore, surface-enhanced Raman scattering (SERS) spectra of 2-thionaphthol are obtained on the Au and Ag NPs modified glass surface, respectively, indicating that the as-synthesized noble metal NPs have potentially high sensitive optical detection application.     

Diamine-linked array of metal (Au,Ag) nanoparticles on glass substrates for reliable surface-enhanced Raman scattering (SERS) measurements

Metal (Au, Ag) nanoparticles (M NPs) (ca. 30–40 nm) prepared by citrate reduction method were arrayed on amine-terminated glass substrates using diamine linkers with different chain lengths. 1,4-diaminobutane (C-4 diamine) produced the uniform and densely-packed array of M NPs on glass substrates at appropriate concentration ranges, whereas diamine linkers with longer chain lengths (C-8 and C-12 diamines) produced more heterogeneous and aggregated array of M NPs. When compared to Ag NPs, Au NPs demonstrated more controllable and higher packing density due to their mono-dispersed size and higher affinity to diamine linkers. Uniformly arrayed M NPs (Au, Ag) on glass substrates exhibited high enhancement factors in SERS measurements of o-chlorothiophenol probes. Au NPs arrayed substrates exhibited an approximate power-law linearity of Raman intensity with probe concentrations (from 10⁻⁷ M to 10⁻⁴ M), demonstrating more reliable SERS substrates than Ag arrayed substrates with higher SERS activity.     

A hydrogen peroxide electrochemical sensor based on Ag nanoparticles grown on ITO substrate

In this article, the Ag nanoparticles were synthesized on indium tin oxide conducting glass (ITO) substrate using the electrochemical deposition method. The morphology analysis of the deposits using scanning electron microscope (SEM) reveals that the sizes and densities of the Ag nanoparticles were tuned by varying the time of electrodeposition. The structure of the deposits was characterized by X-ray diffraction (XRD). The prepared Ag nanoparticles electrode was then applied to detect hydrogen peroxide (H₂O₂) in 0.01 M pH 7.0 phosphate buffer medium. The present electrochemical sensing platform exhibited good electrocatalytic activity towards the reduction of H₂O₂. The detection sensitivity of the sensor was 0.237 mA mM⁻¹. This method is very simple, inexpensive, and undemanding, thus it should be extensively applied in many fields for the detection of H₂O₂.     

金纳米粒子的制备及其表面增强拉曼散射效应的研究

采用多巴胺化学还原法制备了分散性良好的纳米金溶胶,并检测了其作为表面增强拉曼散射(Surface Enhanced Raman Scattering,SERS)基底的性质。粒度和透射电子显微镜测试结果表明金溶胶为平均粒径30nm左右的球形颗粒,并且紫外-可见特征吸收峰出现在520nm,为典型的金纳米颗粒特征吸收峰。以罗丹明6G(R6G)为探针分子证明了金溶胶良好的SERS增强效果,用金溶胶对除草剂敌草快(DQ)进行检测,最低检测限可达1×10-7 mol/L。结果表明所制备的金溶胶具有良好的表面增强拉曼散射活性。     

On the spectral difference between electroluminescence and photoluminescence of Si nanocrystals: a mechanism study of electroluminescence

A highly dense and uniform layer of Au nanoparticles (NPs) on poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS) film has been produced by the pulsed laser deposition (PLD) technique toward the production of an improved efficiency photovoltaic device. The advantage of PLD over other techniques is the easy and precise control of the Au NPs size and spatial distribution, without needing of further NP surface functionalization. The efficiency enhancement factor related to Au NPs doping has been evaluated in a solar cell based on poly-(3-hexylthiophene):[6,6]-phenyl-C₆₁-butyric acid methyl ester (P3HT:PCBM) diffused bilayer. The short-circuit current density, J _SC, increases by 18 % and the power conversion efficiency by 22 %, respectively, in comparison with an equivalent device without Au NPs. The optical and morphological properties of the Au NPs layer have been selected in order to evaluate the contribution of the surface plasmon resonance as enhancement factor of the solar cell efficiency, in a range size where light scattering is negligible.     

Enhanced acetone sensing characteristics by decorating Au nanoparticles on ZnO flower-like structures

A well-organized hierarchical structure of ZnO was developed by chemical bath deposition and used as templates for making gold-coated ZnO (Au/ZnO) hybrid nanostructures. The coverage of Au nanoparticles (Au NPs) on ZnO was controlled by changing the amount of the Au precursor. The Au/ZnO hybrids were applied as gas sensing materials to detect acetone. The improved sensor response, selectivity and short response, and recovery time to acetone vapor due to Au NPs on ZnO nanostructures has been observed and explained by considering the formation of Au/ZnO heterostructures, which are favorable for the diffusion of gas molecules. In addition, the dependence of Au amount on gas sensor properties was systematically investigated. ZnO decorated by 6 wt% Au NPs displayed a 9.05-fold enhancement in gas response to 100 ppm of acetone at 280 °C compared to pristine ZnO.     

Preparation and characterization of reduced graphene oxide supported nickel oxide nanoparticle-based platform for sensor applications

A nanostructured composite film comprising reduced graphene oxide (rGO) and nickel oxide (NiO) nanoparticles (NPs) has been prepared and utilized for development of a simple yet efficient sensor for detection of dopamine and epinephrine in a single run. The hybrid material rGO-NiO nanocomposite was synthesized chemically, and the formation of nanocomposite was confirmed via X-ray diffraction (XRD), transmission electron microscopy (TEM), Raman, UV-Vis, and Fourier transform infrared (FTIR) spectroscopic techniques. The incorporation of NiO NPs on rGO support was found to provide improved sensing characteristics at electrode interface due to enhanced electron mobility on rGO sheet and high catalytic activity of NiO NPs. Subsequently, the synthesized rGO-NiO nanocomposite was deposited onto indium tin oxide (ITO)-coated glass substrate by simple drop-casting method, and the electrode was characterized through atomic force microscopy (AFM) and scanning electron microscopic (SEM) studies. After optimization of experimental conditions electrochemically for its high sensitivity, the fabricated rGO-NiO/ITO electrode was used for simultaneous detection of dopamine and epinephrine by square wave voltammetry (SWV) method. The results showed high sensitivity of 0.545 and 0.638 μA/μM for dopamine and epinephrine respectively in a broad linear range of 0.5–50 μM. Moreover, remarkable detection limits of 0.495 and 0.423 μM were found for dopamine and epinephrine, and the developed sensor exhibited a wide separation of 380 mV between the respective detection peaks of dopamine and epinephrine. Beside this, the proposed sensor was successfully applied in presence of high concentration of interfering agents, ascorbic acid and uric acid, and validated with real serum samples.     

Coarsening-resistant Ag nanoparticles stabilized on amorphous TiO<Subscript>x</Subscript> nanoparticles

Bare Ag nanoparticles (～10 nm) and Ag nanoparticles (1–20 nm) on the surfaces of larger TiO_x nanoparticles were prepared by laser ablation of microparticle aerosols (LAMA). The behaviors of the nanoparticles during high temperature annealing were then studied with ex situ and in situ transmission electron microscopy. For the ex situ heating experiments, Ag and Ag-on-TiO_x NPs were collected onto gold TEM grids and subjected to annealing treatments at 500 °C in argon, vacuum, and air. At this temperature, bare Ag NPs on carbon TEM supports coarsened rapidly in both air and argon atmospheres. In contrast, Ag-on-TiO_x NPs that were heated to 500 °C in flowing argon or in a vacuum did not coarsen significantly and were remarkably stable. Ag-on-TiO_x NPs that were heated to 500 °C in air, however, behaved quite differently. The TiO_x crystallized upon heating and a significant loss of Ag were observed from the surfaces of the TiO_x, likely due to sublimation. These results demonstrate that the surface defect structure and chemistry of the oxide support strongly influence the thermal stability of Ag NPs produced by LAMA.     

Laser generated Ag and Ag–Au composite nanoparticles for refractive index sensor

Localized surface plasmon resonance (LSPR) wavelength of metal nanoparticles (NPs) is highly sensitive to size, shape and the surrounding medium. Metal targets were laser ablated in liquid for preparation of spherical Ag and Ag@Au core–shell NP colloidal solution for refractive index sensing. The LSPR peak wavelength and broadening of the NPs were monitored in different refractive index liquid. Quasi-static Mie theory simulation results show that refractive index sensitivity of Ag, Ag–Au alloy and Ag@Au core–shell NPs increases nearly linearly with size and shell thickness. However, the increased broadening of the LSPR peak with size, alloy concentration and Au shell thickness restricts the sensing resolution of these NPs. Figure-of-merit (FOM) was calculated to optimize the size of Ag NPs, concentration of Ag–Au alloy NPs and Au shell thickness of Ag@Au core–shell NPs. The refractive index sensitivity (RIS) and FOM were optimum in the size range 20–40 nm for Ag NPs. Laser generated Ag@Au NPs of Au shell thickness in the range of 1–2 nm showed optimum FOM, where thin layer of Au coating can improve the stability of Ag NPs.     

倒置器件结构及局域等离子体效应对CdSe量子点LED发光性能的改进

研究了倒置器件结构以及CdSe量子点发光材料与金属纳米粒子之间的相互作用对量子点的电致发光性能的影响。利用TiO₂作为电子传输/注入层,成功地制备了倒置结构的量子点电致发光器件。通过对单载流子器件电压-电流特性的分析,证明了ITO作为阴极到TiO₂的电子注入特性与Al作为阴极时的效果几乎相同。观察到金属纳米粒子产生的局域等离子体效应提高了器件的效率,使得效率随电流增大而降低的速度明显减小。在电流密度为200 mA/cm²时,电致发光器件的效率大约提高了42%。     

Excimer laser photofragmentation of metallic nanoparticles

Copper nanoparticles (Cu NPs) were prepared by different chemical methods possessing different sizes. While, silver nanoparticles (Ag NPs) were prepared by borohydride reduction method. The influences the changes in sizes of Ag NPs and Cu NPs were demonstrated by the absorption spectra. When Ag NPs and Cu NPs irradiated with 193 and 308 nm excimer laser, respectively; the maximum absorption decreased as the number of pulses increased up to 10 thousands pulse; due to the size reduction. The TEM photography gives good criteria about the size reduction process. Moreover, the mechanism of photofragmentation was described.     

密排银颗粒薄膜的制备及其SERS应用

银纳米颗粒通过自组装形成二维结构薄膜具有独特的光学性质,其提供的大量“热点”使其成为优越的表面增强拉曼散射(Surface enhanced Raman Scattering,SERS)基底.本文采用水/正己烷界面上自组装的方法得到了由密排的银纳米颗粒构成的薄膜,并以Rhodamine 6G为探针分子,比较了不同尺寸银...     

Elucidating synthesis of noble metal nanoparticles/graphene oxide in free-scavenger γ-irradiation

Three representative noble metal (Ag, Au and Pt) nanoparticles decorated graphene oxide (NMNPs/GO) composites were fabricated via γ-irradiation without scavenger. The NMNPs/GO composites exhibited the pure and well-dispersed particles structure, which directly illustrated that the GO could be acted as scavenger to benefit reduction and growth of NMNPs. Compared with irradiated GO (IGO), the GO substrate of composites had the lower relative content of hydroxyl groups, meanwhile, the relative contents of carbonyl groups (Pt > Au > Ag) were increased with increasing valence of noble metal. Such results illustrated that the abundant hydroxyl groups could convert the hydrated electrons, hydroxyl and hydrogen radicals to promote the growth of NMNPs on the surface of GO. In addition, the Raman signals of Ag NPs/GO composites were significantly enhanced (6.18 fold more than pristine GO, respectively), exhibiting obvious surface-enhanced Raman scattering activity. Therefore, this paper revealed that the GO could convert the hydrated electrons and radicals to synthetizing NMNPs/GO composites during γ-ray irradiation.     

Simple method to prepare size‐controllable gold nanoparticles in solutions and their applications on surface‐enhanced Raman scattering

We report here, for the first time, a simple method to prepare size‐controllable Au nanoparticles (NPs) in aqueous solutions from bulk Au substrates. First, chitosan (Ch)‐capped Au‐containing complexes were prepared by electrochemical oxidation–reduction cycles in 0.1 N NaCl and 1 g/l Ch solutions. Then the solutions were heated from room temperature to boiling at different heating rates to synthesize size‐controllable Au NPs. The particle sizes of the prepared Au(111) NPs could be controlled from 5 to 30 nm with an increase of the heating rate during preparation. Experimental results indicate that the prepared Au(111) NPs with diameters ranging from 10 to 30 nm can serve as surface‐enhanced Raman scattering active probes for molecules of rhodamine 6G. Copyright © 2010 John Wiley & Sons, Ltd.     

Synthesis of PMA stabilized silver nanoparticles by chemical reduction process under a two-step UV irradiation

Poly(methacrylic acid) (PMA) stabilized silver nanoparticles (Ag NPs), also used in the surface modification of clothing fibers, were fabricated via chemical reduction processes under UV irradiation. To obtain an uniform size distribution it has been designed a new “two-step” process which employs two different UV radiation densities in order to control the kinetics of NPs nucleation. The as produced nanoparticles were characterized by UV-vis absorption spectroscopy and TEM microscopy. The results show the reduction of the Ag ions and the nanoparticles nucleation in the first step. In the second step, the final Ag NPs size distribution is controlled through a quick cross-linking of the PMA that freezes out any further modification. A narrow size distribution with more than 80% NPs smaller than 10 nm and none larger than 25 nm was obtained and the long-term stability (one month) of the colloidal solution was verified.     

电极材料及偏压极性对氧化物介质击穿行为的影响及机制

忆阻器和能量存储电容器具有相同的三明治结构,然而两个器件需要的操作电压有明显差异,因此在同一个器件中,研究操作电压的影响因素并对操作电压进行调控,实现器件在不同领域的应用是十分必要的一个工作.本文利用反应磁控溅射技术在ITO导电玻璃、Pt/Si基底上生长了多晶ZrO_2和非晶TaO_x薄膜,选用不同金属材料Au, Ag和Al用作上电极构建了多种金属/氧化物介质/金属三明治结构的电容器,研究了器件在不同偏压极性下的击穿强度.结果发现:底电极是ITO的ZrO_2基电容器在负偏压下的击穿电场比Pt电极器件稍大.不管底电极是ITO还是Pt, Ag作为上电极时器件的击穿强度均存在明显的偏压极性依赖性,正偏压下的击穿电场减小了一个数量级;相反,在Al作为上电极的Al/TaO_x/Pt器件中,正向偏压比负向偏压下的击穿电场增加了近2倍.上述器件的不同击穿行为分别可以由氧化物电极和介质界面层间氧的迁移和重排、电化学活性金属电极的溶解迁移和还原以及化学活性金属电极与氧化物界面的氧化还原反应来解释.该实验结果对有不同操作电压要求的器件,如忆阻器和介质储能电容器等在器件设计和操作方面具有指导意义.