Effect of Glass Substrates on the Formation of Gold-Silver Colloids in Nanocomposite Thin Films

A sol-gel route to synthesize nanocomposite thin films containing phase separated metal colloids of gold (Au) and silver (Ag) was developed. Ag—Au colloids were prepared in silica films using dip coating technique. The annealing of the samples in air results in the formation of phase separated Ag and Au colloids in SiO₂ thin films, showing the surface plasmon peaks at 410 nm and 528 nm. For the synthesis of phase separated Ag and Au colloids on float glass substrates, formation of the silver colloids was found strongly dependent on the surface of the float glass. On the tin rich surface formation of both gold and silver colloids took place, whereas, on the tin poor surface the formation of only gold colloids was observed. The surface dependence of the formation of silver colloids was attributed to the presence of tin as Sn²⁺ state on the glass surface, which oxidizes into Sn⁴⁺ during heat treatment, reducing Ag⁺ into silver colloids.     

室温氧化还原反应制备AgCuSe三元纳米棒

AgCuSe nanorods were prepared at room temperature by a redox reaction. The as-prepared product was characterized by X-ray powder diffraction, transmission electron microscopy and X-ray photoelectron spectroscopy.X-ray powder diffraction shows that the as-prepared product is the tetragonal phase of AgCuSe. Transmission electron microscopy shows that the sample consists of nanorods with a diameter varying from 5 nm to 20 nm and a length varying from 200 nm to 600 nm. X-ray photoelectron spectroscopy shows that the purity of the sample is high. The formation mechanism of AgCuSe and the growth mechanism of AgCuSe nanorods were discussed.Thermodynamic calulations show that the final product in the synthetic system is pure AgCuSe. The solvent ethylenediamine did not only acts a didentate ligand to form relatively state Ag + and Cu + complexes, but also dissolved Se and enhanced the reactivity of Se. It played an important role in controlling the nucleation and growth of AgCuSe nanorods.     

Two-dimensional polymer formation on surfaces: insight into the roles of precursor mobility and reactivity

We report on a combined scanning tunneling microscopy (STM), X-ray photoelectron spectroscopy (XPS), and density functional theory (DFT) study on the surface-assisted assembly of the hexaiodo-substituted macrocycle cyclohexa-m-phenylene (CHP) toward covalently bonded polyphenylene networks on Cu(111), Au(111), and Ag(111) surfaces. STM and XPS indicate room temperature dehalogenation of CHP on either surface, leading to surface-stabilized CHP radicals (CHPRs) and coadsorbed iodine. Subsequent covalent intermolecular bond formation between CHPRs is thermally activated and is found to proceed at different temperatures on the three coinage metals. The resulting polyphenylene networks differ significantly in morphology on the three substrates: On Cu, the networks are dominated by "open" branched structures, on the Au surface a mixture of branched and small domains of compact network clusters are observed, and highly ordered and dense polyphenylene networks form on the Ag surface. Ab initio DFT calculations allow one to elucidate the diffusion and coupling mechanisms of CHPRs on the Cu(111) and Ag(111) surfaces. On Cu, the energy barrier for diffusion is significantly higher than the one for covalent intermolecular bond formation, whereas on Ag the reverse relation holds. By using a Monte Carlo simulation, we show that different balances between diffusion and intermolecular coupling determine the observed branched and compact polyphenylene networks on the Cu and Ag surface, respectively, demonstrating that the choice of the substrate plays a crucial role in the formation of two-dimensional polymers.     

Luminescent di- and polynuclear organometallic gold(I)-metal (Au2, {Au2Ag}n and {Au2Cu}n) compounds containing bidentate phosphanes as active antimicrobial agents

The reaction of new dinuclear gold(I) organometallic complexes containing mesityl ligands and bridging bidentate phosphanes [Au(2)(mes)(2)(μ-LL)] (LL=dppe: 1,2-bis(diphenylphosphano)ethane 1a, and water-soluble dppy: 1,2-bis(di-3-pyridylphosphano)ethane 1b) with Ag(+) and Cu(+) lead to the formation of a family of heterometallic clusters with mesityl bridging ligands of the general formula [Au(2)M(μ-mes)(2) (μ-LL)][A] (M=Ag, A=ClO(4)(-), LL=dppe 2a, dppy 2b; M=Ag, A=SO(3)CF(3)(-), LL=dppe 3a, dppy 3b; M=Cu, A=PF(6)(-), LL=dppe 4a, dppy 4b). The new compounds were characterized by different spectroscopic techniques and mass spectrometry The crystal structures of [Au(2)(mes)(2)(μ-dppy)] (1b) and [Au(2)Ag(μ-mes)(2)(μ-dppe)][SO(3)CF(3)] (3a) were determined by a single-crystal X-ray diffraction study. 3a in solid state is not a cyclic trinuclear Au(2)Ag derivative but it gives an open polymeric structure instead, with the {Au(2)(μ-dppe)} fragments "linked" by {Ag(μ-mes)(2)} units. The very short distances of 2.7559(6)?? (Au-Ag) and 2.9229(8)?? (Au-Au) are indicative of gold-silver (metallophilic) and aurophilic interactions. A systematic study of their luminescence properties revealed that all compounds are brightly luminescent in solid state, at room temperature (RT) and at 77?K, or in frozen DMSO solutions with lifetimes in the microsecond range and probably due to the self-aggregation of [Au(2)M(μ-mes)(2)(μ-LL)](+) units (M=Ag or Cu; LL=dppe or dppy) into an extended chain structure, through Au-Au and/or Au-M metallophilic interactions, as that observed for 3a. In solid state the heterometallic Au(2)M complexes with dppe (2a-4a) show a shift of emission maxima (from ca. 430 to the range of 520-540?nm) as compared to the parent dinuclear organometallic product 1a while the complexes with dppy (2b-4b) display a more moderate shift (505 for 1b to a max of 563?nm for 4b). More importantly, compound [Au(2)Ag(μ-mes)(2)(μ-dppy)]ClO(4) (2b) resulted luminescent in diluted DMSO solution at room temperature. Previously reported compound [Au(2)Cl(2)(μ-LL)] (LL dppy 5b) was also studied for comparative purposes. The antimicrobial activity of 1-5 and Ag[A] (A=ClO(4)(-), SO(3)CF(3)(-)) against gram-positive and gram-negative bacteria and yeast was evaluated. Most tested compounds displayed moderate to high antibacterial activity while heteronuclear Au(2)M derivatives with dppe (2a-4a) were the more active (minimum inhibitory concentration 10 to 1?μg?mL(-1)). Compounds containing silver were ten times more active to gram-negative bacteria than the parent dinuclear compound 1a or silver salts. Au(2)Ag compounds with dppy (2b, 3b) were also potent against fungi.     

Effect of molecule-substrate interaction on thin-film structures and molecular orientation of pentacene on silver and gold

Evaporated pentacene thin films with thicknesses from several nm to 150 nm on gold and silver substrates have been studied by ultraviolet photoelectron spectroscopy (UPS), near-edge X-ray absorption fine structure (NEXAFS), scanning tunneling microscopy (STM), and atomic force microscopy (AFM). It was found that pentacene thin-film structures, particularly their molecular orientations, are strongly influenced by the metal substrates. UPS measurements revealed a distinct change in the valence band structures of pentacene on Au compared to those on Ag, which is attributed to the different packing between adjacent molecules. Using NEXAFS, we observed 74+/-5 degrees and 46+/-5 degrees molecular tilt angles on Ag and Au, respectively, for all measured thicknesses. We propose that pentacene molecules stand up on the surface and form the "thin-film phase" structure on Ag. On Au, pentacene films grow in domains with molecules either lying flat or standing up on the substrate. Such a mixture of two crystalline phases leads to an average tilt angle of 46 degrees for the whole film and the change in valence band structures. STM and distance-voltage (z-V) spectroscopy studies confirm the existence of two crystalline phases on Au with different conducting properties. z-V spectra on the low conducting phase clearly indicate its nature as "thin-film phase".     

铟颗粒上具有不同直径氧化铟纳米锥的原位合成与光致发光特性

以Au作催化剂, 通过金属铟与氧气在850～1000 ℃的氧化反应, 在单质铟表面原位大面积生长出了In2O3纳米锥. 通过反应温度的改变实现了纳米锥的可控合成. 采用激光拉曼光谱、X射线衍射、扫描电镜和透射电镜对产物进行了表征分析. 结果表明, 纳米锥为立方相单晶结构的In2O3, 其直径和高度分别在0.1～0.6 μm和0.2～2.9 μm范围内可调控. 提出了In2O3纳米锥可能的生长机理. 在室温下研究了它们的发光性质, 发现了发光峰位于416和439 nm强的蓝光发光, 这一蓝光发光起源于氧化铟纳米锥中氧空位中的电子与铟-氧空位中心中的空穴之间的复合.     

Ag/Au Alloy LSPR Engineering by Co‐deposition of RF‐Sputtering and RF‐PECVD

Silver‐Gold alloy/diamond like carbon (Ag‐Au/DLC) nanocomposite films were prepared by co‐deposition of RF‐sputtering and RF‐PECVD on glass substrates by using acetylene gas and silver‐gold target. The deposition process was carried out at room temperature in one minute with the variable parameters of initial pressures and RF powers. X‐ray diffraction analysis demonstrated the formation of Ag/Au alloy nanoparticles with a face‐centered cubic (FCC) structure. Localized surface plasmon and optical properties of Ag‐Au alloy nanoparticles were studied by UV‐visible spectrophotometry which showed that increasing RF power and initial pressure cause a redshift in all samples. Moreover, the effect of RF power and initial pressure on the size and shape of nanoparticles were studied by 2D Atomic force microscopy images. Energy dispersive X‐ray spectroscopy revealed the formation of Ag‐Au/DLC nanoparticles and the percentages of C, Ag, Au and O in all samples. The applied method for Ag/Au alloy preparation is the one step and low‐cost method which makes the samples ready for sensing application.     

Fabrication of nanorattles with passive shell

This investigation describes the formation of a metal nanorattle with a pure metal shell by varying experimental parameters. The galvanic replacement reaction between silver and chloroauric acid was adopted to prepare hollow metal nanoparticles. This approach is extended to produce nanorattles of Au cores and Au shells by starting with Au(core)Ag(shell) nanoparticles as templates. The effect of temperature on the nanostructure of the final product is also considered. The composition of the shell in nanorattles can be controlled by varying the reaction temperature (to form pure gold or gold-silver alloy, for example). X-ray absorption fine structure spectroscopy is conducted to elucidate the fine structure of these nanoparticles. Partial alloying between the Au core and the Ag shell is observed by extended X-ray absorption fine structure (EXAFS).     

Application of surface science techniques to study a gilded Egyptian funerary mask: A multi-analytical approach

A wide range of analytical techniques has been used to study an Egyptian funerary mask of the Ptolemaic period (305-30 bc ). Secondary electron (SE) and back-scattering (BS) images, recorded by a scanning electron microscope (SEM), provided a detailed representation of the metallurgical techniques used to construct the gilded mask. It is confirmed, that the golden leaf used to cover the mask is the product of an antique refinery practice, so called, cementation process of naturally occurring alloy of gold and silver, namely electrum. Complementary results of SEM-electron dispersion spectroscopy (EDS) and electron probe microanalysis (EPMA)–wavelength dispersion spectroscopy (WDS) provided chemical compositions of the golden leaf as well as in the plaster base of the mask. X-ray photoemission spectroscopy (XPS) revealed the presence of Au, Ag, Si, S, Cl, Ca, and N, in addition to O and C. Relative concentration of Au/Ag at the surface has been measured by XPS to be 70% to 30%. XPS depth profiling verified silver-enrichment at the surface, as ratio of gold to silver is measured to be 80% to 20% at the depth of 15 nm. XPS chemical mapping images of gold and silver confirmed a rather inhomogeneous character of Au/Ag relative concentration at the surface. The main diffraction peaks in the X-ray diffraction (XRD) spectrum coincide with diffraction peaks of pure gold, silver metals, and magnesium calcite Mg_0.03Ca_0.97CO₃. Whereas, Raman spectroscopy results implied the existence of Ag₂S, a tarnishing compound, on the golden area of the mask.     

Thermal stability of Ag–Au,Cu–Au,and Ag–Cu bimetallic nanoparticles supported on highly oriented pyrolytic graphite

The formation of Ag–Au, Cu–Au, and Ag–Cu bimetallic particles on the surface of highly oriented pyrolytic graphite was studied by X-ray photoelectron spectroscopy. Samples with the core–shell structure of particles were prepared by sequential thermal vacuum deposition. The thermal stability of the samples was studied over a wide range of temperatures (25-400°C) under ultrahigh-vacuum conditions. The heating of the samples to ~250°C leads to the formation of bimetallic alloy particles with a relatively uniform distribution of metals in the bulk. The thermal stability of the samples with respect to sintering depends on the nature of the supported metals. Thus, the Ag–Au particles exhibited the highest thermal resistance (~350°C) under ultrahigh-vacuum conditions, whereas the Ag–Cu particles agglomerated even at ~250°C.     

Solvothermal preparation,and characterization,of Cu–Ag nanoparticles

Cu–Ag nanoparticles have been successfully synthesized by one-pot solvothermal treatment of a mixture of AgNO₃ and Cu(OAc)₂·H₂O in ethylene glycol solution at 180 °C for 10 h. The samples were characterized by UV–visible absorption, X-ray diffraction (XRD), and extended X-ray absorption fine structure (EXAFS) spectroscopy, transmission electron microscopy (TEM), and energy-dispersive X-ray spectroscopy (EDS). The results showed that Cu–Ag nanoparticles and a small amount of phase-separated Cu–Ag alloy nanoparticles with an average diameter of 100 ± 30 nm were synthesized by the solvothermal treatment procedure. The mechanism of formation is discussed.     

多孔铜基催化剂的制备及对苯甲醇的选择性催化氧化

采用去合金化法制备了多孔铜(PC), 并以此为还原剂和模板与含有贵金属离子的溶液进行置换反应, 简单有效地制备了多孔M/PC(M=Ag, Au, Pt, Pd)双金属催化剂, 并对样品的形貌\, 结构和化学组成进行了表征, 利用苯甲醇气相选择性催化氧化实验评价了其催化性能. 实验结果表明, 所制备的多孔铜基催化剂具有良好的双金属协同催化效应, 对苯甲醇气相选择性氧化具有很好的催化活性和选择性, 其中Ag/PC具有最优的催化性能.     

Temperature-induced phase transitions of the ordered superlattice assembly of Au nanoclusters

Superlattices of monolayer protected metallic and semiconducting nanoclusters have attracted significant attention due to their promising applications in nanotechnology. In this paper, we investigate the effect of temperature on the ordered superlattice structure of relatively larger sized Au nanoclusters passivated with dodecanethiol [ca. Au1415(RS)328] with the help of in situ temperature controlled X-ray diffraction (XRD) and infrared spectroscopy (IR) in conjunction with thermogravimetric (TG) and differential scanning calorimetric (DSC) analysis. In brief, monolayer protected Au nanoclusters (AuMPC) were prepared by a modified Brust synthesis technique, where dodecanethiol itself acts as both phase transfer and simultaneous capping agent during the reduction process, generating an average particle size of 3.72 +/- 0.4 nm after repeated solvent extraction and careful fractionation experiments. These particles are characterized with the help of UV-vis, transmission electron microscopic (TEM), IR, and NMR techniques, where effective capping as well as the superlattice formation on the TEM grid is evident from the combined analysis of these results. In situ low-angle XRD analysis shows that the particles undergo an irreversible phase transition in the temperature range of 100-115 degrees C, which is also reflected in the data from in situ IR analysis. However, the DSC analysis does not account for this phase transition, although the reversible phase transition due to the alkyl chain dynamics is in good agreement with the previously reported results. These results indicate the formation of temperature-induced, diffusion-limited phase transition involving nonequilibrium fractal structures, which is in good agreement with the previous available theoretical studies. The determination of the temperature window for the stability of these ordered assemblies would be used to understand the effect of thermal stress for device applications.     

Electrochemical solid-state phase transformations of silver nanoparticles

Adenosine triphosphate (ATP)-capped silver nanoparticles (ATP-Ag NPs) were synthesized by reduction of AgNO(3) with borohydride in water with ATP as a capping ligand. The NPs obtained were characterized using transmission electron microscopy (TEM), UV-vis absorption spectroscopy, X-ray diffraction, and energy-dispersive X-ray analysis. A typical preparation produced ATP-Ag NPs with diameters of 4.5 ± 1.1 nm containing ~2800 Ag atoms and capped with 250 ATP capping ligands. The negatively charged ATP caps allow NP incorporation into layer-by-layer (LbL) films with poly(diallyldimethylammonium) chloride at thiol-modified Au electrode surfaces. Cyclic voltammetry in a single-layer LbL film of NPs showed a chemically reversible oxidation of Ag NPs to silver halide NPs in aqueous halide solutions and to Ag(2)O NPs in aqueous hydroxide solutions. TEM confirmed that this takes place via a redox-driven solid-state phase transformation. The charge for these nontopotactic phase transformations corresponded to a one-electron redox process per Ag atom in the NP, indicating complete oxidation and reduction of all Ag atoms in each NP during the electrochemical phase transformation.     

Static investigation of adsorption and hetero‐diffusion of copper,silver, and gold adatoms on the (111) surface

In this work, we have used the static molecular simulations combined with an interatomic potential derived from the embedded‐atom method to study the adsorption and hetero‐diffusion on the (111) surface of Cu, Ag, and Au adatoms by using LAMMPS code. The investigation is performed for six heterogeneous systems such as Ag/Au(111), Ag/Cu(111), Au/Ag(111), Au/Cu(111), Cu/Ag(111), and Cu/Au(111). First, we have investigated the relaxation trends and the bond lengths of the atoms in the systems. The calculation results show that, the top layer spacing between the first and second layers of the Au(111), Ag(111), and Cu(111) substrates is contracted. This contraction is found to be more important in the Au(111) substrate. On the other hand, the strong reduction of the binding length is found in Au/Cu(111) for the different adsorption sites. In addition, the binding, adsorption, and static activation energies for all studied systems were examined. The results indicated that the binding and adsorption energies reached their maximum values in the Au/Cu(111) and Au/Ag(111) systems, respectively. Moreover, the static activation barriers for hopping diffusion on the (111) surfaces are found to be low compared with those found in the (100) and (110) surfaces. Therefore, our calculations showed that the difference in energy between the hcp and fcc sites on the (111) surfaces is very small. Copyright © 2017 John Wiley & Sons, Ltd.     

添加Cu2S对Bi-Pb-Sr-Ca-Cu-O体系超导性的影响

本文对Cu_2S添加的Bi-Pb-Sr-Ca-Cu-O体系进行了低温电阻、X射线衍射和XPS研究．实验结果表明，加入少量的Cu_2S能够降低高T_c相的形成温度，改善超导性能，加入Cu_2S引起了Cu 2p_(3/2)谱的主峰向低结合能方向移动，并减少其卫星峰的面积．这表明Cu_2S的加入减少了Cu~(2+)的量，即导致空穴载流子浓度的减小．     

Electronic structure and conductivity of nanocomposite metal (Au,Ag, Cu,Mo)-containing amorphous carbon films

In this work, we study the influence of the incorporation of different metals (Me = Au, Ag, Cu, Mo) on the electronic structure of amorphous carbon (a-C:Me) films. The films were produced at room temperature using a species selective bias pulsed dual-cathode arc deposition technique. Compositional analysis was performed with secondary neutral mass spectroscopy whereas X-ray diffraction was used to identify the formation of metal nanoclusters in the carbon matrix. The metal content incorporated in the nanocomposite films induces a drastic increase in the conductivity, in parallel with a decrease in the band-gap corrected from Urbach energy. The electronic structure as a function of the Me content has been monitored by X-ray absorption near edge structure (XANES) at the C K-edge. XANES showed that the C host matrix has a dominant graphitic character and that it is not affected significantly by the incorporation of metal impurities, except for the case of Mo, where the modifications in the line shape spectra indicated the formation of a carbide phase. Subtle modifications of the spectral line shape are discussed in terms of nanocomposite formation.     

Synthesis of core/shell nanoparticles of Au/CdSe via Au-Cd bialloy precursor

We present a novel method for the preparation of ultrasmall Au/CdSe core/shell particles. Au-Cd bialloy particles of 4.7 nm diameter were prepared as the precursor. The Cd component in the precursor reacted with the Se source at a temperature of 205 degrees C and was heated to 250 degrees C, leading to formation of a Au/CdSe core/shell structure. The sizes of Au/CdSe nanoparticles have a narrow distribution with an average size of 6.0 nm and Au core of 2.2 nm diameter. The X-ray diffraction pattern and the images of the high-resolution electron transmission microscopy show that the Au cores and the CdSe shells of Au/CdSe core/shell nanoparticles are both well crystallized, and the CdSe shells are in a cubic phase. The absorption spectrum of the Au/CdSe nanoparticles combines the absorption behaviors of the Au cores and the CdSe shells.     

Control of Surface Plasmon Resonance of Au/SnO2 by Modification with Ag and Cu for Photoinduced Reactions under Visible‐Light Irradiation over a Wide Range

Gold particles supported on tin(IV) oxide (0.2 wt % Au/SnO₂) were modified with copper and silver by the multistep photodeposition method. Absorption around λ=550 nm, attributed to surface plasmon resonance (SPR) of Au, gradually shifted to longer wavelengths on modification with Cu and finally reached λ=620 nm at 0.8 wt % Cu. On the other hand, the absorption shifted to shorter wavelength with increasing amount of Ag and reached λ=450 nm at 0.8 wt % Ag. These Cu‐ and Ag‐modified 0.2 wt % Au/SnO₂ materials (Cu‐Au/SnO₂ and Ag‐Au/SnO₂) and 1.0 wt % Au/SnO₂ were used for mineralization of formic acid to carbon dioxide in aqueous suspension under irradiation with visible light from a xenon lamp and three kinds of light‐emitting diodes with different wavelengths. The reaction rates for the mineralization of formic acid over these materials depend on the wavelength of light. Apparent quantum efficiencies of Cu‐Au/SnO₂, Au/SnO₂, and Ag‐Au/SnO₂ reached 5.5 % at 625 nm, 5.8 % at 525 nm, and 5.1 % at 450 nm, respectively. These photocatalysts can also be used for selective oxidation of alcohols to corresponding carbonyl compounds in aqueous solution under visible‐light irradiation. Broad responses to visible light in formic acid mineralization and selective alcohol oxidation were achieved when the three materials were used simultaneously.     

Coinage metal complexes of 2-diphenylphosphino-3-methylindole

Coordination of P,N indolyl-phosphine ligands to Au(I), Ag(I) and Cu(I) metal ions under weakly basic conditions results in easy deprotonation of the indolyl N-H function and effective formation of a family of homo- and heterobimetallic complexes MM'(PPh(2)C(9)H(7)N)(2) (M = M' = Au (2), Ag (5); M = Au, M' = Cu (3), Ag (4)). The latter (4) exists as an inseparable mixture of four different complexes, which are in equilibrium driven by slow dynamics. The reaction of silver(I) and copper(I) ions with PPh(2)(C(9)H(8)N) affords a rare tetranuclear Z-shaped cluster Ag(2)Cu(2)(PPh(2)C(9)H(7)N)(4) (6), which exhibits red luminescence in solid state (650 nm) and a weak dual emission in solution with the main component in the near-IR region (746 nm).