A Unique Au–Ag–Au Triangular Motif in a Trimetallic Halonium Dication: Silver Incorporation in a Gold(I) Catalyst

As a result of explorations into the solution chemistry of silver/gold mixtures, a unique diphosphine trimetallic chloronium dication was discovered that incorporates silver–arene chelation and a triangular mixed gold/silver core in the solid state. Notably, it was isolated from a Celite prefiltered solution initially thought to be silver‐free. The crystal structure also incorporates the coordination to silver of one fluorine atom of one SbF₆^? counterion. The structure was compared to two new, but well‐precedented, phosphine digold chloride cations. DFT calculations supported significant silver–halide and silver–arene interactions in the mixed gold/silver complex and metallophilic interactions in all three complexes. Comparison of computed data revealed that the ωB97X‐D functional, which has a long‐range corrected hybrid with atom–atom dispersion corrections, gave a better fit to the experimental data compared with the PBE0 functional, which has previously failed to capture aurophilic interactions. Preliminary studies support the presence of the mixed gold/silver structure in solution.     

Characteristics of polypyrrole electrodeposited onto roughened substrates composed of gold–silver bimetallic nanoparticles

In this work, the characteristics of polypyrrole (PPy) films electrodeposited onto an electrochemically roughened gold substrate with bimetallic silver and gold nanoparticles were first investigated. First, a silver substrate was roughened by a triangular‐wave oxidation–reduction cycle (ORC) in an aqueous solution containing 0.1 M HCl. Subsequently, a gold substrate was roughened by a similar ORC treatment in this used solution. The results revealed that the surface of the roughened gold substrate demonstrated two different kinds of deposition domains because of the modification of silver nanoparticles. Encouragingly, some novel characteristics of PPy deposited onto this substrate were observed, in comparison with those on the roughened gold substrate without the modification of silver nanoparticles. They included a denser and more compact surface morphology, higher oxidation degree, increased conductivity, and improved surface‐enhanced Raman scattering. Furthermore, the nucleation and growth mechanism for PPy electropolymerization on this silver‐modified roughened gold substrate was distinguishable from that on the unmodified one. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 2724–2731, 2006     

Experimental study on effect of different parameters on size and shape of triangular silver nanoparticles prepared by a simple and rapid method in aqueous solution

This paper continues our previous work on preparation of truncated triangular silver nanoparticles. The method proceeds with reaction of silver nitrate with hydrazine in the presence of sodium citrate in aqueous solution, in which triangular nanoparticles are formed in a few minutes with some spherical ones. In particular range of reactants, especially high reductant concentration, only spherical nanoparticles are formed. In further investigation we observed that spherical nanoparticles shape could change to triangular by aging. This means that controlled growth of nanoparticles could lead to the formation of triangular ones. Therefore, a method was devised to slow down the rate of reduction by adding Fe³⁺ to the reaction solution. The results show that in this case more triangular nanoparticles are formed compared to the original one. This result also confirms that with the increasing hydrazine concentration, growth becomes less important compared to nucleation and smaller triangles are formed.     

Ultrathin gold nanoframes through surfactant-free templating of faceted pentagonal silver nanoparticles

Ultrathin gold nanoframes (up to 1.6 nm) were prepared via templating upon well-defined faceted silver morphologies. Starting with silver decahedra, small quantities of gold (1-10 mol% relative to the amount of silver) were selectively deposited on the nanoparticle edges under optimized reducing conditions. Silver dissolution in hydrogen peroxide yielded well-defined gold frames that retained their structural integrity in the ultrathin nanowire regime below 2 nm. The frame formation protocol was also successfully applied to other silver nanoparticle shapes featuring pentagonal twinning and (111) facets (e.g., pentagonal faceted rods and icosahedra). The demonstrated approach can be applied in the controlled preparation of ultrathin metal nanowires complementary to lithography and in the production of ultrafine noble-metal nanostructures for catalytic applications.     

Gold surface plasmon crystal structure based‐on polystyrene template for biosensor application

In this communication, we assembled ordered polystyrene (PS) microsphere array as a template with the drop‐coating method, and the oxygen plasma was used to etch the template to adjust the spacing between the PS microspheres. Nano‐triangular gold array and silver nano‐pyramid array were obtained by ion beam sputtering to deposit precious metal gold and silver. We observed the surface morphology of Au and Au/Ag composite films by scanning electron microscope and characterized the films by X‐ray diffraction and ultraviolet/visible light spectrophotometer. The results show that the etching time of oxygen plasma has an obvious effect in adjusting the spacing between PSs and has a significant effect on the morphology of Au structure.     

Gold and silver nanoparticles: a class of chromophores with colors tunable in the range from 400 to 750 nm

This paper presents several solution-phase methods for the large-scale synthesis of metal nanoparticles with controllable compositions (e.g., spherical nanoparticles of gold/silver alloys), morphologies (e.g., nanospheres, triangular nanoplates, circular nanodisks, and nanocubes of silver), and structures (e.g., solid vs. hollow colloids). Spectral measurements indicated that the positions of surface plasmon resonance (SPR) bands for these nanoparticles could be tuned by varying all these parameters. The number of SPR peaks was found to increase as the symmetry of the nanoparticles decreased. In addition to their use as chromophores with strong extinction coefficients, these nanoparticles could serve as a platform to probe binding events of chemical and biochemical species on their surfaces. Gold nanoshells with hollow interiors were, in particular, shown to exhibit a much higher sensitivity to environmental changes than gold solid colloids with roughly the same size.     

Synthesis and properties of silver and gold nanocomposites in poly-1-vinyl-1,2,4-triazole matrix

Novel multifunctional hybrid nanocomposites with silver and gold nanoparticles stabilized by original polymer matrix based on poly-1-vinyl-1,2,4-triazole were synthesized and studied using UV and IR spectroscopy, X-ray diffraction analysis and transmission electron microscopy. The obtained nanocomposites comprise silver or gold nanoparticles of spherical and elliptical shape with size 3–20 nm and 1–10 nm, respectively.     

Electrochemical behaviour of silver and gold single-crystal surfaces covered with a monolayer of adsorbed sulphur

The behaviour of sulphur adsorbed at a silver and gold/electrolyte interface has been studied by a combination of radiotracer and classical electrochemical methods. Sulphur forms stable monolayers on single-crystal silver surfaces in aqueous NaF between ?0.4 and ?1.0 V (MSE). The double-layer capacity is substantially lowered and the pzc shfted. The sulphur can be removed by cathodic treatment, but the silver surface cannot be returned to its original clean condition by this method.     

有机分子CTAB对银纳米颗粒形貌的影响

报道了一种有效调节银纳米颗粒形貌的特殊方法.在不同浓度的CTAB有机分子作用下,片状三角形银纳米颗粒形貌发生改变,形成圆形和纺锤形等特殊形貌的银纳米片,研究了CTAB浓度对银纳米颗粒形貌的影响,从实验结果分析了银纳米颗粒形貌发生改变的主要因素.     

Structures of mixed gold-silver cluster cations (Ag(m)Au(n)+, m+n<6): ion mobility measurements and density-functional calculations

The collision cross sections of Ag(m)Au(n)+ (m+n)<6 cluster ions were determined. For bimetallic clusters, we observe a significant intracluster charge transfer leaving most of the ions positive charge on the silver atoms. The mixed trimeric ions Ag2Au+ and AgAu2+ are triangular like the pure gold and silver trimers. Most of the tetrameric clusters are rhombus shaped, with the exception of Ag3Au+, which has a Y structure with the gold atom in the center. Among the pentamers we find distorted X structures for all systems. For Ag2Au3+ we find an additional isomer which is a trigonal bipyramid. These findings are in line with predictions based on density-functional theory calculations, i.e., all these structures either represent the global minima or are within less than 0.1 eV of the predicted global minimum.     

In situ synthesis of water dispersible bovine serum albumin capped gold and silver nanoparticles and their cytocompatibility studies

A simple and convenient one step room temperature method is described for the synthesis of bovine serum albumin (BSA) capped gold and silver nanoparticles. BSA reduces silver ions to silver nanoparticles but does not directly reduce gold ions to gold nanoparticles at room temperature and varying pH conditions. However, when silver and gold ions are simultaneously added to BSA, silver ions get reduced to metallic silver first and these in turn reduce gold ions to gold nanoparticles through a galvanic exchange reaction. The so synthesized silver and gold nanoparticles are easily water dispersible and can withstand addition of salt even at high concentrations. It is shown that the capped protein retains its secondary structure and the helicity to a large extent on the nanoparticles surface and that the protein capping makes the nanoparticles cytocompatible.     

Shape‐Dependent Catalytic Activity of Silver Nanoparticles for the Oxidation of Styrene

Metal nanoparticles with different shapes have different crystallographic faces. It is therefore of interest to study the effect of the shape of metal nanoparticles on their catalytic activity in various organic and inorganic reactions. Truncated triangular silver nanoplates with well‐defined planes were synthesized by a simple solvothermal approach. The activity of these truncated triangular silver nanoparticles was compared with that of cubic and near‐spherical silver nanoparticles in the oxidation of styrene in colloidal solution. It was found that the crystal faces of silver nanoparticles play an essential role in determining the catalytic oxidation properties. The silver nanocubes had the {100} crystal faces as the basal plane, whereas truncated triangular nanoplates and near‐spherical nanoparticles predominantly exposed the most‐stable {111} crystal faces. As a result, the rate of the reaction over the nanocubes was more than 14 times higher than that on nanoplates and four times higher than that on near‐spherical nanoparticles.     

Surface plasmon mapping of dumbbell-shaped gold nanorods: the effect of silver coating

We report on the identification of surface plasmons in individual gold dumbbell-shaped nanoparticles (AuDBs), as well as AuDBs coated with silver. We use spatially resolved electron energy-loss spectroscopy in a scanning electron microscope, which allows us to map plasmon-energy and intensity spatial distributions. Two dominant plasmon resonances are experimentally resolved in both AuDBs and silver-coated AuDBs. The intensity of these features is peaked either at the tips or at the sides of the nanoparticles. We present boundary element method simulations in good agreement with the experiment, allowing us to elucidate the nature of such modes. While the lower-energy, tip-focused plasmon is of longitudinal character for all dumbbells under consideration, the second side-bound plasmon has a more involved symmetry, starting as a longitudinal quadrupole in homogeneous AuDBs and picking up transversal components when silver coating is added. The longitudinal dipolar mode energy is found to blue-shift upon coating with silver. We find that the substrate produces sizable shifts in the plasmons of silver-coated AuDBs. Our analysis portraits a complex plasmonic scenario in metal nanoparticles coated with silver, including a transition from the original homogeneous gold dumbbell plasmons to the modes of homogeneous silver rods. We believe that these findings can have potential application to plasmon engineering.     

纳米银三角片的光诱导法可控制备及其抗菌活性

采用一种快速高效的光诱导法合成了纳米银三角片,系统地考察了光照时间、柠檬酸钠用量、OH-用量和合成方法对银纳米三角片的合成产率、尖端形貌及其稳定性的影响。研究结果表明,采用光诱导法合成纳米银三角片的最优条件为光照时间3.5 h,反应物物质的量之比n_AgNO3：n_Na3C6H5O7：n_NaBH4=1：10：0.8,OH-浓度0.125 mmol·L^-1,合成出粒径70~80 nm的纳米银三角片,透射电镜和紫外可见分光光度的表征结果表明：光诱导法相对于直接化学还原法制得的纳米银三角片具有较好的微观形态、产率及稳定性。抗菌测试结果表明三角片形态的纳米银比球型颗粒形态的纳米银具有更优异的抗菌性能。     

纳米银三角片的光诱导法可控制备及其抗菌活性

采用一种快速高效的光诱导法合成了纳米银三角片,系统地考察了光照时间、柠檬酸钠用量、OH-用量和合成方法对银纳米三角片的合成产率、尖端形貌及其稳定性的影响。研究结果表明,采用光诱导法合成纳米银三角片的最优条件为光照时间3.5 h,反应物物质的量之比n_(AgNO_3)∶n_(Na_3C_6H_5O_7)∶n_(NaBH_4)=1∶10∶0.8,OH-浓度0.125 mmol·L~(-1),合成出粒径70~80 nm的纳米银三角片,透射电镜和紫外可见分光光度的表征结果表明:光诱导法相对于直接化学还原法制得的纳米银三角片具有较好的微观形态、产率及稳定性。抗菌测试结果表明三角片形态的纳米银比球型颗粒形态的纳米银具有更优异的抗菌性能。     

火试金法测定铅冶炼渣中的金、银含量

建立了铅冶炼渣中的金银含量的测定方法,采用火试金法富集铅冶炼渣中的金、银,铅扣经灰吹后,形成金银合粒,合粒中除有金银外,还残留微量的铅铋杂质,合粒经硝酸分金后,实现金银分离,得到金粒和分金溶液。合粒中杂质保留在分金溶液中,分金溶液经酸处理,采用电感耦合等离子体发射光谱(ICP-OES)法测定其中杂质量和微量的金量。金粒质量补正分金溶液中微量金量即为样品中的金量,合粒质量减去金粒质量和杂质量即为银量。ICP-OES法测定杂质解决了合粒中铅铋残留和分金失误造成微量金进入分金溶液现象。方法精密度较好,加标回收率分别为银98.6%～100%,金96.2%～102%。方法准确、方便、快捷,能很好地满足铅冶炼渣中金、银含量的测定。     

三角形银纳米片的合成及其影响因素

报道了一种在不需光照的条件下制备三角形银纳米片的新方法.在表面活性剂BRIJ35存在下,将硝酸银用硼氢化钠和柠檬酸钠还原,在不同温度范围内反应形成各种尺度的三角形银纳米片,探讨了硼氢化钠浓度、BRIJ35浓度和表面活性剂的种类和溶液pH值等因素对银纳米颗粒形貌和尺寸的影响.     

火试金法测定铅冶炼渣中的金、银含量

建立了铅冶炼渣中的金银含量的测定方法,采用火试金法富集铅冶炼渣中的金、银,铅扣经灰吹后,形成金银合粒,合粒中除有金银外,还残留微量的铅铋杂质,合粒经硝酸分金后,实现金银分离,得到金粒和分金溶液。合粒中杂质保留在分金溶液中,分金溶液经酸处理,采用电感耦合等离子体发射光谱(ICP-OES)法测定其中杂质量和微量的金量。金粒质量补正分金溶液中微量金量即为样品中的金量,合粒质量减去金粒质量和杂质量即为银量。ICP-OES法测定杂质解决了合粒中铅铋残留和分金失误造成微量金进入分金溶液现象。方法精密度较好,加标回收率分别为银98.6%～100%,金96.2%～102%。方法准确、方便、快捷,能很好地满足铅冶炼渣中金、银含量的测定。     

Cyclic Triradicals Composed of Iminonitroxide–Gold(I) with Intramolecular Ferromagnetic Interactions

A triangular gold(iminonitroxide‐2‐ide) trimer complex ( 5 ) was prepared and investigated to determine its magnetic properties. The results showed that the metalloid triradical is highly stable, even in solution under aerated conditions. The intramolecular exchange interaction of 5 was found to be positive (J_intra/k_B≈+29 K), thus showing that 5 is in a quartet ground state. In addition, a silver sandwich complex ( 5 ‐Ag⁺‐ 5 ) was prepared and its electronic and magnetic properties were also clarified.     

Synthesis of silver nanoprisms in formamide

Polygonal (mainly triangular) silver nanoprisms were prepared by reducing silver perchlorate in formamide in the presence of polyethylene glycol (PEG) at room temperature. The reduction of silver ions by formamide leads to the deposition of arrays of triangular shaped silver nanoparticles on the glass walls of the container, accompanied by evolution of CO2 gas. In the presence of poly(N-vinyl-2-pyrrolidone) (PVP) and PEG (1:1), both nanospheres and nanoprisms are formed.