Adsorption of carbon monoxide on silver/palladium alloys

The adsorption of carbon monoxide on epitaxial (100) and (111) planes of Ag/Pd alloys with definite surface compositions has been studied by means of LEED, Auger electron spectroscopy and work function measurements. The formation of ordered adsorbed structures is prevented by even small amounts of silver in the surfaces. The maximum variation of the work function with CO adsorption bears no simple relationship to the surface composition. From measured adsorption isotherms the isosteric heats of adsorption have been evaluated. For CO adsorption on pure Pd planes the adsorption energies E_ad are either constant or decrease slowly up to high coverages, whereas a continuous decrease was observed with the alloys indicating the energetical heterogeneity. The results are discussed on the basis of our knowledge about the nature of the CO chemisorption and about the electronic structure of Ag/Pd alloys.     

SERS characterization of metallic silver nanoparticle self‐assembly within thin films

Clusters of silver nanoparticles are generated by the thermally initiated reduction of silver carboxylates (long‐chain fatty acids) in the thin polymer films. The size, shape, and aggregation of these nanoparticles are affected by the reduction reaction in the presence of capping agents. In order to understand the mechanism(s) controlling the silver structure formation, it is essential to understand the surface coordination chemistry occurring during this process. We now report the first application of surface‐enhanced Raman spectroscopy (SERS) to directly characterize adsorbates on the surfaces of silver nanoparticles within a thin film imaging construction containing multiple components. In addition, SERS investigation of model silver substrates was used to confirm the identify of specific adsorbates of silver complexes. This is a powerful tool for revealing the chemistry involved with the control of silver nanoparticle aggregation during thermally induced metallic silver formation within thin films. Both the catechol‐reducing agent and the phthalazinone (PAZ) particle aggregation agent are observed on the metallic silver surface at the initial particle formation and during its crystal growth. However, careful attention to excitation wavelength is required in order to observe all the surface species. PAZ appears to be more effective at stabilizing individual silver particles than other aggregation agents investigated. An understanding of the roles of the aggregation/reducing agents in the growth and aggregation of silver nanoparticles is important for preparing different types of silver particles for specific applications including silver‐based thermal imaging systems. Copyright © 2008 John Wiley & Sons, Ltd.     

Dispersion and rheology of surfactant-mediated silver nanoparticle suspensions

Polycrystalline silver (Ag) nanoparticles were dispersed in solvent mixtures consisting of 2-butoxyethyl acetate (BCA) and diethylene glycol monoethyl ether acetate (CA) in a BCA:CA weight ratio of 5:1. Three commercially available polymeric surfactants were used, and the gravitational sedimentation, agglomerate-size distribution, isothermal adsorption, and rheological behavior of the nanoparticle suspensions were examined. One of the surfactants (hereafter termed 9250) was found effective in stabilizing the Ag nanoparticle suspensions. Both the adsorption isotherm and the Fourier transform infrared spectroscopy revealed the preferential adsorption of the 9250 surfactant molecules on the nanoparticle surface, forming a Langmuir-type monolayer adsorption in the given solvents so that a steric stabilization was rendered. An optimal surfactant concentration of 5 wt.% (in terms of the solids weight) was determined experimentally. In addition, the Ag suspensions with a broad range of solids concentration (? = 1-16 vol.%) showed a shear-thinning flow character over a shear-rate range from 1 to 4000 s⁻¹, revealing that an attractive interparticle interaction was operative. Relative viscosity (η_r) of the nanoparticle suspensions deviated from the linearity when ? was greater than ∼10 vol.%; at which, the attractive potential began to dominate the interparticle interactions. This η_r-? dependence was compared with various existing models and the (viscosity) predictive capability of the models was discussed.     

Investigating mechanical properties of polymethylmethacrylate/silver nanoparticle composites by molecular dynamics simulation

The molecular dynamics simulation (MD) was carried out to investigate the mechanical properties of pristine polymethylmethacrylate (PMMA) and the composites of PMMA mixed with the silver nanoparticles (PMMA/AgNPs) at two AgNP weight fractions at 0.60 and 1.77 wt%. From the stress–strain profiles by the tensile process, it can be seen that the improvement on Young’s modulus is insignificant at these lower AgNP fractions. The tensile strength of pristine PMMA can be slightly improved by the embedded AgNPs at 1.77 wt%, because the local density and strength of PMMA in the vicinity of AgNP surface within about 8.2 Å are improved. For the temperature effect on the mechanical properties of pristine PMMA and PMMA/AgNP composite, the Young’s moduli and strength of pristine PMMA and PMMA/AgNP composite significantly decrease at temperatures of 450 and 550 K, which are close to the predicted melting temperature of pristine PMMA about 460 K. At these temperatures, the PMMA materials become more ductile and the AgNPs within the PMMA matrix display higher mobility than those at 300 K. When the tensile strain increases, the AgNPs tend to get closer and the fracture appears at the PMMA part, leading to the close values of Young’s modulus and ultimate strength for pristine PMMA and PMMA/AgNP composite at 450 and 550 K.

Open image in new window

Graphical abstract Stress–strain curves of pristine PMMA, polymethylmethacrylate (PMMA)/silver nanoparticles (AgNP) (0.60%), and PMMA/AgNP (1.77%). Inset images: local shear strain of pristine PMMA (red) and PMMA/AgNP (1.77%) (green).

     

Preparation and characterization of conducting polymer/silver hexacyanoferrate nanocomposite

In this work, we present an alternative route to prepare silver hexacyanoferrate(II)/polyaniline (PANI) composite thin films. Differently from the electrochemical method, used to synthesize the conducting polymer film on a electrode surface, this new chemical route makes use of dialysis membrane as a solid support to synthesize the silver hexacyanoferrate(III) compound, and subsequently uses this composite membrane as oxidizing agent to polymerize the aniline monomer. The spectroscopic (UV-vis and IR region) and electrochemical characterization (cyclic voltammetry) indicates that the polymeric composite remains optically active and conductive. The X-ray analysis shows that the composite membrane/Ag₃[Fe_III(CN)₆] has an crystalline structure that can be assigned to the Ag₃[Fe_III(CN)₆] structure, and after reaction with aniline solution it became less crystalline. Additionally the SEM measurements shown that the reaction of silver ions with hexacyanoferrate(III) across the membrane results in a well defined and aliened Ag₃[Fe_III(CN)₆] crystals and when this crystalline compound reacts with aniline monomer silver wire of 100 nm of diameter by 6 μm longer are formed together with the conducting polymer polyaniline/Ag_x[Fe_II(CN)₆] composite.     

Preparation, characterization, and photocatalytic properties of silver carbonate

Silver carbonate (Ag₂CO₃) short rods were prepared using a precipitation method. It was characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), diffuse reflective spectra (DRS) and photocatalytic degradation of organic pollutants and destruction of E. coli measurements. The results of DRS suggested that the optical transition of Ag₂CO₃ was indirectly allowed, and its band gap was determined to be 2.08 eV. The prepared Ag₂CO₃ displayed a high activity towards degradation of phenol and MB under visible light. The total organic carbon (TOC) value decreased during the photocatalytic process, which suggests that phenol was truly photodegraded. The stability of Ag₂CO₃ was greatly improved when Na₂CO₃ was added into the photocatalytic system. In addition, Ag₂CO₃ displayed enhanced photocatalytic activities for the destruction of E. coli due to its photogenerated electron-hole pairs.     

Synthesis, characterization, and electrical properties studies of cadmium selenide nanoparticle

A new solvothermal route was used for the preparation of CdSe nanoparticles at 160 °C for 10 h using ethylenediamine as a solvent. X-ray powder diffraction and transmission electron microscope were employed to characterize the size, morphology, and crystalline structure of the as-prepared sample. The formation process was discussed and it revealed a uniform hexagonal shape of CdSe nanoparticle with good dispersion, with an average size of 35 nm. Fourier transform infrared and ultraviolet-visible spectroscopies were used to follow the reaction and to determine the optical band gap. DC and AC electrical conductivities were studied and the activation energies were determined as well as the conduction mechanism. The results indicated that CdSe behaves as a semiconducting material. The dielectric properties were measured as a function of temperature at different frequencies ranging from 100 Hz to 100 kHz. The increase of the dielectric constant with increasing temperature was discussed on the basis of increasing polarizability, while its decrease with increasing frequency is attributed to the dielectric dispersion.     

Mycorrhizal fungi influence on silver uptake and membrane protein gene expression following silver nanoparticle exposure

The rapid growth of nanotechnology and the high demand for nanomaterial use have greatly increased the risk of particle release into the environment. Understanding nanomaterial interactions with crop species and their associated microorganisms is critical to food safety and security. In the current study, tomato was inoculated with mycorrhizal fungi and subsequently exposed to 12, 24, or 36 mg/kg of 2- or 15-nm silver nanoparticles (Ag-NPs). Mycorrhizal (M) and non-mycorrhizal (NM) tomatoes exposed to 36 mg/kg of 2-nm Ag-NPs accumulated 1300 and 1600 μg/g silver in their tissues, respectively. Mycorrhizal plants accumulated 14% less silver compared to non-mycorrhizal plants. To begin to understand the mechanisms by which plants accumulate NPs, the expression of two aquaporin channel genes, the plasma membrane intrinsic protein (PIP) and the tonoplast membrane intrinsic protein (TIP), and one potassium channel (KC) gene were studied. In non-mycorrhizal plants, the expression of KC, PIP, and TIP was eight, five, and nine times higher than the control, respectively. These expressions for mycorrhizal plants were 5.8, 3.5, and 2 times higher than controls, respectively. The expression of KC and PIP, which are located on the plasma membrane, was 3.5 and 2.5, respectively, times higher than TIP, which is located on the tonoplast. PIP expression was significantly higher in NM tomatoes exposed to 12 mg/kg of 2-nm Ag-NPs compared to M plants. These results show that mycorrhizal colonization decreases Ag accumulation in NP-exposed plants and also moderates changes in expression level of membrane transport proteins.     

Interaction between silver nanoparticle and bovine hemoglobin at different temperatures

The binding of silver nanoparticles to bovine hemoglobin (BHb) was studied by fluorescence, UV–Visible, and circular dichroism (CD) spectroscopic techniques at different temperatures of 20, 37, and 42 °C. The absorption spectrum of soret band, in the presence of silver nanoparticle, showed a significant spectral change, which indicated the heme groups of BHb were directly attacked and degraded by silver nanoparticle. The fluorescence data explained that the nanoparticle binding to BHb occurred at a single binding site, which demonstrated a dynamic quenching procedure. Nanoparticles could reduce the fluorescence of tryptophanyl residues of BHb to a lesser extent. Circular dichroism studies demonstrated a conformational change of BHb in the presence of silver nanoparticles. The helicity of BHb was reduced by increasing silver nanoparticle concentration at different temperatures. Thermodynamic analysis of the protein interaction by silver nanoparticles suggested that the binding process is only entropy driven.     

Synthesis,characterization, conductivity and sensor application study of polypyrrole/silver doped nickel oxide nanocomposites

Conducting polymer composites of polypyrrole (PPy) and silver doped nickel oxide (Ag-NiO) nanocomposites were synthesised by in situ polymerisation of pyrrole with different contents of Ag-NiO nanoparticles. The formation of nanocomposites were studied by Fourier transform infrared (FTIR) and UV–vis spectroscopy, field emission scanning electron microscopy (FE-SEM), X-ray diffraction (XRD), thermogravimetric analysis (TGA), differential scanning calorimetry (DSC) and AC and DC conductivity measurements. The sensitivity of ammonia gas through the nanocomposite was analysed with respect to different contents of nanoparticles. Spectroscopic studies showed the shift in the absorption bands of polymer nanocomposite than that of pure PPy indicating the strong interaction between the nanoparticles and polymer chain. FESEM revealed the uniform dispersion of nanoparticles with spherically shaped metal oxide particles in PPy matrix. The XRD pattern indicated a decrease in amorphous domain of PPy with increase in loading of nanoparticles. The higher thermal stability and glass transition temperature of polymer nanocomposites than that of pure PPy were revealed from the TGA and DSC respectively. The dielectric properties, DC and AC conductivity of nanocomposites were much higher than PPy and these electrical properties increases with the loading of nanoparticles. The nanocomposites showed an enhancement in sensitivity towards ammonia gas detection than PPy.     

Optical absorption coefficient of nickel,palladium platinum and copper,silver, gold between 20 and 120 eV

Electron-energy loss spectra recorded up to 120 eV are used to compute the complex dielectric constant and then the optical absorption coefficient.     

Generation and thermally adjustable catalysis of silver nanoparticle immobilized temperature-sensitive nanocomposite

The rise in environmental issues due to the catalytic degradation of pollutants in water has received much attention. In this report, a facile method was developed for the generation of a novel thermosensitive Ag-decorated catalyst, SiO₂@PNIPAM@Ag (the average particle size is around 540 nm), through atom transfer radical polymerization (ATRP) and mild reducing reactions. First, poly(N-isopropylacrylamide) (PNIPAM) was used to create a shell around mercapto-silica spheres that allowed for enhanced catalyst support dispersion into water. Second, through a mild reducing reaction, these Ag nanoparticles (NPs) were then anchored to the surface of SiO₂@PNIPAM spheres. The resulting catalyst revealed catalytic activity to degrade various nitrobenzenes and organic dyes in an aqueous solution with sodium borohydride (NaBH₄) at ambient temperature. The catalytic activity can be adjusted in different temperatures through the aggregation or dispersion of Ag catalyst on the polymer supporters, which is due to the thermosensitive PNIPAM shell. The ease of preparation and efficient catalytic activity of the catalyst can make it a promising candidate for the use in degrading organic pollutants for environmental remediation.

Open image in new window

Graphical abstract ?

     

Analytical characterization of gold nanoparticle primary particles,aggregates, agglomerates,and agglomerated aggregates

Gold nanoparticles have been studied for many biomedical applications. However, alterations in the gold nanoparticles’ environment frequently lead to the formation of aggregates and agglomerates, which have not been well characterized. These new structures could significantly change the biological impact of the nanoparticles, so the appropriate characterization of these structures prior to biological administration is vital for the correct interpretation of toxicology results. By varying the solvent or heating under pressure, four reproducible gold nanoparticles structures were created: 10 nm primary particles, aggregates of the primary particles that contain non-reversible bonds between the individual nanoparticles, agglomerates of primary particles that contain reversible interactions between the individual nanoparticles, and agglomerated aggregates that have reversible bonds linking individual aggregates. Ultraviolet–visible (UV–Vis) spectroscopy, thermal gravitational analysis, and neutron activation analysis were each found to accurately measure the concentration of the primary particles. The primary particles measured 10 nm by dynamic light scattering (DLS) and had a spherical morphology by transmission electron microscopy (TEM) while the aggregates measured 110 nm by DLS and had a distorted morphology by TEM. The agglomerate and aggregated agglomerate samples both measured >1,000 nm by DLS, but the individual particles had significantly different morphologies by TEM. Multiple other analytical techniques, including ultracentrifugation, gel electrophoresis, and X-ray diffraction, also showed unique traits for each structure. The structural differences did not change in the presence of cell culture media or rat serum. In addition, the primary particles, aggregates, and agglomerates each had a unique UV–Vis spectrum, allowing for an inexpensive, rapid method to differentiate between the structures.     

Synthesis and characterization of magnetic Fe/CNTs composites with controllable Fe nanoparticle concentration

Fe/CNTs composites, with different concentrations of Fe nanoparticles (NPs) on carbon nanotube (CNT) surfaces, were successfully fabricated via a facile solvothermal method. The lengths of CNTs are up to 10 μm and the mean diameter of the Fe nanoparticles is about 25 nm. The structures, composition and magnetic properties of the Fe/CNTs were characterized by XRD, FTIR, FE-SEM, TEM and PPMS. We found that the concentrations of Fe nanoparticles depositing on the CNTs could be controlled by adjusting the initial mass ratio of ferrocene to CNTs. The Fe/CNTs composites display good ferromagnetic properties at room temperature, with a saturation magnetization of 125 emu/g-Fe and a coercivity of 276 Oe. The Curie temperature of the sample is about 1038 K, slightly lower than that (1043 K) of the bulk iron.     

Positioning of cationic silver nanoparticle by using AFM lithography and electrostatic interaction

One-dimensional metal lines of silver nanoparticles with a nano-sized width were generated onto silicon surface by using a nano-level lithography technique, field induced oxidation (FIO) by AFM, on self-assembled monolayer-modified Si wafers. This FIO technique provided SiO₂ lines a width of less than 100 nm. Short-time immersion of partially anodized silicon surface which is covered by a cationic silanol surfactant ((CH₃O)₃SiCH₂CH₂CH₂N(CH₃)₃⁺Cl⁻)-monolayer into quaternary ammonium (HSCH₂CH₂N(CH₃)₃⁺Br⁻)-covered silver nanoparticles readily and reproducibly gave nano-metal lines of silver onto silicon wafers. Hydrophilicity of the whole wafer surface was indispensable for homogeneously wetting the anodized SiO₂ area with a nanodimensional width.     

Laser sintering of silver nanoparticle thin films: microstructure and optical properties

We present a method for the sintering of silver (Ag) nanoparticle thin films by millisecond pulsed laser irradiation. The microstructure of sintered thin films and sintering behaviors of nanoparticles were systematically investigated in this paper. Absorption spectra of sintered thin films showed blue-shifted surface plasmon resonances (SPR) from 500 nm to 480 nm and red-shifted from 480 nm to 550 nm when laser power was varied from 100 W to 140 W and from 140 W to 200 W, respectively. This indicates a new technique to control light absorption through joining nanoparticles with laser sintering. According to theoretical calculations based on a heat diffusion model, the melting temperature of these Ag nanoparticles was estimated to be 440 °C during laser irradiation.     

Layer by layer growth of silver chloride nanoparticle within the pore channels of SBA-15/SO3H mesoporous silica (AgClNP/SBA-15/SO3K): Synthesis,characterization and antibacterial properties

The growth of silver chloride nanoparticles within the pore channels of functionalized SBA-15 mesoporous was achieved by sequential dipping steps in alternating bath of potassium chloride and silver nitrate under ultrasound irradiation at pH=9. The effects of sequential dipping steps in growth of the AgCl nanoparticles have been studied. The growth and formation of AgCl nanoparticles inside the sulfonated SBA-15 were characterized by X-ray diffraction (XRD), Fourier transformation infrared spectroscopy (FTIR), scanning electron microscopy (SEM) and transmission electron microscopy (TEM). Antibacterial activity of the synthesized materials was investigated against Escherichia coli (E.coli) using the conventional diffusion-disc method. The materials showed high antibacterial activity.     

The preparation and characterization of nanoparticle TiO2/Ti films and their photocatalytic activity

Nanoparticle TiO₂/Ti films were prepared by a sol–gel process using Ti(OBu)₄ as raw material, the as-prepared film samples were also characterized by TG-DTA, XRD, TEM, SEM, XPS, DRS, PL, SPS and EFISPS testing techniques. TiO₂ nanoparticles experienced two processes of phase transition, i.e. amorphous to anatase and anatase to rutile at the calcining temperature range from 450 to 700 °C. TiO₂ nanoparticles calcined at 600 °C had similar composition, structure, morphology and particle size with the internationally commercial P-25 TiO₂ particles. Thus, the conclusion that 600 °C might be the most appropriate calcining temperature during the preparation process of nanoparticle TiO₂/Ti film photocatalysts could be made by considering the main factors such as the properties of TiO₂ nanoparticles, the adhesion of nanoparticle TiO₂ film to Ti substrate, the effects of calcining temperature on Ti substrate and the surface characteristics and morphology of nanoparticle TiO₂/Ti film for the practice view. The Ti element mainly existed on the nanoparticle TiO₂/Ti(3) film calcined at 600 °C as the chemical state of Ti⁴⁺, while O element mainly existed as three kinds of chemical states, i.e. crystal lattice oxygen, hydroxyl oxygen and adsorbed oxygen with increasing band energy. Its photoluminescence (PL) spectra with a peak at about 380 nm could be observed using 260 nm excitation, possibly resulting from the electron transition from the bottom of conduction band to the top of valence band. The PL peak position was nearly the same as the onset of its diffuse reflection spectra (DRS) and surface photovoltage spectroscopy (SPS), demonstrating that the effects of the quantum size on optical property were greater than that of the Coulomb and surface polarization. The PL spectra with two peaks related to the anatase and rutile, respectively, could be observed using the excited wavelength of 310 nm. Weak PL spectra could be observed using the excited wavelength of 450 nm, resulting from surface states. In addition, during the experimental process of the photocatalytic degradation phenol, the photocatalytic activity of nanoparticle TiO₂/Ti film with three layers calcined at 600 °C was the highest.     

Synthesis and characterization of nanophased silver tungstate

Silver tungstate (Ag₂WO₄) nanoparticles in two different morphologies are prepared by controlling the reaction kinetics of aqueous precipitation. X-ray diffraction studies reveal that the silver tungstate nanoparticles are in the α-phase. SEM images show the rod-like and fiber-like morphologies of the nanoparticles with high aspect ratios. The TGA and DTA studies show the high thermal stability of the nanorods. The average crystallite sizes (20–30 nm) of the rod-like silver tungstate estimated from TEM is consistent with the XRD results