Encapsulation of transition metal species into zeolites and molecular sieves as redox catalysts: Part I-preparation and characterisation of nanosized TiO2, CdO and ZnO semiconductor particles anchored in NaY zeolite

In this paper, we report the preparation and characterisation of nanometer-sized TiO2, CdO, and ZnO semiconductor particles trapped in zeolite NaY. Preparation of these particles was carried out via the traditional ion exchange method and subsequent calcination procedure. It was found that the smaller cations, i.e., Cd2+ and Zn2+ could be readily introduced into the SI′ and SII′ sites located in the sodalite cages, through ion exchange; while this is not the case for the larger Ti species, i.e., Ti monomer [TiO]2+ or dimer [Ti2O3]2+ which were predominantly dispersed on the external surface of zeolite NaY. The subsequent calcination procedure promoted these Ti species to migrate into the internal surface of the supercages. These semiconductor particles confined in NaY zeolite host exhibited a significant blue shift in the UV-VIS absorption spectra, in contrast to the respective bulk semiconductor materials, due to the quantum size effect (QSE). The particle sizes calculated from the UV-VIS optical absorption spectra using the effective mass approximation model are in good agreement with the atomic absorption data.

Influence of oxidation and reduction conditions upon the morphology of silica-supported polycrystalline silver catalysts

The effect of oxidation and reduction conditions upon the morphology of polycrystalline silver catalysts has been investigated by means of in situ Fourier-transform infrared (FTIR) spectroscopy. Characterization of the sample was achieved by inspection of the νas(COO) band profile of adsorbed formate, recorded after dosing with formic acid at ambient temperature. Evidence was obtained for the existence of a silver surface reconstructed by the presence of subsurface oxygen in addition to the conventional family of Ag(111) and Ag(110) crystal faces. Oxidation at 773 K facilitated the reconstruction of silver planes due to the formation of subsurface oxygen species. Prolonged oxygen treatment at 773 K also caused particle fragmentation as a consequence of excessive oxygen penetration of the silver catalyst at defect sites. It was also deduced that the presence of oxygen in the gas phase stabilized the growth of silver planes which could form stronger bonds with oxygen. In contrast, high-temperature thermal treatment in vacuum induced significant sintering of the silver catalyst. Reduction at 773 K resulted in substantial quantities of dissolved hydrogen (and probably hydroxy species) in the bulk silver structure. Furthermore, enhanced defect formation in the catalyst was also noted, as evidenced by the increased concentration of formate species associated with oxygen-reconstructed silver faces.

Experimental impact and finite element analysis of a composite, portable road safety barrier

This thesis provides an experimental and computational platform for investigating the performance and behaviour of water filled, plastic portable road safety barriers in an isolated impact scenario. A schedule of experimental impact tests were conducted assessing the impact response of an existing design of road safety barrier utilising a novel horizontal impact testing system. A coupled finite element and smooth particle hydrodynamic model of the barrier system was developed and validated against the results of the experimental tests. The validated model was subsequently used to assess the effect of certain composite materials on the impact performance of the water filled, portable road safety barrier system.

Cascaded DC-DC converter connection of photovoltaic modules

New residential scale photovoltaic (PV) arrays are commonly connected to the grid by a single dc-ac inverter connected to a series string of pv panels, or many small dc-ac inverters which connect one or two panels directly to the ac grid. This paper proposes an alternative topology of nonisolated per-panel dc-dc converters connected in series to create a high voltage string connected to a simplified dc-ac inverter. This offers the advantages of a "converter-per-panel" approach without the cost or efficiency penalties of individual dc-ac grid connected inverters. Buck, boost, buck-boost, and Cu´k converters are considered as possible dc-dc converters that can be cascaded. Matlab simulations are used to compare the efficiency of each topology as well as evaluating the benefits of increasing cost and complexity. The buck and then boost converters are shown to be the most efficient topologies for a given cost, with the buck best suited for long strings and the boost for short strings. While flexible in voltage ranges, buck-boost, and Cu´k converters are always at an efficiency or alternatively cost disadvantage.

Removal of phosphorus using NZVI derived from reducing natural goethite

Nano zero valent iron (NZVI) prepared by reducing natural goethite in hydrogen at 550 °C was used to remove phosphate. The effect of particle size, reaction time, NZVI dose, pH, initial phosphorus concentration, and oxygen amount in reaction system on phosphorus removal was investigated. The characterization of X-ray fluorescence (XRF), X-ray diffraction (XRD), N2 adsorption and desorption (BET analysis), transmission electron microscope (TEM), field emission scanning electron microscope with a energy dispersive X-ray detector (FESEM/EDS) and X-ray photoelectron spectroscopy (XPS) indicated that nanoscale of iron (around 80–150 nm length and 5–30 nm width) was prepared successfully with high dispersion and relative large surface area around 22 m2/g. The results of batch experiments and XPS analysis suggested that this kind of NZVI had a good performance on removal of phosphate (over 99%) despite in slightly acidic media as the initial concentration of P was 5 mg/L. The reason was ascribed to the effective corrosion of this NZVI under the function of proton and dissolved oxygen in spite of the existence of thin passive films.

Excursion guidance criteria to guide control of peak emission and exposure to airborne engineered particles

The overall aim of our research was to characterize airborne particles from selected nanotechnology processes and to utilize the data to develop and test quantitative particle concentration-based criteria that can be used to trigger an assessment of particle emission controls. We investigated particle number concentration (PNC), particle mass (PM) concentration, count median diameter (CMD), alveolar deposited surface area, elemental composition, and morphology from sampling of aerosols arising from six nanotechnology processes. These included fibrous and non-fibrous particles, including carbon nanotubes (CNTs). We adopted standard occupational hygiene principles in relation to controlling peak emission and exposures, as outlined by both Safe Work Australia, (1) and the American Conference of Governmental Industrial Hygienists (ACGIH®). (2) The results from the study were used to analyses peak and 30-minute averaged particle number and mass concentration values measured during the operation of the nanotechnology processes. Analysis of peak (highest value recorded) and 30-minute averaged particle number and mass concentration values revealed: Peak PNC20–1000 nm emitted from the nanotechnology processes were up to three orders of magnitude greater than the local background particle concentration (LBPC). Peak PNC300–3000 nm was up to an order of magnitude greater, and PM2.5 concentrations up to four orders of magnitude greater. For three of these nanotechnology processes, the 30-minute average particle number and mass concentrations were also significantly different from the LBPC (p-value < 0.001). We propose emission or exposure controls may need to be implemented or modified, or further assessment of the controls be undertaken, if concentrations exceed three times the LBPC, which is also used as the local particle reference value, for more than a total of 30 minutes during a workday, and/or if a single short-term measurement exceeds five times the local particle reference value. The use of these quantitative criteria, which we are terming the universal excursion guidance criteria, will account for the typical variation in LBPC and inaccuracy of instruments, while precautionary enough to highlight peaks in particle concentration likely to be associated with particle emission from the nanotechnology process. Recommendations on when to utilize local excursion guidance criteria are also provided.

Size characterization of airborne SiO2 nanoparticles with on-line and off-line measurement techniques : an interlaboratory comparison study

Results of an interlaboratory comparison on size characterization of SiO2 airborne nanoparticles using on-line and off-line measurement techniques are discussed. This study was performed in the framework of Technical Working Area (TWA) 34—“Properties of Nanoparticle Populations” of the Versailles Project on Advanced Materials and Standards (VAMAS) in the project no. 3 “Techniques for characterizing size distribution of airborne nanoparticles”. Two types of nano-aerosols, consisting of (1) one population of nanoparticles with a mean diameter between 30.3 and 39.0 nm and (2) two populations of non-agglomerated nanoparticles with mean diameters between, respectively, 36.2–46.6 nm and 80.2–89.8 nm, were generated for characterization measurements. Scanning mobility particle size spectrometers (SMPS) were used for on-line measurements of size distributions of the produced nano-aerosols. Transmission electron microscopy, scanning electron microscopy, and atomic force microscopy were used as off-line measurement techniques for nanoparticles characterization. Samples were deposited on appropriate supports such as grids, filters, and mica plates by electrostatic precipitation and a filtration technique using SMPS controlled generation upstream. The results of the main size distribution parameters (mean and mode diameters), obtained from several laboratories, were compared based on metrological approaches including metrological traceability, calibration, and evaluation of the measurement uncertainty. Internationally harmonized measurement procedures for airborne SiO2 nanoparticles characterization are proposed.

NSAM-derived total surface area vs. SMPS-derived "mobility equivalent" surface area for different environmentally relevant aerosols

The surface area of inhaled particles deposited in the alveolar region, as reported by the TSI nanoparticle surface area monitor (NSAM), was compared with the corresponding value estimated by a TSI scanning mobility particle sizer (SMPS) for a range of environmentally relevant aerosols, including petrol emissions, ETS, laser printer emissions, cooking emissions and ambient aerosols. The SMPS values were based on a mobility size distribution assuming spherical particles using the appropriate size-dependent alveolar-deposition factors provided by the ICRP. In most cases, the two instruments showed good linear agreement. With petrol emissions and ETS, the linearity extended to over 103 μm2 cm-3. With printer emissions, there was good linearity up to about 300 μm2 cm-3 while the NSAM increasingly overestimated the surface area at higher concentrations. The presence of a nucleation event in ambient air caused the NSAM to over-estimate the surface area by a factor of 2. We summarize these results and conclude that the maximum number concentration up to which the NSAM is accurate clearly depends on the type of aerosol being sampled and provide guidance for the use of the instrument.

Effect of atmospheric ageing on volatility and ROS of biodiesel exhaust nano-particles

Generally, the magnitude of pollutant emissions from diesel engines is ultimately coupled to the structure of fuel molecules. The presence of oxygen, level of unsaturation and the carbon chain length of respective molecules influence the combustion chemistry. It is speculated that increased oxygen content in the fuel may lead to the increased oxidative potential (Stevanovic, S. 2013). Also, upon the exposure to UV and ozone in the atmosphere, the chemical composition of the exhaust is changed. The presence of an oxidant and UV is triggering the cascade of photochemical reactions as well as the partitioning of semi-volatile compounds between the gas and particle phase. To gain an insight into the relationship between the molecular structures of the esters, their volatile organic content and the potential toxicity of diesel exhaust particulate matter, measurements were conducted on a modern common rail diesel engine. This research also investigates the contribution of atmospheric conditions on the transfer of semi-volatile fraction of diesel exhaust from the gas phase to the particle phase and the extent to which semi-volatile compounds (SVOCs) are related to the oxidative potential, expressed through the concentration of reactive oxygen species (ROS) (Stevanovic, S. 2013)...

An effort towards understanding the sources of impurities in generating nanoparticles via liquid-phase methods

Generating nano-sized materials of a controlled size and chemical composition is essential for the manufacturing of materials with enhanced properties on an industrial scale, as well as for research purposes, such as toxicological studies. Among the generation methods for airborne nanoparticles (also known as aerosolisation methods), liquid-phase techniques have been widely applied due to the simplicity of their use and their high particle production rate. The use of a collison nebulizer is one such technique, in which the atomisation takes place as a result of the liquid being sucked into the air stream and injected toward the inner walls of the nebulizer reservoir via nozzles, before the solution is dispersed. Despite the above-mentioned benefits, this method also falls victim to various sources of impurities (Knight and Petrucci 2003; W. LaFranchi, Knight et al. 2003). Since these impurities can affect the characterization of the generated nanoparticles, it is crucial to understand and minimize their effect.

Validating SMPS-measured size distribution of double-mode spherical Silica nanoparticles by Transmission Electron Microscope (TEM)

A nanoparticles size is one of their key physical characteristics that can affect their fate in a human’s respiratory tract (in case of inhalation) and also in the environment. Hence, measuring the size distribution of nanoparticles is absolutely essential and contributes greatly to their characterization. For years, Scanning Mobility Particle Sizers (SMPS), which rely on measuring the electrical mobility diameter of particles, have been used as one of the most reliable real-time instruments for the size distribution measurement of nanoparticles. Despite its benefits, this instrument has some drawbacks, including equivalency problems for non-spherical particles (i.e. assuming a non-spherical particle is equal to a spherical particle of diameter d due to the same electrical mobility), as well as limitations in terms of its use in workplaces, because of its large size and the complexity of its operation...

Personal exposure to ultrafine particles : the influence of time-activity patterns

Exposure to ultrafine particles (UFPs) is deemed to be a major risk affecting human health. Therefore, airborne particle studies were performed in the recent years to evaluate the most critical micro-environments, as well as identifying the main UFP sources. Nonetheless, in order to properly evaluate the UFP exposure, personal monitoring is required as the only way to relate particle exposure levels to the activities performed and micro-environments visited. To this purpose, in the present work, the results of experimental analysis aimed at showing the effect of the time-activity patterns on UFP personal exposure are reported. In particular, 24 non-smoking couples (12 during winter and summer time, respectively), comprised of a man who worked full-time and a woman who was a homemaker, were analyzed using personal particle counter and GPS monitors. Each couple was investigated for a 48-h period, during which they also filled out a diary reporting the daily activities performed. Time activity patterns, particle number concentration exposure and the related dose received by the participants, in terms of particle alveolar-deposited surface area, were measured. The average exposure to particle number concentration was higher for women during both summer and winter (Summer: women 1.8×104 part. cm-3; men 9.2×103 part. cm-3; Winter: women 2.9×104 part. cm-3; men 1.3×104 part. cm-3), which was likely due to the time spent undertaking cooking activities. Staying indoors after cooking also led to higher alveolar-deposited surface area dose for both women and men during the winter time (9.12×102 and 6.33×102 mm2, respectively), when indoor ventilation was greatly reduced. The effect of cooking activities was also detected in terms of women’s dose intensity (dose per unit time), being 8.6 and 6.6 in winter and summer, respectively. On the contrary, the highest dose intensity activity for men was time spent using transportation (2.8 in both winter and summer).

Role of particle size and composition in metal adsorption by solids deposited on urban road surfaces

Despite common knowledge that the metal content adsorbed by fine particles is relatively higher compared to coarser particles, the reasons for this phenomenon has gained little research attention. The research study discussed in the paper investigated the variations in metal content for different particle sizes of solids associated with pollutant build-up on urban road surfaces. Data analysis confirmed that parameters favourable for metal adsorption to solids such as specific surface area, organic carbon content, effective cation exchange capacity and clay forming minerals content decrease with the increase in particle size. Furthermore, the mineralogical composition of solids was found to be the governing factor influencing the specific surface area and effective cation exchange capacity. There is high quartz content in particles >150µm compared to particles <150µm. As particle size reduces below 150µm, the clay forming minerals content increases, providing favourable physical and chemical properties that influence adsorption.

Understanding mild acid pretreatment of sugarcane bagasse through particle scale modeling

Sugarcane bagasse is an abundant and sustainable resource, generated as a by-product of sugarcane milling. The cellulosic material within bagasse can be broken down into glucose molecules and fermented to produce ethanol, making it a promising feedstock for biofuel production. Mild acid pretreatment hydrolyses the hemicellulosic component of biomass, thus allowing enzymes greater access to the cellulosic substrate during saccharification. A particle-scale mathematical model describing the mild acid pretreatment of sugarcane bagasse has been developed, using a volume averaged framework. Discrete population-balance equations are used to characterise the polymer degradation kinetics, and diffusive effects account for mass transport within the cell wall of the bagasse. As the fibrous material hydrolyses over time, variations in the porosity of the cell wall and the downstream effects on the reaction kinetics are accounted for using conservation of volume arguments. Non-dimensionalization of the model equations reduces the number of parameters in the system to a set of four dimensionless ratios that compare the timescales of different reaction and diffusion events. Theoretical yield curves are compared to macroscopic experimental observations from the literature and inferences are made as to constraints on these “unknown” parameters. These results enable connections to be made between experimental data and the underlying thermodynamics of acid pretreatment. Consequently, the results suggest that data-fitting techniques used to obtain kinetic parameters should be carefully applied, with prudent consideration given to the chemical and physiological processes being modeled.