Photochemical synthesis of polygonal gold nanoparticles

In this paper, we propose a method to generate gold nanoparticles capable of absorbing near infrared light (NIR) radiation through a photochemical reaction. This approach does not require the use of either surfactants or polymers, reducing the difficulties that may arise in further chemical modifications for the gold nanoparticles. The gold nanoparticles with either triangular or hexagonal shapes were generated using the photo-reduction method, mixing hydrogen tetrachloroaurate with sodium oxalate, a reducing agent, in aqueous solution under illumination of a mercury lamp (λ_max = 306 nm) for more than 10 min. The size of the gold nanoparticles varies from 25 to 200 nm, which mainly depends on the duration of light illumination and the concentration of sodium oxalate. Furthermore, we demonstrate that the presence of the gold nanoparticles in aqueous solutions can effectively elevate the temperature of the solutions under irradiation of NIR light (808 nm) within a few minutes. The gold nanoparticles can be potentially used as suitable photothermal agents for hyperthermia.     

Optimization of components in high-yield synthesis of block copolymer-mediated gold nanoparticles

The optimization to achieve stable and high-yield gold nanoparticles in block copolymer-mediated synthesis has been examined. Gold nanoparticles are synthesized using block copolymer P85 in gold salt HAuCl₄·3H₂O solution. This method usually has a very limited yield which does not simply increase with the increase in the gold salt concentration. We show that the yield can be enhanced by increasing the block copolymer concentration but is limited to the factor by which the concentration is increased. On the other hand, the presence of an additional reductant (trisodium citrate) in 1:1 molar ratio with gold salt enhances the yield by manyfold. In this case (with additional reductant), the stable and high-yield nanoparticles having size about 14 nm can be synthesized at very low block copolymer concentrations. These nanoparticles thus can be efficiently used for their application such as for adsorption of proteins.     

金催化的硅纳米线的可控制备及光学特性研究

硅纳米线是新型一维半导体纳米材料的典型代表。利用阳极氧化铝薄膜为模版复制出具有有序纳米结构的金膜,在金的催化辅助下对单晶硅进行湿法刻蚀,得到尺寸、形状、分布可控的硅纳米线阵列,并对其光学特性进行了研究。研究结果表明,金代替银作为催化剂,可以有效地抑制二次刻蚀,金的化学性质相对于银更加稳定,克服了银膜在较高的温度或较长刻蚀时间下产生的结构性破坏,得到形貌规整、尺寸可控的硅纳米线阵列。对该阵列在400 nm~1 200 nm波段的反射率、透过率进行了测试,并对比分析了金模板催化与传统方法机理的异同。测试结果表明,相较于传统金属辅助化学刻蚀法,文中提出的金模板催化法制备的硅纳米线阵列尺寸及分布更加均匀可控,在宽光谱范围内的抗反射性得到了显著提高。     

Phyllanthin-assisted biosynthesis of silver and gold nanoparticles: a novel biological approach

Abstract  The anisotropic gold and spherical–quasi-spherical silver nanoparticles (NPs) were synthesized by reducing aqueous chloroauric acid (HAuCl₄) and silver nitrate (AgNO₃) solution with the extract of phyllanthin at room temperature. The rate of reduction of HAuCl₄ is greater than the AgNO₃ at constant amount of phyllanthin extract. The size and shape of the NPs can be controlled by varying the concentration of phyllanthin extract and thereby to tune their optical properties in the near-infrared region of the electromagnetic spectrum. The case of low concentration of extract with HAuCl₄ offers slow reduction rate along with the aid of electron-donating group containing extract leads to formation of hexagonal- or triangular-shaped gold NPs. Transmission electron microscopy (TEM) analysis revealed that the shape changes on the gold NPs from hexagonal to spherical particles with increasing initial concentration of phyllanthin extract. The Fourier transform infrared spectroscopy and thermogravimetric analyses reveal that the interaction between NPs and phyllanthin extract. The cyclic voltammograms of silver and gold NPs confirms the conversion of higher oxidation state to zero oxidation state. Graphical abstract  Anisotropic gold and silver nanoparticles were synthesized by a simple procedure using phyllanthin extract as reducing agent. The rate of bioreduction of AgNO₃ is lower than the HAuCl₄ at constant concentration of phyllanthin extract. The required size of the nanoparticles can be prepared by varying the concentration of phyllanthin with AgNO₃ and HAuCl₄.      

Silver-enhanced conductivity of magnetoplasmonic nanochains

A method for improving the electrical properties of one-dimensional conducting structures by reductive deposition of metallic silver on a gold surface is presented. Fe₃O₄@Au core–shell nanoparticles were used to fabricate conducting magnetoplasmonic nanochains (MPNCs) through magnetic-field-induced assembly. The MPNCs were prepared on a solid substrate. Their dimension was controlled by adjusting the pH of the colloidal solution. The nanochains (NCs) were placed across gold microelectrodes, and additional metal was deposited by highly specific chemical enhancement of the colloidal gold using a silver enhancement solution. Silver-enhanced MPNCs show a remarkable morphology and an impressive enhancement in electrical properties compared to the as-prepared MPNCs.     

Role of ions in the colloidal synthesis of gold nanowires

Gold nanocrystals of different shapes have been made by a wet chemical approach based on a two-step, seed-mediated synthesis. In this paper, we demonstrate a one-step synthetic method for achieving simple and systematic control over the shape of gold nanoparticles. Gold nanowires, which have been prepared by multi-step approaches, are produced in very high yield in this single-step technique. The width of the rods can be varied over a broader range compared to previously reported methods. Rectangle-, cube- or tetrapod-like gold nanocrystals can also be prepared in aqueous solution at room temperature. The formation of various shapes, in the presence of silver nitrate, requires bromide ion and alkylammonium surfactant ion of appropriate hydrocarbon tail length. The shape, dimension and yield of the nanocrystals depend on the nature and concentrations of the stabilizing cationic surfactants and other additives, such as salts, in addition to the reactants.     

Ultrathin silver‐coated gold nanoparticles as suitable substrate for surface‐enhanced Raman scattering

Surface‐enhanced Raman scattering (SERS) is an extremely powerful tool for the analysis of the composition of bimetallic nanoparticle (BNP) surfaces because of the different adsorption schemes adopted by several molecules on different metals, such as Au and Ag. The preparation of BNPs normally implies a change in the plasmonic properties of the core metal. However, for technological applications it could be interesting to synthesize core–shell structures preserving these original plasmonic properties. In this work, we present a facile method for coating colloidal gold nanoparticles (NPs) in solution with a very thin shell of silver. The resulting bimetallic Au@Ag system maintains the optical properties of gold but shows the chemical surface affinity of silver. The effectiveness of the coating method, as well as the progressive silver enrichment of the outermost part of the Au NPs, has been monitored through the SERS spectra of several species (chloride, luteolin, thiophenol and lucigenin), which show different behaviors on gold and silver surfaces. A growth mechanism of the Ag shell is proposed on the basis of the spectroscopic and microscopic data consisting in the formation and deposit of Ag clusters on the Au NP surface. Copyright © 2009 John Wiley & Sons, Ltd.     

钙钛矿薄膜气相制备的晶粒尺寸优化及高效光伏转换

钙钛矿薄膜的气相制备是一种极具潜力的工业化生产工艺,但薄膜的质量控制目前远落后于溶液制备法.本文通过建立PbI_2薄膜向钙钛矿薄膜完全转化过程中反应时间、晶粒尺寸与温度的关系,实现了薄膜的质量优化及大面积钙钛矿薄膜的制备,将薄膜的平均晶粒粒径从0.42μm优化到0.81μm.基于空间电荷限制电流模型对缺陷密度的研究显示,钙钛矿薄膜的缺陷密度由5.90×10~(16)cm~(–3)降低到2.66×10~(16)cm~(–3).光伏器件(FTO/TiO_2/C_(60)/MAPbI_3/spiro-OMeTAD/Au结构)测试显示,面积为0.045cm~2器件的平均光电转换效率从14.00%提升到17.42%,最佳光电转换效率达到17.80%,迟滞因子减小至4.04%.同时,基于180℃制备的1cm~2器件的光电转换效率达到13.17%.     

Surface‐enhanced Raman scattering from polystyrene on gold clusters

Surface‐enhanced Raman scattering (SERS) constitutes a spectroscopic method of rapidly growing importance, and polystyrene is a widely used compound of great industrial importance. In this work, SERS data were obtained from polystyrene samples prepared by vapor deposition of gold and plasma‐induced polymerization of styrene gas. A thorough examination of this data is presented. The relationships between sample preparation parameters, gold‐cluster morphology, and SERS intensity were elucidated. Using Wilson's notation, vibrations were assigned to all bands between 250 and 1750 cm⁻¹ in the ordinary Raman and SERS spectra of polystyrene. The correct assignment of these bands would be a significant achievement because they have been controversial in the literature for ∼30 years. Our assignments were made by reviewing the literature and comparing the assignments found there to spectral data acquired during this study; they were confirmed using density functional theory (DFT) calculations performed on the styrene monomer. The orientation of polystyrene's phenyl ring, relative to the gold surface, was determined. It has been suggested that reactions involving silver catalyze polystyrene degradation during SERS, but we found that silver is not necessary for the degradation to occur. Copyright © 2009 John Wiley & Sons, Ltd.     

Formation of ordered arrays of gold particles by nanoindentation templating

Ordered arrays of gold‐rich particles, with diameters ranging from 50 nm to 180 nm, have been formed on a silicon (100) surface through pre‐patterning by nanoindentation. Indentation and gold deposition of the sample is followed by thermal processing, causing the gold to become trapped at the indentation sites. We suggest that gold trapping is via an alloying process with the underlying Si substrate where the native oxide is structurally compromised by the indentation process. The final size for a given particle is directly dependent on the size of the indentation site. It has also been demonstrated that excess gold found on the surface outside of these indentation sites can be readily removed via simple mechanical abrasion without affecting the particles within the indent. (© 2014 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Direct monitoring of gold nanorod growth

The seed-mediated growth of gold nanorods is shown to be strongly dependent on the reaction time and chemical environment of the reaction solution. The versatile seed-mediated approach in aqueous surfactant solutions has been used in this study for the synthesis of gold nanorods. Changes in the aspect ratio of gold nanorods were reflected in shifts of the plasmon resonance peaks and were monitored using UV-Visible absorption spectroscopy (UV-Vis) to follow the different stages of gold nanorod formation as a function of time and varying amounts of silver ion. Unlike the use of strong reducing agents to make spherical gold nanoparticles, the growth of gold nanorods requires weak reducing conditions, leading to an unknown degree of gold reduction. Therefore, cyclic voltammetry was used to electrochemically interrogate the entire reaction from gold seed to gold nanorod as a function of time. Data obtained revealed that time-dependent gold species are involved in gold nanorod formation.     

An application of the dust grain charging model to determination of secondary electron spectra

Dust grains – objects of different shapes with a size distribution from micro to nanometers – are generally considered as a part of many space as well as laboratory plasmas. Among various dust charging processes, electron-induced secondary emission plays an important role in plasmas containing a noteworthy portion of high-energy electrons. Since a part of secondary electrons has not the energy high enough to overcome the surface potential barrier, the resulting grain charge is determined not only by the secondary emission yield (related to the grain material and size) but also by the secondary electron spectrum. We have developed a model of secondary electron emission from small dust grains. In the present contribution, we discuss the profile of a secondary emission yield that can be received from the model and the measured equilibrium grain charge, both as functions of an incident electron beam energy. A comparison of these quantities leads to an estimation of secondary electron spectra. We have found that: (1) the energy spectrum of secondary electrons does not change with the energy of primary electrons and (2) the energy spectrum depends on the target material being harder for gold and silver than for glass grains.     

Sensitive surface-enhanced Raman scattering substrates based on anti-pyramidal gold architectures decorated with silver nanoparticles

Abstract

A micro-structured gold surface, consisting of a periodic square–based anti–pyramidal array (Klarite) with a smooth boundary surface on which silver nanoparticles (diameter: 60?nm) were deposited, produced an active surface enhanced Raman scattering substrate. With p-aminothiophenol as a probe molecule, the Raman activity of the micro–structured surface was compared before and after deposition of the silver nanoparticles. Experimental results show that the Raman spectra on the silver/p-aminothiophenol/Klarite structure is stronger than that on the silver/p-aminothiophenol/gold film and the Raman spectra on the silver/p-aminothiophenol/gold film is stronger than that on silver/p-aminothiophenol, p-aminothiophenol/Klarite structure, p-aminothiophenol/gold film, which is confirmed by numerical simulations. A similar result is obtained with crystal violet as test molecule.     

Comparing the interparticle coupling effect on sensitivities of silver and gold nanoparticles

The wavelength shift of surface plasmon resonance peak resulting from the electromagnetic coupling noble metal nanoparticle increases with the increase in the dielectric constant of the medium and the decrease in the interparticle separation distance. In this work, the discrete dipole approximation method was used to calculate the extinction efficiency spectra of the silver–silver and gold–gold nanoparticle pairs. This work shows that the silver coupled-particle system has higher plasmon resonance sensitivity as compared to the gold coupled-particle system. However, the silver coupled-particle system has lower and a faster near-exponential decay of sensitivity enhancement factor than the gold coupled-particle system. Thus, the silver coupled-particle may be more suited for sensing applications as compared to the gold coupled-particle, but the interparticle coupling effect displays more pronounced effect on the gold coupled-particle system as compared to the silver coupled-particle system.     

Stabilization of catalytically active gold species in Fe-modified zeolites

The influence of iron additive on redox, electronic and catalytic properties of gold incorporated into zeolite catalysts has been studied by means of TEM, XPS, XRD, TPR, ICP and AES. The interaction of gold with iron modifier was observed in Y-zeolites and mordenites with different cations and method of Fe incorporation (impregnation or ion exchange). This interaction leads to mutual influence on redox properties of Fe and Au ionic species and facilitates their reduction. Limited diffusion of Au precursor after Fe species deposition in narrow mordenite channels does not permit to incorporate Au in adequate concentration, while in large super-cage of Y-zeolites this limitation is absent. The structure of Y-zeolites favors formation of active gold species. Catalytic tests in CO oxidation show that Fe additive stabilizes the gold active species active at low-temperature (partly charged clusters) and makes them insensitive to redox treatments.     

Synthesis of camptothecin-loaded gold nanomaterials

Camptothecin-loaded gold nanomaterials have been synthesized by the sodium borohydride reduction method under a strong basic condition. The obtained gold nanomaterials have been characterized by transmission electron microscopy (TEM), atomic force microscopy (AFM) and UV-vis absorption spectroscopy. The camptothecin-loaded gold colloidal solution was very stable and can be stored for more than two months at room temperature without obvious changes. The color of the colloidal solution can change from wine red to purple and blue during the acidifying process. It was revealed that the release of camptothecin and the aggregation of gold nanoparticles can be controlled by tuning the solution pH. The present study implied that the gold nanomaterials can be used as the potential carrier for CPT delivery.     

A novel method of nanocrystal fabrication based on laser ablation in liquid environment

Metal nanoparticles can be prepared by a novel technique that consists of the laser ablation of a solid target immersed in a water solution of a metal salt. Silicon was chosen as the most adequate target to synthesize silver and gold nanoparticles from a water solution of either AgNO₃ or HAuCl₄. The influence of both the silver nitrate concentrations and the irradiation time of the Si target on the optical properties of the Au and Ag nanoparticles have been investigated. The crystalline nature of the metal nanoparticles has been determined by X-ray diffraction (XRD). Average size and particle size distribution have been measured by means of TEM. The absorbance spectra show the characteristic band of the surface resonant plasmon of silver and gold nanoparticles.     

Acoustic cavitation for engineering of gold sols in silver nitrate solutions

Binary gold-silver nanostructures of preformed gold nanoparticles (25nm) in silver nitrate solutions are produced by a two step sonication (20kHz). Ultrasonic treatment of gold-silver mixtures is carried out in the presence of sodium dodecyl sulfate in water or 2-propanol, and poly(vinyl pyrrolidone) in ethylene glycol solutions. Gold-silver nano-worms, which consist of ripened gold particles connected by ultrasonically reduced silver, are formed after 1h of sonication in the presence of sodium dodecyl sulfate aqueous solution. In 2-propanol bimetallic nano-worms have a well defined core-shell structure. Polygonal alloy nanoparticles with gold as a core material and a silver shell are produced after 180min of sonication in the presence of poly(vinyl pyrrolidone) in ethylene glycol solution. Bimetallic gold-silver nanostructures have defected face centered cubic structure and represent polycrystals with a large number of crystallites randomly oriented. For the first time, the mechanism of gold particle design by ultrasound is examined in detail. The role of additives (sodium dodecyl sulfate, polyvinyl pyrrolidone, ethylene glycol and 2-propanol) as reductants of silver at the gold contact surface or stabilizers of particles is highlighted.     

Surface composition of native gold and Ag/Au alloys

The surface composition of Ag/Au alloys has been studied by X-ray photoelectron spectroscopy (XPS). Surface segregation of Ag is observed, particularly for alloys having low Ag content. The content of Ag in the first surface monolayer is in accordance with data from ion scattering and with a theoretical model for segregation in ordered solutions. The surface of native gold was found to be enriched with silver in the case of mine gold, and the degree of segregation was significantly higher than for an alloy having similar bulk composition. The surface of mine gold taken from an oxidized zone contained less silver than did that of usual mine gold. The surface of placer gold was depleted of silver as compared to the bulk. These data show the surface composition of native gold to differ markedly from that of an alloy having the same bulk Ag content, and to depend on the genesis of the native gold sample.     

Peptide-induced patterning of gold nanoparticle thin films

In this work, the use of patterned proteins and peptides for the deposition of gold nanoparticles on several substrates with different surface chemistries is presented. The patterned biomolecule on the surface acts as a catalyst to precipitate gold nanoparticles from a precursor solution of HAuCl₄ onto the substrate. The peptide patterning on the surfaces was accomplished by physical adsorption or covalent attachment. It was shown that by using covalent attachment with a linker molecule, the influence of the surface properties from the different substrates on the biomolecule adsorption and subsequent nanoparticle deposition could be avoided. By adjusting the reaction conditions such as pH or HAuCl₄ concentration, the sizes and morphologies of deposited gold nanoparticle agglomerates could be controlled. Two biomolecules were used for this experiment, 3XFLAG peptide and bovine serum albumin (BSA). A micro-transfer molding technique was used to pattern the peptides on the substrates, in which a pre-patterned poly(dimethylsiloxane) (PDMS) mold was used to deposit a lift-off pattern of polypropylmethacrylate (PPMA) on the various substrates. The proteins were either physically adsorbed or covalently attached to the substrates, and an aqueous HAuCl₄ solution was applied on the substrates with the protein micropatterns, causing the precipitation of gold nanoparticles onto the patterns. SEM, AFM, and Electron Beam Induced Current (EBIC) were used for characterization.