Photocatalysis on supported gold and silver nanoparticles under ultraviolet and visible light irradiation

Studies of the optical properties and catalytic capabilities of noble metal nanoparticles (NPs), such as gold (Au) and silver (Ag), have formed the basis for the very recent fast expansion of the field of green photocatalysis: photocatalysis utilizing visible and ultraviolet light, a major part of the solar spectrum. The reason for this growth is the recognition that the localised surface plasmon resonance (LSPR) effect of Au NPs and Ag NPs can couple the light flux to the conduction electrons of metal NPs, and the excited electrons and enhanced electric fields in close proximity to the NPs can contribute to converting the solar energy to chemical energy by photon-driven photocatalytic reactions. Previously the LSPR effect of noble metal NPs was utilized almost exclusively to improve the performance of semiconductor photocatalysts (for example, TiO2 and Ag halides), but recently, a conceptual breakthrough was made: studies on light driven reactions catalysed by NPs of Au or Ag on photocatalytically inactive supports (insulating solids with a very wide band gap) have demonstrated that these materials are a class of efficient photocatalysts working by mechanisms distinct from those of semiconducting photocatalysts. There are several reasons for the significant photocatalytic activity of Au and Ag NPs. (1) The conduction electrons of the particles gain the irradiation energy, resulting in high energy electrons at the NP surface which is desirable for activating molecules on the particles for chemical reactions. (2) In such a photocatalysis system, both light harvesting and the catalysing reaction take place on the nanoparticle, and so charge transfer between the NPs and support is not a prerequisite. (3) The density of the conduction electrons at the NP surface is much higher than that at the surface of any semiconductor, and these electrons can drive the reactions on the catalysts. (4) The metal NPs have much better affinity than semiconductors to many reactants, especially organic molecules. Recent progress in photocatalysis using Au and Ag NPs on insulator supports is reviewed. We focus on the mechanism differences between insulator and semiconductor-supported Au and Ag NPs when applied in photocatalytic processes, and the influence of important factors, light intensity and wavelength, in particular estimations of light irradiation contribution, by calculating the apparent activation energies of photo reactions and thermal reactions.

Control of core-shell structure and elemental composition of binary quantum dots

The possibility of initial stage control of the elemental composition and core/shell structure of binary SiC quantum dots by optimizing temporal variation of Si and C incoming fluxes and surface temperatures is shown via hybrid numerical simulations. Higher temperatures and influxes encourage the formation of a stoichiometric outer shell over a small carbon-enriched core, whereas lower temperatures result in a larger carbon-enriched core, Si-enriched undershell, and then a stoichiometric SiC outer shell. This approach is generic and is applicable to a broad range of semiconductor materials and nanofabrication techniques. © 2007 American Institute of Physics.

Self-interaction of surface polaritons at the narrow-gap n-type semiconductor metal interface

The non-linear self-interaction of the potential surface polaritons (SP) which is due to the free carriers dispersion law where nonparabolicity is studied. The SP propagate at the interface between n-type semiconductor and a metal. The self interaction of the SP is shown to be different in semiconductors with normal and inverse zone structures. The results of the SP field envelope evolution are given. The obtained nonlinear frequency shift has been compared with shifts which are due to another self-interaction mechanisms. This comparison shows that the nonlinear self-interaction mechanism, which is due to free carriers spectrum nonparabolicity, is especially significant in narrow-gap semiconductor materials.

Nonlinear surface magnetoplasmons at the electron semiconductor-metal interface

The nonlinear self-interaction of the potential surface magnetoplasmons, propagating across the external magnetic field at the n-type semiconductor-metal interface is described in this manuscript. The studied nonlinearity is due to the free carriers dispersion law nonparabolicity and we show that it acts differently in semiconductor materials with normal and inverse band structures. The results of the nonlinear evolution of the surface magnetoplasmons are presented as well.

Steel–concrete–steel sandwich system in Arctic offshore structure: Materials, experiments, and design

The gravity based structure (GBS) with external Steel–Concrete–Steel (SCS) sandwich ice-resistant wall has been developed for the Arctic oil and gas drilling. This paper firstly reported the experimental studies on the mechanical properties of steel and concretes under Arctic low temperature. With the test data, design equations were developed to incorporate the influences of the low temperature on these mechanical properties. Two types of Arctic GBS structure with flower-conical SCS sandwich shell type and plate type of ice-resistant wall have been developed for the Arctic offshore structure. Besides the studies on the materials, two SCS sandwich prototype shells and plates were, respectively, prepared and tested under patch loading that simulated the localized ice-contact pressure. The structural behaviors of the SCS sandwich structure under patch loading were reported and discussions were made on the influences of different parameters on the structural behavior of the structure. Analytical models were developed to predict the punching shear resistances of the SCS sandwich structure through modifying the code provisions. The accuracies of the developed analytical models were checked through validations against 27 tests in the literature. Corresponding design procedures on resistances of SCS sandwich structure were recommended based on these discussions and validations.

Consumers' emotional judgement of materials durability and disposal

The literature demonstrates that understanding relating to the use of materials in product design has been investigated from both engineering and design perspectives. However, none of these studies have explored the consumers’ concepts of the materials; rather they have focused on participants’ discussions of material samples. Consumers’ emotional reactions to the materials themselves or the consumers’ reaction to the durability of the materials have not been previously explored in depth. This research has investigated these issues and has found that consumers have very specific concepts about materials. Furthermore, the combinations of consumer concepts that are likely to elicit an emotional judgement by the consumer have also been identified. It was found that consumers are conscious of the durability of their products and the materials that they are made from. This knowledge contributes to the support of environmentally conscious design, as well as user-centered design knowledge and practice. An understanding of the emotion consumers attribute to the effect wear and aging had on the materials’ physical appearance has been achieved. This understanding of consumers’ emotional reactions to materials can contribute not only to design considerations but to knowledge regarding the promotion of prolonged product-user relationships.

Influence of rapid thermal annealing (RTA) on the structural and electrical properties of SnS films

The performance of optoelectronic devices critically depends on the quality of active layer. An effective way to obtain a high quality layers is by creating excess of metal atoms through various heat treatments. Recently, rapid thermal annealing (RTA) has proved a versatile technique for the post-treatment of semiconductor materials as compared to other techniques due to its precise control over the resources. Thus, we carried out a set of experiments on SnS films to explore the influence of RTA treatment on their properties. From these experiments we noticed that the films treated at 400 °C for 1 min in N2 atmosphere have a low electrical resistivity of ~5 Ωcm with relatively high Hall mobility and carrier density of 99 cm2/Vs and 1.3 × 1016 cm−3, respectively. The observed results, therefore, emphasise that it is possible to obtain good quality SnS films through RTA treatment without disturbing their crystal structure.

Mesoporous silica- and silicon-based materials as carriers for poorly water soluble drugs

New chemical entities with unfavorable water solubility properties are continuously emerging in drug discovery. Without pharmaceutical manipulations inefficient concentrations of these drugs in the systemic circulation are probable. Typically, in order to be absorbed from the gastrointestinal tract, the drug has to be dissolved. Several methods have been developed to improve the dissolution of poorly soluble drugs. In this study, the applicability of different types of mesoporous (pore diameters between 2 and 50 nm) silicon- and silica-based materials as pharmaceutical carriers for poorly water soluble drugs was evaluated. Thermally oxidized and carbonized mesoporous silicon materials, ordered mesoporous silicas MCM-41 and SBA-15, and non-treated mesoporous silicon and silica gel were assessed in the experiments. The characteristic properties of these materials are the narrow pore diameters and the large surface areas up to over 900 m²/g. Loading of poorly water soluble drugs into these pores restricts their crystallization, and thus, improves drug dissolution from the materials as compared to the bulk drug molecules. In addition, the wide surface area provides possibilities for interactions between the loaded substance and the carrier particle, allowing the stabilization of the system. Ibuprofen, indomethacin and furosemide were selected as poorly soluble model drugs in this study. Their solubilities are strongly pH-dependent and the poorest (< 100 µg/ml) at low pH values. The pharmaceutical performance of the studied materials was evaluated by several methods. In this work, drug loading was performed successfully using rotavapor and fluid bed equipment in a larger scale and in a more efficient manner than with the commonly used immersion methods. It was shown that several carrier particle properties, in particular the pore diameter, affect the loading efficiency (typically ~25-40 w-%) and the release rate of the drug from the mesoporous carriers. A wide pore diameter provided easier loading and faster release of the drug. The ordering and length of the pores also affected the efficiency of the drug diffusion. However, these properties can also compensate the effects of each other. The surface treatment of porous silicon was important in stabilizing the system, as the non-treated mesoporous silicon was easily oxidized at room temperature. Different surface chemical treatments changed the hydrophilicity of the porous silicon materials and also the potential interactions between the loaded drug and the particle, which further affected the drug release properties. In all of the studies, it was demonstrated that loading into mesoporous silicon and silica materials improved the dissolution of the poorly soluble drugs as compared to the corresponding bulk compounds (e.g. after 30 min ~2-7 times more drug was dissolved depending on the materials). The release profile of the loaded substances remained similar also after 3 months of storage at 30°C/56% RH. The thermally carbonized mesoporous silicon did not compromise the Caco-2 monolayer integrity in the permeation studies and improved drug permeability was observed. The loaded mesoporous silica materials were also successfully compressed into tablets without compromising their characteristic structural and drug releasing properties. The results of this research indicated that mesoporous silicon/silica-based materials are promising materials to improve the dissolution of poorly water soluble drugs. Their feasibility in pharmaceutical laboratory scale processes was also confirmed in this thesis.

Photoluminescence enhancement and quenching in metal-semiconductor quantum dot hybrid arrays

Hybrid monolayer arrays of metal and semiconductor quantum dots have been prepared to study the exciton-plasmon interaction. We observed crossover from strong quenching to enhancement in photoluminescence of the quantum dots as a function of the emission wavelength for fixed interparticle spacings. Remarkably, the enhancement is observed even for extremely short separation at which strong quenching has been observed and predicted earlier. A significant redshift in emission maxima is also observed for quantum dots with quenched emission. The possible role of collective phenomena as well as strong interactions in such ordered hybrid arrays in controlling the emission is discussed. (C) 2011 American Institute of Physics. doi:10.1063/1.3553766]

Design and Development of Thermoelectric Generator

In this paper we discuss the fabrication, working and characteristics of a thermoelectric generator made up of p and n type semiconductor materials. The device consists of Fe0.2Co3.8Sb11.5Te0.5 (zT = 1.04 at 818 K) as the n-type and Zn4Sb3 (zT= 0.8 at 550 K) as the p-type material synthesized by vacuum hot press method. Carbon paste has been used to join the semiconductor legs to metal (Molybdenum) electrodes to reduce the contact resistance. The multi-couple (4 legs) generator results a maximum output power of 1.083 mW at a temperature difference of 240 K between the hot and cold sides. In this investigation, an I-V characteristic, maximum output power of the thermoelectric module is presented. The efficiency of thermoelectric module is obtained as eta= 0.273 %.

Influence of Surface Texture and Roughness of Softer and Harder Counter Materials on Friction During Sliding

Surface texture influences friction during sliding contact conditions. In the present investigation, the effect of surface texture and roughness of softer and harder counter materials on friction during sliding was analyzed using an inclined scratch testing system. In the experiments, two test configurations, namely (a) steel balls against aluminum alloy flats of different surface textures and (b) aluminum alloy pins against steel flats of different surface textures, are utilized. The surface textures were classified into unidirectionally ground, 8-ground, and randomly polished. For a given texture, the roughness of the flat surfaces was varied using grinding or polishing methods. Optical profilometer and scanning electron microscope were used to characterize the contact surfaces before and after the experiments. Experimental results showed that the surface textures of both harder and softer materials are important in controlling the frictional behavior. The softer material surface textures showed larger variations in friction between ground and polished surfaces. However, the harder material surface textures demonstrated a better control over friction among the ground surfaces. Although the effect of roughness on friction was less significant when compared to textures, the harder material roughness showed better correlations when compared to the softer material roughness.

Synthesis, characterization and low temperature electrical conductivity of Polyaniline/NiFe2O4 nanocomposites

Conducting polymer/ferrite nanocomposites with an organized structure provide a new functional hybrid between organic and inorganic materials. The most popular among the conductive polymers is the polyaniline (PANI) due to its wide application in different fields. In the present work nickel ferrite (NiFe2O4) nanoparticles were prepared by sol-gel citrate-nitrate method with an average size of 21.6nm. PANI/NiFe2O4 nanoparticles were synthesized by a simple general and inexpensive in-situ polymerization in the presence of NiFe2O4 nanoparticles. The effects of NiFe2O4 nanoparticles on the dc-electrical properties of polyaniline were investigated. The structural components in the nanocomposites were identified from Fourier Transform Infrared (FTIR) spectroscopy. The crystalline phase of nanocomposites was characterized by X-Ray Diffraction (XRD). The Scanning Electron Micrograph (SEM) reveals that there was some interaction between the NiFe2O4 particles and polyaniline and the nanocomposites are composed of polycrystalline ferrite nanoparticles and PANI. The dc conductivity of polyaniline/NiFe2O4 nanocomposites have been measured as a function of temperature in the range of 80K to 300K. It is observed that the room temperature conductivity sigma(RT) decreases with increase in the relative content of NiFe2O4. The experimental data reveals that the resistivity increases for all composites with decrease of temperature exhibiting semiconductor behaviour.

Temperature dependent electrical characterisation of Pt/HfO2/n-GaN metal-insulator-semiconductor (MIS) Schottky diodes

This paper reports an improvement in Pt/n-GaN metal-semiconductor (MS) Schottky diode characteristics by the introduction of a layer of HfO2 (5 nm) between the metal and semiconductor interface. The resulting Pt/HfO2/n-GaN metal-insulator-semiconductor (MIS) Schottky diode showed an increase in rectification ratio from 35.9 to 98.9(@ 2V), increase in barrier height (0.52 eV to 0.63eV) and a reduction in ideality factor (2.1 to 1.3) as compared to the MS Schottky. Epitaxial n-type GaN films of thickness 300nm were grown using plasma assisted molecular beam epitaxy (PAMBE). The crystalline and optical qualities of the films were confirmed using high resolution X-ray diffraction and photoluminescence measurements. Metal-semiconductor (Pt/n-GaN) and metal-insulator-semiconductor (Pt/HfO2/n-GaN) Schottky diodes were fabricated. To gain further understanding of the Pt/HfO2/GaN interface, I-V characterisation was carried out on the MIS Schottky diode over a temperature range of 150 K to 370 K. The barrier height was found to increase (0.3 eV to 0.79 eV) and the ideality factor decreased (3.6 to 1.2) with increase in temperature from 150 K to 370 K. This temperature dependence was attributed to the inhomogeneous nature of the contact and the explanation was validated by fitting the experimental data into a Gaussian distribution of barrier heights. (C) 2015 Author(s).