Photochemical formation of silver and gold nanostructures at the air-water interface and their electrocatalytic properties

In this paper, we report a simple method of fabricating silver and gold nanostructures at the air - water interface, which can be spontaneously assembled through the reduction of AgNO3 and HAuCl4 with ultraviolet (UV) irradiation in the presence of polyacrylic acid (PAA), respectively. It was found that the building blocks in the silver nanostructure are mainly interwoven silver nanofilaments, while those of the gold nanostructure are mainly different sizes of gold nanoparticles and some truncated gold nanoplates, and even coalescence into networks. At the air - water interface, these silver and gold nanostructures can be easily transferred onto the surface of indium tin oxide (ITO) slides and used for electrochemical measurements. After a replacement reaction with H2PdCl4, the silver nanostructure is transformed into a Ag - Pd bimetallic nanostructure, with good electrocatalytic activity for O-2 reduction. The gold nanostructure can also show high electrocatalytic activity to the oxidation of nitric oxide (NO) with a detection limit of about 10 mu M NaNO2 at S/N = 3.

Plasmonic gold nanostructures: optical properties and application in mercury detection

This thesis investigates the application of plasmonic gold nanostructures for mercury detection. Various gold and silver single nanostructures and gold nanostructure assemblies were characterised in detail by correlated single nanostructure spectroscopy and electron microscopy. Several routes for mercury detection were explored: plasmon resonance energy transfer (PRET) upon Hg2+ binding to immobilised gold nanoparticle-organic ligand hybrid structures and amalgamation of single immobilised gold nanorods upon chemical and upon electrochemical reduction of Hg2+ ions. The amalgamation approach showed large potential with extraordinary shifts of the nanorods’ scattering spectra upon exposure to reduced mercury; a result of compositional and morphological change induced in the nanorod by amalgamation with mercury. A shift of 5 nm could be recorded for a concentration as low 10 nM Hg2+. Through detailed time-dependent experiments insights into the amalgamation mechanism were gained and a model comprising 5 steps was developed. Finally, spectroelectrochemistry proved to be an excellent way to study in real time in-situ the amalgamation of mercury with gold nanorods paving the way for future work in this field.

Molecular recognition of 2,4,6-trinitrotoluene by 6-aminohexanethiol and surface-enhanced Raman scattering sensor

2,4,6-trinitrotoluene (TNT) is one of the most commonly used nitro aromatic explosives in landmine, military and mining industry. This article demonstrates rapid and selective identification of TNT by surface-enhanced Raman spectroscopy (SERS) using 6-aminohexanethiol (AHT) as a new recognition molecule. First, Meisenheimer complex formation between AHT and TNT is confirmed by the development of pink colour and appearance of new band around 500 nm in UV-visible spectrum. Solution Raman spectroscopy study also supported the AHT:TNT complex formation by demonstrating changes in the vibrational stretching of AHT molecule between 2800-3000 cm−1. For surface enhanced Raman spectroscopy analysis, a self-assembled monolayer (SAM) of AHT is formed over the gold nanostructure (AuNS) SERS substrate in order to selectively capture TNT onto the surface. Electrochemical desorption and X-ray photoelectron studies are performed over AHT SAM modified surface to examine the presence of free amine groups with appropriate orientation for complex formation. Further, AHT and butanethiol (BT) mixed monolayer system is explored to improve the AHT:TNT complex formation efficiency. Using a 9:1 AHT:BT mixed monolayer, a very low detection limit (LOD) of 100 fM TNT was realized. The new method delivers high selectivity towards TNT over 2,4 DNT and picric acid. Finally, real sample analysis is demonstrated by the extraction and SERS detection of 302 pM of TNT from spiked.

Using Polycarbonate Membranes as Templates for the Preparation of Au Nanostructures for Surface-Enhanced Raman Scattering

Polycarbonate membranes (PCM) of various pores sizes (400, 200, 100 and 50 nm) were used as templates for gold deposition. The electrodeposition from gold ions resulted in the formation of gold nanotubes when large pores size PCMs (400 and 200 nm) were used. On the other hand, gold nanowires were predominant for the PCMs with smaller pores size (100 and 50 nm). Surface-enhanced Raman scattering (SERS) from the probe molecule 4-mercaptopyridine (4-MPy) was obtained from all these nanostructures. The SERS efficiency of the substrates produced using the PC M templates were compared to two commonly used SERS platforms: a roughened gold electrode and gold nanostructures electrodeposited through organized polystyrene spheres (PSS). The SERS signal of the probe molecule increased as the pore diameter of the PCM template decreased. Moreover, the SERS efficiency from the nanostructures produced using 50 nm PCM templates was four and two times better than the signal from the roughened gold electrode and the PSS template, respectively. The SERS substrates prepared using PCM templates were more homogenous over a larger area (ca. 1 cm(2)), presented better spatial and sample to sample reproducibility than the other substrates. These results show that SERS substrates prepared using PCM templates are promising for the fabrication of planar SERS platforms for analytical/bioanalytical applications.

Application of Ru(bpy)(3)(2+) in control and formation of gold surface nanostructure through oxidation-reduction cycling

It was studied that the nanostructure formed on a gold surface via a simple oxidation-reduction cycles (ORC) in 0.1 M KCl containing Ru(bpy)(3)(2+) with different concentrations. Atomic force microscopy (AFM) and energy-dispersed spectroscopy (EDS) were used to characterize the nanostructure formed on the gold surface. Sweep-step voltammetry and corresponding electroluminescence (ECL) response, in situ electrochemical quartz crystal microbalance (EQCM) measurement were used to monitor the ORC. procedure. It was found that the surface structure became more uniform in the presence of Ru(bpy)(3)(2+), and the surface roughness was decreasing with the increasing of Ru(bpY)(3)(2+) concentration, suggesting a simple and effective method to control the formation of nanostructure on the gold surface.

Premonolayer oxidation of nanostructured gold : an important factor influencing electrocatalytic activity

The study of the electrodeposition of polycrystalline gold in aqueous solution is important from the viewpoint that in electrocatalysis applications ill-defined micro- and nanostructured surfaces are often employed. In this work, the morphology of gold was controlled by the electrodeposition potential and the introduction of Pb(CH3COO)2•3H2O into the plating solution to give either smooth or nanostructured gold crystallites or large dendritic structures which have been characterized by scanning electron microscopy (SEM). The latter structures were achieved through a novel in situ galvanic replacement of lead with AuCl4−(aq) during the course of gold electrodeposition. The electrochemical behavior of electrodeposited gold in the double layer region was studied in acidic and alkaline media and related to electrocatalytic performance for the oxidation of hydrogen peroxide and methanol. It was found that electrodeposited gold is a significantly better electrocatalyst than a polished gold electrode; however, performance is highly dependent on the chosen deposition parameters. The fabrication of a deposit with highly active surface states, comparable to those achieved at severely disrupted metal surfaces through thermal and electrochemical methods, does not result in the most effective electrocatalyst. This is due to significant premonolayer oxidation that occurs in the double layer region of the electrodeposited gold. In particular, in alkaline solution, where gold usually shows the most electrocatalytic activity, these active surface states may be overoxidized and inhibit the electrocatalytic reaction. However, the activity and morphology of an electrodeposited film can be tailored whereby electrodeposited gold that exhibits nanostructure within the crystallites on the surface demonstrated enhanced electrocatalytic activity compared to smaller smooth gold crystallites and larger dendritic structures in potential regions well within the double layer region.

An acoustically enhanced gold film Raman sensor on a lithium niobate substrate

The surface enhanced Raman scattering effect has shown immense potential for detecting trace amounts of explosive vapor molecules. To date, efforts to produce a commercially available, reliable SERS sensor have been impeded by an inability to separate the electromagnetic enhancement produced by the metallic nanostructure from other signal enhancing effects. Here, we show a new Raman sensor that uses surface acoustic waves (SAWs) to produce controllable surface structures on gold films deposited on LiNbO3 substrates that modulate the Raman signal of a target compound (thiophenol) adsorbed on the films. We demonstrate that this sensor can dynamically control the Raman signal simply by changing the SAW’s amplitude, allowing the Raman signal enhancement factor to be directly measured with no variation in the concentration of the target compound. The physically adsorbed molecules can be removed from the sensor without physical cleaning or damage, making it possible to reuse it for real-time Raman detection.

Large-Scale and Template-Free Growth of Free-Standing Single-Crystalline Dendritic Ag/Pd Alloy Nanostructure Arrays

Large-scale arrays consist of dendritic single-crystalline Ag/Pd alloy nanostructures are synthesized for the first time. A simple galvanic replacement reaction is introduced to grow these arrays directly on Ag substrates. The morphology of the products strongly depended on the reaction temperature and the concentration of H2PdCl4 solution. The mechanism of the formation of alloy and the dendritic morphology has been discussed. These alloy arrays exhibit high surface-enhanced Raman scattering (SERS) activity and may have potential applications in investigation of "in situ" Pd catalytic reactions using SERS. Moreover, electrocatalytic measurements suggest that the obtained dendritic Ag/Pd alloy nanostructures exhibit electrocatytic activity toward the oxidation of formic acid.

Type I collagen-mediated synthesis and assembly of UV-photoreduced gold nanoparticles and their application in surface-enhanced Raman scattering

We reported a simple method to synthesize gold nanoparticles (NPs) by photoreducing HAuCl4 in acetic acid solution in the presence of type I collagen. It was found that the collagen takes an important role in the formation of gold NPs. The introduction of collagen made the shape of the synthesized gold nanocrystals change from triangular and hexangular gold nanoplates to size-uniform NPs. On the other hand, thanks to the special characters of collagen molecules, such as its linear nanostructure, are positively charged when the pH < 7, and the excellent self-assembly ability, photoreduced gold NPs were assembled onto the collagen chains and formed gold NPs films and networks. A typical probe molecule, 4-aminothiophenol, was used to test the surface-enhanced Raman scattering activity of these gold NPs films and networks and the results indicated good Raman activity on these substrates.

A method for cathodic polymerization of aniline by in situ electrogenerated intermediate at gold surface

Polyaniline (PANI) was cathodically synthesized at an evaporated gold electrode using an in situ electrogenerated intermediate as oxidant during reduction of the dissolved oxygen. The obtained PANI layer showed an electrochemical response similar to that synthesized by the conventionally anodic polymerization, and the average rate for the growth of PANI layer at polycrystalline gold electrode was 1.59 nm h(-1), while that at the Au (111) electrode was 4.93 nm h(-1). Based on these results, the thickness of the resulted layer can be easily controlled at molecular level for potential nanodevice applications. The obtained PANI layer showed morphology from an island-like nanostructure to an ultrathin film, depending on the crystal orientation of the electrode used.

Unique structure and photoluminescence of Au/CdTe nanostructure materials

Unique nanostructure materials with highly ordered spherical aggregates have been obtained by self-organization of single CdTe nanocrystals using gold nanoparticles as seeds, and a red shift of the photoluminescence peak was observed.

Templated assembly of gold nanoparticles into microscale tubules and their application in surface-enhanced Raman scattering

We report a simple procedure to assemble gold nanoparticles into hollow tubular morphology with micrometer scale, wherein the citrate molecule is used not only as a reducing and capping agent, but also as an assembling template. The nanostructure and growth mechanism of microtubes are explored via SEM, TEM, FTIR spectra, and UV-vis spectra studies. The incorporation of larger gold nanoparticles by electroless plating results in an increase in the diameter of microtubes from 900 nm to about 1.2 mu m. The application of the microtubes before and after electroless plating in surface-enhanced Raman scattering (SERS) is investigated by using 4-aminothiophenol (4-ATP) as probe molecules. The results indicate that the microtubes both before and after electroless plating can be used as SERS substrates. The microtubes after electroless plating exhibit excellent enhancement ability.

Surface-enhanced Raman scattering of silver-gold bimetallic nanostructures with hollow interiors

Surface-enhanced Raman scattering (SERS) activity of silver-gold bimetallic nanostructures (a mean diameter of similar to 100 nm) with hollow interiors was checked using p-aminothiophenol (p-ATP) as a probe molecule at both visible light (514.5 nm) and near-infrared (1064 nm) excitation. Evident Raman peaks of p-ATP were clearly observed, indicating the enhancement Raman scattering activity of the hollow nanostructure to p-ATP. The enhancement factors (EF) at the hollow nanostructures were obtained to be as large as (0.8 +/- 0.3)x10(6) and (2.7 +/- 0.5)x10(8) for 7a and 19b (b(2)) vibration mode, respectively, which was 30-40 times larger than that at silver nanoparticles with solid interiors at 514.5 nm excitation. EF values were also obtained at 1064 nm excitation for 7a and b(2)-type vibration mode, which were estimated to be as large as (1.0 +/- 0.3)x10(6) and (0.9 +/- 0.2)x10(7), respectively. The additional EF values by a factor of similar to 10 for b(2)-type band were assumed to be due to the chemical effect. Large electromagnetic EF values were presumed to derive from a strong localized plasmas electromagnetic field existed at the hollow nanostructures.

Controlled synthesis of 2D Au nanostructure assembly with the assistance of sulfonated polyaniline nanotubes

A wet chemical approach is used successfully to produce nanostructured Au material by the reduction of sulfonated polyaniline (SPANI) nanotubes. The Au nanostructures obtained are composed of single crystal Au nanoplates, which are aggregated layer-by-layer into stacks or edge-on-face into clusters at various conditions. The Au nanoplate diameter and thickness can be conveniently controlled in the range of 100 nm to 2 mu m and 10 to 30 nm, respectively, with no accompanying single Au nanoparticles being observed. The formation of the Au nanostructures was controlled by the degradation of SPANI. The gradually and slowly released segments of SPANI served as the reductant during the growth of the 2D Au nanostructures.