Zeolite supported gold nanoparticles for selective photooxidation of aromatic alcohols under visible light irradiation

With new photocatalysts of gold nanoparticles supported on zeolite supports (Au/zeolite), oxidation of benzyl alcohol and its derivatives into the corresponding aldehydes can proceed well with a high selectivity (99%) under visible light irradiation at ambient temperature. Au/zeolite photocatalysts were characterized by UV/Vis, XPS, TEM, XRD, EDS, BET, IR, and Raman techniques. The Surface Plasmon Resonance (SPR) effect of gold nanoparticles, the adsorption capability of zeolite supports, and the molecular polarities of aromatic alcohols were demonstrated to have an essential correlation with the photocatalytic performances. In addition, the effects of light intensity, wavelength range, and the role of molecular oxygen were investigated in detail. The kinetic study indicated that the visible light irradiation required much less apparent activation energy for photooxidation compared with thermal reaction. Based on the characterization data and the photocatalytic performances, we proposed a possible photooxidation mechanism.

Are plasmons responsible for the Raman signal enhancement observed with gold nanoparticle sensors?

The electromagnetic enhancement that occurs in surface enhanced Raman scattering (SERS) substrates containing gold nanoparticles (NPs) is believed to arise through the generation of localised surface plasmons. We present results that show no SERS signals are obtained when 25 nm diameter gold NPs layered quartz substrates exposed to 2-aminopyridine are illuminated with plasmon resonant 532 nm radiation, but SERS signals are observed when the same samples are illuminated with non-resonant 785 nm radiation.

Self-assembled hyperbranched polymer - gold nanoparticle hybrids : understanding the effect of polymer coverage on assembly size and SERS performance

In the past few years, remarkable progress has been made in unveiling novel and unique optical properties of strongly coupled plasmonic nanostructures. However, application of such plasmonic nanostructures in biomedicine remains challenging due to the lack of facile and robust assembly methods for producing stable nanostructures. Previous attempts to achieve plasmonic nano-assemblies using molecular ligands were limited due to the lack of flexibility that could be exercised in forming them. Here, we report the utilization of tailor-made hyperbranched polymers (HBP) as linkers to assemble gold nanoparticles (NPs) into nano-assemblies. The ease and flexibility in tuning the particle size and number of branch ends of a HBP makes it an ideal candidate as a linker, as opposed to DNA, small organic molecules and linear or dendrimeric polymers. We report a strong correlation of polymer (HBP) concentration with the size of the hybrid nano-assemblies and “hot-spot” density. We have shown that such solutions of stable HBP-gold nano-assemblies can be barcoded with various Raman tags to provide improved surface-enhanced Raman scattering (SERS) compared with non-aggregated NP systems. These Raman barcoded hybrid nano-assemblies, with further optimization of NP shape, size and “hot-spot” density, may find application as diagnostic tools in nanomedicine.

Selective reductions using visible light photocatalysts of supported gold nanoparticles

Photocatalytic synthesis using visible light is a desirable chemical process because of its potential to utilize sunlight. Supported gold nanoparticles (Au-NPs) were found to be efficient photocatalysts and the effects of the supports were identified including CeO2, TiO2, ZrO2, Al2O3, and zeolite Y. In particular Au/CeO2 exhibited the high catalytic activity to reduce nitroaromatics to azo compounds, hydrogenate azobenzene to hydroazobenzene, reduce ketones to alcohols, and deoxygenate epoxides to alkenes at ambient temperatures, under irradiation of visible light (or simulated sunlight). The reac-tive efficiency depends on two primary factors: one is the light adsorption of catalysts and another is the driving ability of catalysts corresponding to the reactants. The light absorption by Au-NPs is due to surface plasmon resonance effect or inter-band electron transition; this is related to the reduction ability of the photocatalysts. Irradiation with shorter wavelengths can excite the conduction electrons in Au-NPs to higher energy levels and as a result, induce reduction with more negative reduction potentials. It is known when irradiated with light the Au-NPs can abstract hydrogen from isopropanol forming Au-H species on the Au-NP surface. Hence, we proposed that the active Au-H species will react with the N=O, N=N, C=O double bonds or epoxide bonds, which are weakened by the interaction with the excited electrons in the Au-NPs, and yield the final reductive products. The reacting power of the Au-H species depends on the energy of the excited electrons in Au-NPs: the higher the electronic energy, the stronger the reduction ability of the Au-H species. This finding demonstrates that we can tune the reduction ability of the photocatalysts by manipulating the irradiation wavelength.

Predicting the localized surface plasmon resonances of spherical nanoparticles on substrate : electrostatic eigenmode method

We present experimental results that demonstrate that the wavelength of the fundamental localised surface plasmon resonance for spherical gold nanoparticles on glass can be predicted using a simple, one line analytical formula derived from the electrostatic eigenmode method. This allows the role of the substrate in lifting mode degeneracies to be determined, and the role of local environment refractive indices on the plasmon resonance to be investigated. The effect of adding silica to the casting solution in minimizing nanopaticle agglomeration is also discussed.

Ultra-trace detection of diagnostically important biomarkers using functionalised-Surface Enhanced Raman Spectroscopy (SERS)

Here we report an ultrasensitive method for detecting bio-active compounds in biological samples by means of functionalised nanoparticles interrogated by surface enhanced Raman spectroscopy (SERS). This method is applicable to the recovery and detection of many diagnostically important peptidyl analytes such as insulin, human growth hormone, growth factors (IGFs) and erythropoietin (EPO), as well as many small molecule analytes and metabolites. Our method, developed to detect EPO, demonstrates its utility in a complex yet well defined biological system. Recombinant human EPO (rhEPO) and EPO analogues have successfully been used to treat anaemia in end-stage renal failure, chronic disorders and infections, cancer and AIDS. Current methods for EPO testing are lengthy, laborious and relatively insensitive to low concentrations. In our rapid screening methodology, gold nanoparticles were functionalised with anti-EPO antibodies to provide very high selectivity towards the EPO protein in urine. These “smart sensor” nanoparticles interact with and trap EPO. Subsequent SERS screening allows for the detection and quantisation of ultra trace amounts (<<10-15 M) of EPO in urine samples with minimal sample preparation. We present data showing that the SERS spectrum differentiates between human endogenous EPO and rhEPO in unpurified urine, and potentially distinguishes between purified EPO isoforms. The elimination of sample preparation and direct screening in biological fluids significantly reduces the time required by current methods. Antibody recognition against a variety of biological targets and the availability of portable commercial SERS analysers for rapid onsite testing suggest broad diagnostic applicability in a flexible analytical platform.

Memory effect in the deposition of C20 fullerenes on a diamond surface

In this paper, the deposition of C-20 fullerenes on a diamond (001)-(2x1) surface and the fabrication of C-20 thin film at 100 K were investigated by a molecular dynamics (MD) simulation using the many-body Brenner bond order potential. First, we found that the collision dynamic of a single C-20 fullerene on a diamond surface was strongly dependent on its impact energy. Within the energy range 10-45 eV, the C-20 fullerene chemisorbed on the surface retained its free cage structure. This is consistent with the experimental observation, where it was called the memory effect in "C-20-type" films [P. Melion , Int. J. Mod. B 9, 339 (1995); P. Milani , Cluster Beam Synthesis of Nanostructured Materials (Springer, Berlin, 1999)]. Next, more than one hundred C-20 (10-25 eV) were deposited one after the other onto the surface. The initial growth stage of C-20 thin film was observed to be in the three-dimensional island mode. The randomly deposited C-20 fullerenes stacked on diamond surface and acted as building blocks forming a polymerlike structure. The assembled film was also highly porous due to cluster-cluster interaction. The bond angle distribution and the neighbor-atom-number distribution of the film presented a well-defined local order, which is of sp(3) hybridization character, the same as that of a free C-20 cage. These simulation results are again in good agreement with the experimental observation. Finally, the deposited C-20 film showed high stability even when the temperature was raised up to 1500 K.

SERS based detection of barcoded gold nanoparticle assemblies from within animal tissue

We have explored the potential of deep Raman spectroscopy, specifically surface enhanced spatially offset Raman spectroscopy (SESORS), for non-invasive detection from within animal tissue, by employing SERS-barcoded nanoparticle (NP) assemblies as the diagnostic agent. This concept has been experimentally verified in a clinic-relevant backscattered Raman system with an excitation line of 785 nm under ex vivo conditions. We have shown that our SORS system, with a fixed offset of 2-3 mm, offered sensitive probing of injected QTH-barcoded NP assemblies through animal tissue containing both protein and lipid. In comparison to that of non-aggregated SERS-barcoded gold NPs, we have demonstrated that the tailored SERS-barcoded aggregated NP assemblies have significantly higher detection sensitivity. We report that these NP assemblies can be readily detected at depths of 7-8 mm from within animal proteinaceous tissue with high signal-to-noise (S/N) ratio. In addition they could also be detected from beneath 1-2 mm of animal tissue with high lipid content, which generally poses a challenge due to high absorption of lipids in the near-infrared region. We have also shown that the signal intensity and S/N ratio at a particular depth is a function of the SERS tag concentration used and that our SORS system has a QTH detection limit of 10-6 M. Higher detection depths may possibly be obtained with optimization of the NP assemblies, along with improvements in the instrumentation. Such NP assemblies offer prospects for in vivo, non-invasive detection of tumours along with scope for incorporation of drugs and their targeted and controlled release at tumour sites. These diagnostic agents combined with drug delivery systems could serve as a “theranostic agent”, an integration of diagnostics and therapeutics into a single platform.

Supported gold nanoparticles as photocatalysts utilising the full solar spectrum for organic synthesis

This thesis is an innovative study for organic synthesis using supported gold nanoparticles as photocatalysts under visible light irradiation. It especially examines a novel green process for efficient hydroamination of alkynes with amines. The investigation of other traditional reduction and oxidation reactions also adds significantly to the knowledge of gold nanoparticles and titania nanofibres as photocatalysts for organic synthesis.

High energy states of gold and their importance in electrocatalytic processes at surfaces and interfaces

The ability of metals to store or trap considerable amounts of energy, and thus exist in a non-equilibrium or metastable state, is very well known in metallurgy; however, such behaviour, which is intimately connected with the defect character of metals, has been largely ignored in noble metal surface electrochemistry. Techniques for generating unusually high energy surface states for gold, and the unusual voltammetric responses of such states, are outlined. The surprisingly high (and complex) electrocatalytic activity of gold in aqueous media is attributed to the presence of a range of such non-equilibrium states as the vital entities at active sites on conventional gold surfaces. The possible relevance of these ideas to account for the remarkable catalytic activity of oxide-supported gold microparticles is briefly outlined.

A study of localised galvanic replacement of copper and silver films with gold using scanning electrochemical microscopy

Galvanic replacement represents a highly significant process for the fabrication of bimetallic materials, but to date its application has been limited to either modification of large area metal surfaces or nanoparticles in solution. Here, the localised surface modification of copper and silver substrates with gold through the galvanic replacement process is reported. This was achieved by generation of a localised flux of AuCl4− ions from a gold ultramicroelectrode tip which interacts with the unbiased substrate of interest. The extent of modification with gold can be controlled through the tip–substrate distance and electrolysis time.

The electrochemical corrosion behaviour of quaternary gold alloys when exposed to 3.5% NaCl solution

Lower carat gold alloys, specifically 9 carat gold alloys, containing less than 40 % gold, and alloying additions of silver, copper and zinc, are commonly used in many jewellery applications, to offset high costs and poor mechanical properties associated with pure gold. While gold is considered to be chemically inert, the presence of active alloying additions raises concerns about certain forms of corrosion, particularly selective dissolution of these alloys. The purpose of this study was to systematically study the corrosion behaviour of a series of quaternary gold–silver–copper–zinc alloys using dc potentiodynamic scanning in saline (3.5 % NaCl) environment. Full anodic/cathodic scans were conducted to determine the overall corrosion characteristics of the alloy, followed by selective anodic scans and subsequent morphological and compositional analysis of the alloy surface and corroding media to determine the extent of selective dissolution. Varying degrees of selective dissolution and associated corrosion rates were observed after anodic polarisation in 3.5 % NaCl, depending on the alloy composition. The corrosion behaviour of the alloys was determined by the extent of anodic reactions which induce (1) formation of oxide scales on the alloy surface and or (2) dissolution of Zn and Cu species. In general, the improved corrosion characteristics of alloy #3 was attributed to the composition of Zn/Cu in the alloy and thus favourable microstructure promoting the formation of protective oxide/chloride scales and reducing the extent of Cu and Zn dissolution.

Direct electrochemical formation of alloyed AuPt nanostructured electrocatalysts for the oxidation of formic acid

The formation of highly anisotropic AuPt alloys has been achieved via a simple electrochemical approach without the need for organic surfactants to direct the growth process. The surface and bulk properties of these materials were characterised by scanning electron microscopy (SEM), X-ray diffraction (XRD), energy dispersive X-ray spectroscopy (EDX) and electrochemically by cyclic voltammetry to confirm alloy formation. It was found that AuPt materials are highly active for both the model hydrogen evolution reaction and the fuel cell relevant formic acid oxidation reaction. In particular for the latter case the preferred dehydrogenation pathway was observed at AuPt compared to nanostructured Pt prepared under identical electrochemical conditions which demonstrated the less preferred dehydration pathway. The enhanced performance is attributed to both the ensemble effect which facilitates CO(ads) removal from the surface as well as the highly anisotropic nanostructure of AuPt.

Creating gold nanoprisms directly on quartz crystal microbalance electrodes for mercury vapor sensing

A novel electrochemical route is used to form highly {111}-oriented and size-controlled Au nanoprisms directly onto the electrodes of quartz crystal microbalances (QCMs) which are subsequently used as mercury vapor sensors. The Au nanoprism loaded QCM sensors exhibited excellent response–concentration linearity with a response enhancement of up to ~ 800% over a non-modified sensor at an operating temperature of 28 °C. The increased surface area and atomic-scale features (step/defect sites) introduced during the growth of nanoprisms are thought to play a significant role in enhancing the sensing properties of the Au nanoprisms toward Hg vapor. The sensors are shown to have excellent Hg sensing capabilities in the concentration range of 0.123–1.27 ppmv (1.02–10.55 mg m − 3), with a detection limit of 2.4 ppbv (0.02 mg m − 3) toward Hg vapor when operating at 28 °C, and 17 ppbv (0.15 mg m − 3) at 89 °C, making them potentially useful for air monitoring applications or for monitoring the efficiency of Hg emission control systems in industries such as mining and waste incineration. The developed sensors exhibited excellent reversible behavior (sensor recovery) within 1 h periods, and crucially were also observed to have high selectivity toward Hg vapor in the presence of ethanol, ammonia and humidity, and excellent long-term stability over a 33 day operating period.