Photo-formation of gold nanoparticles: photoacoustic studies on solid monoliths of Au(III)-chitosan-silica aerogels

Photo-formation of gold nanoparticles in the solid monoliths of Au(III)-chitosan-silica aerogels with different Au/NH(2) molar ratios has been investigated using photoacoustic spectroscopy. Upon exposing to 320 nm UV light, a new absorption feature in the visible region around 525 nm could be seen due to the surface plasmon resonance of gold particles that are generated as a result of UV-induced reduction of Au(III) to Au(0). The plasmon band becomes stronger and shows saturation effects upon increasing the UV exposure time. A blue shift of about 7 nm is also noticed on exposing the sample (Au/NH(2)=1/5) for 6h, indicating a slight decrease in the nanoparticle size due to light-induced annealing with increasing the UV exposure time. The PA signals monitored as a function of chopping frequency show omega(-1) dependence, implying the thermally thin character of Au(III)-chitosan-silica aerogels.     

Facile synthesis of gold nanoparticles with narrow size distribution by using AuCl or AuBr as the precursor

Gold(I) halides, including AuCl and AuBr, were employed for the first time as precursors in the synthesis of Au nanoparticles. The synthesis was accomplished by dissolving Au(I) halides in chloroform in the presence of alkylamines, followed by decomposition at 60 degrees C. The relative low stability of the Au(I) halides and there derivatives eliminated the need for a reducing agent, which is usually required for Au(III)-based precursors to generate Au nanoparticles. Controlled growth of Au nanoparticles with a narrow size distribution was achieved when AuCl and oleylamine were used for the synthesis. FTIR and mass spectra revealed that a complex, [AuCl(oleylamine)], was formed through coordination between oleylamine and AuCl. Thermolysis of the complex in chloroform led to the formation of dioleylamine and Au nanoparticles. When oleylamine was replaced with octadecylamine, much larger nanoparticles were obtained due to the lower stability of [AuCl(octadecylamine)] complex relative to [AuCl(oleylamine)]. Au nanoparticles can also be prepared from AuBr through thermolysis of the [AuBr(oleylamine)] complex. Due to the oxidative etching effect caused by Br(-), the nanoparticles obtained from AuBr exhibited an aspect ratio of 1.28, in contrast to 1.0 for the particles made from AuCl. Compared to the existing methods for preparing Au nanoparticles through the reduction of Au(III) compounds, this new approach based on Au(I) halides offers great flexibility in terms of size control.     

Direct deposition of gold nanoparticles onto polymer beads and glucose oxidation with H2O2

Gold nanoparticles (Au NPs) were deposited directly from aqueous solution of diethylenediaminegold(III) complex onto polymer beads commercially available, such as poly(methyl methacrylate) (PMMA), polystyrene (PS), and polyaniline (PANI) without surface modification. The dropwise addition of NaBH4 to reduce Au(III) was found to be very effective to obtain small Au0 NPs with a narrow size distribution except for PANI. The catalytic performance of Au NPs deposited on polymer beads for H2O2 decomposition and glucose oxidation with H2O2 were more significantly affected by the kinds of polymer supports than by the size of Au NPs. The equimolar oxidation of glucose with H2O2 could be operated by controlling the decomposition rate of H2O2 over Au/PMMA.     

Pyrene-assisted synthesis of size-controlled gold nanoparticles in sodium dodecyl sulfate micelles

Gold nanoparticles prepared by chemical reduction in sodium dodecyl sulfate (SDS) solution are size-controlled with the addition of pyrene. Micellar electrokinetic capillary chromatography (MEKC) is applied to the system to examine the size and polydispersity of gold nanoparticles and to show that pyrene has the extraordinary effect in decreasing the size and narrowing the dispersity of gold nanoparticles. The MEKC electropherograms further suggest that pyrene could be oxidized by the aqueous Au(III) complexes first. All the reduced Au complexes were then solubilized in the pyrene-SDS micelles. The growth of gold nanoparticles beyond the embryonic stage was subsequently inhibited by the encapsulating SDS and electrophilic pyrene.     

Photoinduced dissolution and redeposition of Au nanoparticles supported on TiO2

Au particles (mean size ca. 3 nm) supported on TiO(2) particles were irradiated by UV light (>300 nm) in aqueous solutions at 278 K. Photo-induced dissolution of Au nanoparticles followed by redeposition occurred in aqueous solutions containing halogen ions. The dissolution of Au nanoparticles yielded a Au(III) complex with a halogen ion; subsequent reduction of the Au(III) complex caused precipitation of larger Au particles on TiO(2).     

Sonochemical Processes and Formation of Gold Nanoparticles within Pores of Mesoporous Silica

Mesoporous silica with gold nanoparticles inside its pores was prepared by the soaking and ultrasound-induced reduction method. This new composite was characterized by X-ray diffraction (XRD), Brunauer-Emmett-Teller (BET), and high-resolution transmission electron microscopy (HRTEM) techniques. The results showed that nearly spherical-shaped gold nanoparticles, with mean size in diameter of 5.2 nm, are located in the pores, most of which are less than 6 nm in diameter. The ultrasonic irradiation time dependence of optical absorption for the soaked porous solid sample, as suggested by the variation in absorbance at 310 and 544 nm, indicated the reduction of Au (III) ions, and the nucleation and aggregation of gold nanoparticles within pores of mesoporous silica. Additionally, the reaction rates estimated phenomenologically by the absorbance decay at 310 nm for both the porous sample and the corresponding soaking solution presented the enhancement of the sonochemical reduction rate of Au (III) ions within pores of mesoporous silica. It is assumed that the extensive liquid-solid interfacial zones in the pores, due to the high specific surface areas and great porosity of the mesoporous solid, are the major regions where the efficient sonochemical reduction induced by the cavitation takes place. Copyright 2001 Academic Press.     

Voltammetric monitoring of gold nanoparticle formation facilitated by glycyl-L-tyrosine: relation to electronic spectra and transmission electron microscopy images

Voltammetric techniques have been introduced to monitor the formation of gold nanoparticles produced via the reaction of the amino acid glycyl-L-tyrosine with Au(III) (bromoaurate) in 0.05 M KOH conditions. The alkaline conditions facilitate amino acid binding to Au(III), inhibit the rate of reduction to Au(0), and provide an excellent supporting electrolyte for voltammetric studies. Data obtained revealed that a range of time-dependent gold solution species are involved in gold nanoparticle formation and that the order in which reagents are mixed is critical to the outcome. Concomitantly with voltammetric measurements, the properties of gold nanoparticles formed are probed by examination of electronic spectra in order to understand how the solution environment present during nanoparticle growth affects the final distribution of the nanoparticles. Images obtained by the ex situ transmission electron microscopy (TEM) technique enable the physical properties of the nanoparticles isolated in the solid state to be assessed. Use of this combination of in situ and ex situ techniques provides a versatile framework for elucidating the details of nanoparticle formation.     

Hybrid gold-nanoparticle-cored conjugated thiophene dendrimers: synthesis, characterization, and energy-transfer studies

A series of hybrid Au-nanoparticle-dendrimer materials: nanoparticle-cored thiophene dendrimers (NCTDs) were synthesized, characterized, and investigated for their energy-transfer properties. These hybrid nanoparticles were obtained by the simultaneous and in situ reduction of gold(III) chloride and self-assembly of the thiol-containing thiophene dendritic ligands. The dendron ligands were radially attached to the gold nanoparticles and were analyzed by TEM, UV/Vis, (1)H NMR, and FTIR spectroscopies. The solution fluorescence of the attached thiophene dendrons are quenched progressively. Both alkyl-chain length and dendron size have significant influence on the energy-transfer efficiency, as well as on core sizes and size distribution of the Au nanoparticles. In spite of the phenomenon's dependence on nanoparticle size, the energy transfer generally follows the 1/d(2) distance dependence. Single NCTD nanoparticles were also adsorbed on highly ordered pyrolytic graphite (HOPG) and uniform aggregates were observed on mica flat substrates.     

DNA-templated preparation of gold nanoparticles

DNA-mediated gold nanoparticles were prepared by chemical reduction of DNA-Au(III) complex. The DNA-Au(III) was first formed by reacting DNA with HAuCl? at a pH of 5.6. The complex in solution was reacted with hydrazine reducing Au(III) to Au. The reduced Au formed nanodimensional aggregates. The particle distributions were obtained by scanning electron microscopy (SEM) and transmission electron microscopy (TEM). This method resulted in a rather uniform dispersion of Au nanoparticles of near-spherical shape and 45~80 nm in diameter. Gold nanoparticles were embedded and stabilized by DNA.     

Formation of gold and silver nanostructures within polyvinylpyrollidone (PVP) gel

Study on reduction of Au(III) and Ag(I) and the formation of Au and Ag nanostructures was performed on the gels of metal precursor and PVP polymer mixture. Some comparing samples were prepared for better understanding the role of reactants on the reduction of metal ions and further growth of nanocrystals. The results suggest that, in addition to its function of generating stable colloids, PVP not only has a reducing effect on metal ions, but also acts as a crystal growth modifier. At low temperatures, the reducing effect of PVP is strong on Ag(I) ions in AgNO₃, while the reduction of complex Au(III) ions in HAuCl₄ is slow, involving two steps of Au(III)→Au(I)→Au. In the study of temperature disturbance on crystal growth, Au nanoplates of new and well-defined star shape were observed. The differences in the size and shape of nanoparticles are discussed from the colloid chemistry.     

Platinum-catalyzed synthesis of water-soluble gold-platinum nanoparticles

The ability to control composition and size in the synthesis of bimetallic nanoparticles is important for the exploitation of the bimetallic catalytic properties. This paper reports findings of an investigation of a new approach to the synthesis of gold-platinum (AuPt) bimetallic nanoparticles in aqueous solution via one-phase reduction of AuCl(4-) and PtCl(4)(2-) using a combination of reducing and capping agents. Hydrogen served as a reducing agent for the reduction of Pt(II), whereas acrylate was used as a reducing agent for the reduction of Au(III). The latter reaction was found to be catalyzed by the formation of Pt as a result of the reduction of Pt(II). Acrylate also functioned as capping agent on the resulting nanocrystals. By controlling the feed ratios of AuCl(4-) and PtCl(4)(2-) and the relative concentrations of acrylate, an effective route for the preparation of AuPt nanoparticles with bimetallic compositions ranging from approximately 4 to 90% Au and particle sizes ranging from 2 to 8 nm has been demonstrated. The composition, size, and shell properties were characterized using transmission electron microscopy, direct current plasma-atomic emission spectroscopy, Fourier transform infrared spectroscopy, and X-ray diffraction. Implications of the results to the exploration of bifunctional catalysts are also briefly discussed.     

Nucleation and growth of gold nanoparticles on adsorption layers and in ultrathin films of poly(2-vinylpyridine)

Peculiarities of the nucleation and growth of gold nanoparticles on adsorption layers and in ultrathin films of poly(2-vinylpyridine) (PVP) in the chemical reduction of sorbed Au(III) ions and the consequent thermal treatment of systems are studied by X-ray photoelectron spectroscopy and optical spectroscopy. It is shown that nitrogens of PVP pyridine groups coordinate gold atoms. It is revealed that, even at relatively short contact between PVP film saturated with chloroauric acid and the solution of strong reductant NaBH₄, Au(III) ions are reduced to metal. As a result, quasi-metal gold particles are formed. At the same time, when exposing a PVP-Au system to the solution of weak reductant NH₂OH, the process of reduction proceeds in several stages. First, Au(III) ions are reduced to Au(I) followed by the reduction to Au(0) as a result of disproportionation reaction. It is demonstrated for the first time that, upon using NH₂OH, the rate of reduction, as well as the structure of prepared PVP-Au nanocomposite films depends to substantial extent on solution pH. Prolonged annealing of ultrathin nanocomposites at 150 °C, i.e., above the glass transition temperature of polymer matrix, leads to an increase in the sizes of metal particles and the formation of systems characterized by intense absorption within the 500–600-nm range due to the localized plasmon resonance of gold nanoparticles.     

金核银壳纳米粒子薄膜的制备及SERS活性研究

采用柠檬酸化学还原法制备金溶胶, 通过自组装技术在石英片表面制备金纳米粒子薄膜, 在银增强剂混合溶液中反应获得金核银壳纳米粒子薄膜. 用紫外-可见吸收光谱仪和原子力显微镜(AFM)研究了不同条件下制备的金核银壳纳米粒子薄膜的光谱特性和表面形貌, 并以结晶紫为探针分子测量了金核银壳纳米粒子薄膜的表面增强拉曼光谱(SERS). 结果表明, 金纳米粒子薄膜的分布、银增强剂反应时间的长短对金核银壳纳米粒子薄膜的形成均有重要影响. 制备过程中, 可以通过控制反应条件获得一定粒径的、具有良好表面增强拉曼散射活性的金核银壳纳米粒子薄膜.     

Preparation of Au/TiO2 nanocomposites and their catalytic activity for DPPH radical scavenging reaction

Au/TiO2 nanocomposites have been prepared by UV photolysis or chemical reduction of a Au(III) complex formed on a spherical or a rodlike TiO2 support, and their catalytic activity for 1,1-diphenyl-2-picrylhydrazyl (DPPH) radical scavenging reaction was investigated. The chemical reduction with dimethylamine borane (DMAB) provided smaller gold nanoparticles than those synthesized by UV photolysis. Type of the TiO2 also affected the size of gold particles; smaller gold particles were deposited on the spherical TiO2 support than on rodlike one. For the radical scavenging reaction, the Au/TiO2 nanocomposites prepared by chemical reduction exhibited a higher catalytic activity than those photochemically prepared, and rodlike TiO2 provided a higher activity than spherical one. The effects of preparation methods and type of TiO2 supports on the catalytic activity are discussed.     

Biogenic synthesis of Ag, Au and bimetallic Au/Ag alloy nanoparticles using aqueous extract of mahogany (Swietenia mahogani JACQ.) leaves

In this paper, we have demonstrated for the first time, the superb efficiency of aqueous extract of dried leaves of mahogany (Swietenia mahogani JACQ.) in the rapid synthesis of stable monometallic Au and Ag nanoparticles and also Au/Ag bimetallic alloy nanoparticles having spectacular morphologies. Our method was clean, nontoxic and environment friendly. When exposed to aqueous mahogany leaf extract, competitive reduction of Au(III) and Ag(I) ions present simultaneously in same solution leads to the production of bimetallic Au/Ag alloy nanoparticles. UV-visible spectroscopy was used to monitor the kinetics of nanoparticles formation. UV-visible spectroscopic data and TEM images revealed the formation of bimetallic Au/Ag alloy nanoparticles. Mahogany leaf extract contains various polyhydroxy limonoids which are responsible for the reduction of Au(III) and Ag(I) ions leading to the formation and stabilization of Au and Ag nanopaticles.     

Bimetallic (Ag)Au nanoparticles prepared by the seed growth method: two-dimensional assembling, characterization by energy dispersive X-ray analysis, X-ray photoelectron spectroscopy, and surface enhanced raman spectroscopy, and proposed mechanism of growth

Layered core-shell bimetallic silver-gold nanoparticles were prepared by overdeposition of Au over Ag seeds by the seed-growth method using tetrachloroauric acid, with hydroxylamine hydrochloride as the reductant. The effects of pH, reduction rate, and seeding conditions on the morphology and surface plasmon extinction of the bimetallic nanoparticles were investigated. Nanoparticles prepared by a rapid reduction in the neutral ambient and assembled into two-dimensional nanoparticulate films by adsorption of 2,2'-bipyridine were characterized by energy-dispersive X-ray analysis, X-ray photoelectron spectroscopy, surface-enhanced Raman scattering spectroscopy, and transmission electron microscopy. The results are consistent with Ag core and Ag/Au-alloyed shell composition of the nanoparticles. Evidence of the presence of Ag on the surface of the nanoparticles, of enrichment of the Ag/Au alloy shell by Ag toward or at the nanoparticle surface, and of modification of the nanoparticle surface by adsorbed chlorides is also provided. Reduction of the size of the Ag seeds, alloying of Ag and Au in the shell of the nanoparticles, and modification of their surfaces by adsorbed chlorides are tentatively attributed to positive charging of the nanoparticles during the electrocatalytic overdeposition of Au over Ag seeds.     

Microstructured Au/TiO2 model catalyst systems

The preparation of microstructured Au/TiO2 model catalysts as a first step toward micrometer-scale parallel studies on model catalysts and toward studies of mesoscopic effects in catalytic reactions was investigated by atomic force microscopy and X-ray photoelectron spectroscopy. The model systems, which consist of micrometer-size active areas covered with Au nanoparticles that are separated by similarly sized inactive areas free of Au particles, are fabricated by combining optical lithography methods for microstructuring and ultrahigh vacuum evaporation for Au nanoparticle deposition and by applying suitable cleaning steps. It is demonstrated that practically perfect microstructures with Au nanoparticles of catalytically relevant sizes (2-3-nm diameter) on a clean TiO2 substrate can be produced this way and that the processing steps do not affect the deposited Au nanoparticles, neither in size nor in lateral distribution.     

Electronic and chemical properties of supported Au nanoparticles

Oxidation and reduction behaviors of Au nanoparticles with different sizes on highly ordered pyrolytic graphite (HOPG) and silica were studied using X-ray photoelectron spectroscopy (XPS). For Au nanoparticles smaller than 6 nm in diameter, we found a novel oxygen species formed in Au nanoparticles, which is absent in larger particles and Au bulk crystals. This new oxygen species is attributed to the subsurface oxygen: for a complete understanding of the structures of catalytically active Au, the new oxygen species should be taken into account. In this context, it is worth mentioning that the subsurface oxygen species has been suggested to play an important role in heterogeneous catalysis. With decreasing Au particle size, a positive core level shift can be observed, which can be mostly attributed to the final state effects. Increase of the number of undercoordinated atoms with decreasing particle size is evidenced by a reduced splitting between 5d_3/2 and 5d_5/2 states and a band narrowing. Our results on electronic structures of Au nanoparticles on silica are compared to those on other substrates such as zirconia and titania to shed light onto the metal-support interactions.     

乳液聚合法制备纳米金/聚苯乙烯复合粒子

以氯金酸为前驱体,十二烷基硫醇和硼氢化钠分别作为稳定剂和还原剂,采用相转移法制备了单分散的金纳米粒子.将金纳米粒子通过乳液聚合的方法制备了纳米金/聚苯乙烯复合粒子.通过紫外-可见吸收光谱(UV-Vis)研究了纳米金和纳米金/聚苯乙烯复合粒子的光吸收特性,使用傅立叶变换红外光谱(FT-IR)、X射线衍射(XRD)、透射电子显微镜(TEM)和动态光散射(DLS)对产物的组成、晶体结构、形貌、以及粒径进行了表征.结果表明,复合粒子为粒径分布较窄的球形,其中的金纳米粒子为面心立方结构.热失重分析(TGA)说明制备的纳米金/聚苯乙烯复合粒子具有很好的热稳定性.     

Functionalized gold nanoparticles as phosphorescent nanomaterials and sensors

Ligand-capped gold nanoparticles were synthesized by capping monothiol derivatives of 2,2'-dipyridyl onto the surface of Au nanoparticles (Au-BT). The average size of the metal core is around 4 nm, with a shell of approximately 340 bipyridine ligands around the Au nanoparticle. The high local concentration of the chelating ligands ( approximately 5 M) around the Au nanoparticle makes these particles excellent ion sponges, and their complexation with Eu(III)/Tb(III) ions yields phosphorescent nanomaterials. Absorption spectral studies confirm a 1:3 complexation between Eu(III)/Tb(III) ions and bipyridines, functionalized on the surface of Au nanoparticles. The red-emitting Au-BT:Eu(III) complex exhibits a long lifetime of 0.36 ms with six line-like emission peaks, whereas the green-emitting Au-BT:Tb(III) complex exhibits a lifetime of 0.7 ms with four line-like emission peaks. These phosphorescent nanomaterials, designed by linking BT:Eu(III) complexes to Au nanoparticles, were further utilized as sensors for metal cations. A dramatic decrease in the luminescence was observed upon addition of alkaline earth metal ions (Ca(2+), Mg(2+)) and transition metal ions (Cu(2+), Zn(2+), Ni(2+)), resulting from an isomorphous substitution of Eu(III) ions, whereas the luminescence intensity was not influenced by the addition of Na(+) and K(+) ions. Direct interaction of bipyridine-capped Au nanoparticles with Cu(2+) ions brings the nanohybrid systems closer, leading to the formation of three-dimensional superstructures. Strong interparticle plasmon interactions were observed in these closely spaced Au nanoparticles.