用小角X射线散射研究纳米粒子的粒度分布

采用小角X射线散射中的对数高斯分布函数的方法，确定了纳米粒子的粒度分布。通过理论分析、计算，对氧化锌纳粒子进行实验测试。结果表明，氧化锌纳米粒子的平均半径尺寸为3．34nm，分布的标准偏差为1．35。     

Graphene layer number dependent size distribution of silver nanoparticles

We observe that silver atoms deposited by thermal evaporation deposition onto n-layer graphene films condense upon annealing to form nanoparticles with an average diameter and density that is determined by the layer numbers of graphene films. The optical microscopy and Raman spectroscopy were utilized to identify the number of the graphene layers and the SEM (scanning electron microscopy) was used to observe the morphologies of the particles. Systematic analysis revealed that the average sizes of the nanoparticles increased with the number of graphene layers. The density of nanoparticles decreased as the number of graphene layers increased, revealing a large variation in the surface diffusion strength of nanoparticles on the different substrates. The mechanisms of formation of these layer-dependent morphologies of silver nanoparticles are related to the surface free energy and surface diffusion of the n-layer graphenes.     

The electronic behaviors of TiO2/MnO2/carbon clusters composite materials obtained by the calcination of a TiO(acac)2/Mn(acac)3/epoxy resin complex

The calcination of a TiO(acac)₂/Mn(acac)₃/epoxy resin complex under an oxygen atmosphere successfully produced nano-sized TiO₂/MnO₂/carbon clusters composite material. The surface characterizations of the resulting composites indicate that they are composed of nano-sized particles of TiO₂, MnO₂ and carbon clusters. ESR spectral examination suggests the possibility of an electron transfer in the process of MnO₂ → carbon clusters → TiO₂. The visible light-responsive oxidation–reduction function of the composite materials has also been confirmed.     

Handling the particle size and distribution of Fe3O4 nanoparticles through ball milling

A series of samples consisting of spinel Fe₃O₄ nanoparticles with controlled particle sizes and increasing concentration has been obtained through ‘mild’ ball milling (BM) experiments by using an organic carrier liquid. We have succeeded in producing quite narrow particle size distributions with mean values d7–10 nm by an appropriate choice of the milling time for each concentration. The method proved to be practical to tailor the final particle size without formation of undesirable phases. All samples showed superparamagnetic behavior at room temperature, with transition to a blocked state at T_B10–20 K. The mean value and distribution width of the size distributions for the three samples studied were obtained from M(H) cycles recorded at T>T_B showing good agreement with X-ray diffraction and electron microscopy results. The effect of increasing interparticle interactions was to shift T_B upwards, as inferred from magnetization measurements. Mössbauer spectra at low temperatures showed no evidence of enhanced spin disorder.     

Modeling size dependence of melting temperature of metallic nanoparticles

A model has been developed to account for the dependence of melting temperature of nanoparticles on their size, shape and lattice type. This model is consistent with reported experimental data and shows better consistency than the liquid drop and bond energy model. A general equation is proposed which correlates with the bond energy model formula and has high potential for application in research and development. The model also leads to an equation showing the limiting size for nanoparticles.     

Adhesion of silver nanoparticles on the montmorillonite surface

Adhesion of silver nanoparticles on the montmorillonite substrate was investigated using molecular modeling (force field calculations) and experiment (infrared spectroscopy, high-resolution transmission electron microscopy). Modeling revealed the preferred orientation of silver nanoparticles on the silicate substrate and showed the strong dependence of total energy and stability of nanocomposite structure on two factors: (1) the mutual crystallographic orientation of nanoparticle and substrate structure and (2) the size and thickness of the nanoparticle. The size of silver single crystalline domains calculated by modeling was in good agreement with the experimental observations. Molecular modeling in confrontation with high-resolution transmission electron microscopy analysis showed the prediction possibility as to the nanoparticles structure and stability of nanocomposite.     

Fabrication and photochromic study of titanate nanotubes loaded with silver nanoparticles

Pure anatase-TiO₂ and/or titanate nanotubes, photochromic Ag loaded titanium dioxide nanotubes (TNTs) and AgCl loaded titanate nanotubes were synthesized by hydrothermal method. The pH value during the neutralization process plays a crucial role in controlling the morphology and composition of the nanotubes. All these nanotubes were confirmed by XRD, TEM, EDS and XPS analysis. Most of them have open ends with inner/outer diameters of 7/10 nm and several hundred nanometers in length. For photochromic behavior in the case of AgCl-titanate nanotubes, the red color can be clearly observed after irradiation by red light, while the yellow, green, blue ones displayed pale black after the corresponding irradiation. On the other hand, Ag loaded TNT sample exhibited multicolor photochromism corresponding to that of incident light. The photoreduction of silver halide to Ag particle in the case of loaded AgCl particles and a particle-plasmon-assisted electron transfer from Ag nanoparticles to TiO₂ in the case of loaded Ag particles are considered to be responsible for this different behavior.     

The effect of the aminating temperature on the synthesis of gallium nitride nanowires doped with magnesium

GaN nanowires doped with Mg have been synthesized at different temperature through ammoniating the magnetron-sputtered Ga₂O₃/Au layered films deposited on Si substrates. X-ray diffraction (XRD), Scanning electron microscope (SEM), high-resolution TEM (HRTEM) equipped with an energy-dispersive X-ray (EDX) spectrometer and photoluminescence (PL) were used to analyze the structure, morphology, composition and optical properties of the as-synthesized sample. The results show that the ammoniating temperature has a great impact on the properties of GaN. The optimally ammoniating temperature of Ga₂O₃/Au layer is 900 C for the growth of GaN nanowires(NWs). The band gap emission (358 nm) relative to that (370 nm) of undoped GaN NWs has an apparent blueshift, which can be ascribed to the doping of Mg. Finally, the growth mechanism is also briefly discussed.     

Ease of control and switching between ordered free-standing arrays of ZnO nanotubes and nanorods on conductive transparent substrates

Free-standing arrays of ZnO nanotubes and nanorods have selectively been synthesized on indium tin oxide substrates using a template-based electrodeposition method for the first time. The effect of deposition voltage on the growth pattern of Zn in the alumina template has been investigated, providing a tailored ability to reliably produce either nanotubes or nanorods. An annular tungsten base electrode, derived from the anodization of the alumina template, has been found to be crucial to the growth of nanotubes. This method may be adapted for the fabrication of free-standing arrays of other metal and metal oxide nanotubes and nanorods on conducting substrates.     

银纳米颗粒阵列的表面增强拉曼散射效应研究

利用具有高密度拉曼热点的金属纳米结构作为表面增强拉曼散射(SERS)基底,可以显著增强吸附分子的拉曼信号.本文通过阳极氧化铝模板辅助电化学法沉积制备了高密度银(Ag)纳米颗粒阵列;利用扫描电子显微镜和反射谱表征了样品的结构形貌和表面等离激元特性;用1, 4-苯二硫醇(1, 4-BDT)为拉曼探针分子,研究了Ag纳米颗粒阵列的SERS效应.通过优化沉积时间,制备出高SERS探测灵敏度的Ag纳米颗粒阵列,检测极限可达10~(-13)mol/L;时域有限差分法模拟结果证实了纳米颗粒间存在强的等离激元耦合作用,且发现纳米颗粒底端的局域场增强更大.研究结果表明Ag纳米颗粒阵列可作为高效的SERS基底.     

Power dependence of size of laser ablated colloidal silver nanoparticles

Silver nanoparticles have been produced by laser ablation of silver metal in nanopure water without any chemical additives. It has been observed that laser power has a control over the size of the nanoparticles. Increasing laser power shows a clear blue shift in the absorption peak of fabricated nanoparticles indicating that the average size of the particles decreases with increasing laser power. Ablation for longer period reduces the average size of nanoparticles which is attributed to the re-ablation of fabricated nanoparticles. A good correlation has been observed between the peak of the absorption spectrum measured by UV-VIS spectroscopy and the average particle size measured by scanning electron microscope imaging method. The value of the coefficient of correlation is determined to be 0.965.     

Effect of nanoscale size and medium on metal work function in oleylamine-capped gold nanocrystals

The work function is an important material property with several applications in photonics and optoelectronics. We aimed to characterize the work function of clusters resulting from gold nanocrystals capped with oleylamine surfactant and drop-casted onto gold substrate. We used scanning Kelvin probe microscopy to investigate the work function, and complemented our study mainly with X-ray diffraction and X-ray photoelectron spectroscopy. The oleylamine works as an electron blocking layer through which the electrical conduction takes place by tunneling effect. The surface potential appears to depend on the size of the clusters, which can be ascribed to their difference in effective work function with the substrate. The charge state of gold clusters is discussed in comparison with theory, and their capacitance is calculated from a semi-analytical equation. The results suggest that at the nanoscale the work function is not an intrinsic property of a material but rather depends on the size and morphology of the clusters, including also effects of the surrounding materials.     

Fabrication, study of optical properties and structure of most stable (CdP2)n nanoclusters

CdP₂ nanoclusters were fabricated by incorporation into pores of zeolite Na–X and by laser ablation. Absorption and photoluminescence (PL) spectra of CdP₂ nanoclusters in zeolite were measured at the temperatures of 4.2, 77 and 293 K. Both absorption and PL spectra consist of two bands blue shifted with respect to bulk crystal. We performed the calculations aimed to find the most stable clusters in the size region up to size of the zeolite Na–X supercage. The most stable clusters are (CdP₂)₆ and (CdP₂)₈ with binding energies of 9.30 and 10.10 eV per (CdP₂)₁ formula unit, respectively. Therefore, we attributed two bands observed in absorption and PL spectra to these stable clusters. The Raman spectrum of CdP₂ clusters in zeolite was explained to be originated from (CdP₂)₆ and (CdP₂)₈ clusters as well. The PL spectrum of CdP₂ clusters produced by laser ablation consists of the asymmetric band with low-energy tail that has been attributed to emission of both (CdP₂)₈ cluster and CdP₂ microcrystals.     

Surface‐enhanced Raman scattering of silylated graphite oxide sheets sandwiched between colloidal silver nanoparticles and silver piece

Graphite oxide (GO) was successfully silylated by 3‐mercaptopropyltrimethoxysilane. The surface‐enhanced Raman scattering spectrum of the silylated GO sheets sandwiched between colloidal silver nanoparticles and silver piece is presented. The Raman signal shows a 10⁴ enhancement compared to that of bulk GO. The large Raman enhancement is most likely a result of electromagnetic (EM) coupling between the colloidal silver nanoparticles (localized surface plasmon) and the silver piece (surface plasmon polariton), creating large localized EM fields at their interface, where the silylated GO sheets reside in this sandwich architecture. Copyright © 2009 John Wiley & Sons, Ltd.     

Surface enhanced Raman spectroscopy of aromatic compounds on silver nanoclusters

Surface enhanced Raman spectroscopy (SERS) has been used to characterize multilayers of three different aromatic compounds in the proximity of silver nanoclusters. SERS of mercapto benzoic acid (MBA), which adsorbs onto the silver nanoclusters through the sulfur moiety, exhibits frequency shifts in comparison to the Raman spectrum of crystalline MBA. Conversely, benzoic acid and benzophenone that adsorb through the oxygen species lack these frequency shifts, and show only a typical SERS enhancement. We employed X-ray photoelectron spectroscopy (XPS), to probe the nature of the binding between the silver and the three different aromatic compounds. Thereafter, we assigned the major Raman peaks of all three molecules to specific molecular vibrations. Overall, this enables us to determine the origin of the observed shifts in the SERS spectrum of MBA and similar molecules.     

Characterization of the structure and the size distribution of branched polymers formed by co-polymerization of MMA and EGDMA

Free radical co-polymerization of methyl methacrylate (MMA) and ethyl glycol dimethyl methacrylate (EGDMA) in solution leads to the formation of polydisperse branched PMMA which grows in size until the system gels. The structure and the size distribution of the PMMA aggregates were characterized at infinite dilution using static and dynamic light scattering and size exclusion chromatography (SEC). The reaction extent was measured using SEC and Raman spectroscopy. The results show that the structure and size distribution of PMMA aggregates formed close to the gel point are compatible with those of percolating clusters. The structure factor of semi-dilute solutions of PMMA aggregates is the same as that of dilute solutions at distance scales much smaller than the correlation length of the concentration fluctuations (). However, the cut-off function of the pair correlation function at for semi-dilute solutions is more gradual than the cut-off function at for dilute solutions. Received 11 May 1998 and Received in final form 22 October 1998     

The effect of the deposition parameters on size, distribution and antimicrobial properties of photoinduced silver nanoparticles on titania coatings

Controlled photodeposition of silver nanoparticles (AgNP) on titania coatings using two different sources of UV light is described. Titania (anatase) thin films were prepared by the sol-gel dip-coating method on silicon wafers. AgNPs were grown on the titania surface as a result of UV illumination of titania films immersed in aqueous solutions of silver nitrate. UV xenon lamp or excimer laser, both operating at the wavelength 351 ± 5 nm, was used as illumination sources. The AFM topography of AgNP/TiO₂ nanocomposites revealed that silver nanoparticles could be synthesized by both sources of illumination, however the photocatalysis carried out by UV light from xenon lamp illumination leads to larger AgNP than those synthesized using the laser beam. It was found that the increasing concentration of silver ions in the initial solution increases the number of Ag nanoparticles on the titania surface, while longer time of irradiation results the growth of larger size nanoparticles. Antibacterial tests performed on TiO₂ covered by Ag nanoparticles revealed that increasing density of nanoparticles enhances the inhibition of bacterial growth. It was also found that antibacterial activity drops by only 10-15% after 6 cycles compared to the initial use.     

Investigation of spatial self-phase modulation of silver nanoparticles in clay suspension

We have investigated the spatial self-phase modulation (SSPM) phenomena in a clay suspension containing silver nanoparticles. Silver nanoparticles (Ag-NPs) were synthesized in the space of lamellar structure of montmorillonite (MMT) by using chemical reducing agent. The UV-vis spectra of the obtained Ag-NPs showed that the intensity surface plasmon resonance (SPR) peaks increase with increasing in concentration of AgNO₃. The results from Ag-NPs UV-vis spectra were in good agreement with the structure studies performed by TEM. The SSPM phenomena manifestation of the non-linear optical property appeared only when MMT suspension filled with Ag-NPs as shown in the existence of far-field pattern. This property increased with the increase of Ag-NPs concentration and limited to small range.     

A green approach to fabricate CuO nanoparticles

Uniform copper oxide (tenorite) nanoparticles have been prepared via a green pathway by thermal decomposition, using a novel supramolecular complex, in which β-cyclodextrin is selected to encapsulate the precursor copper(II) acetate.     

Enhancement of Raman scattering of light by ultramarine microcrystals in presence of silver nanoparticles

Approximately 10²‐fold enhancement of Raman scattering by ultramarine microcrystals is reported by means of interaction with silver nanoparticles in films and powders. Theoretical modeling predicts the maximal 10¹⁰‐fold enhancement in close vicinity of a silver spherical nanoparticle (0.24 nm) with rapid decay of enhancement factor to 1 in the range of approximately 50 nm. Experimental enhancement factor is treated as overall effect within the small portion of every microcrystal in the close vicinity of silver nanoparticle(s). The results are considered as an important extension of traditional surface enhanced molecular Raman spectroscopy towards bigger inorganic probes. Copyright © 2012 John Wiley & Sons, Ltd.