Effects of Alloyed and Oxide Phases on Methanol Oxidation of Pt-Ru/C Nanocatalysts of the Same Particle Size

Funda����o de Amparo �� Pesquisa do Estado de S��o Paulo (FAPESP)

Kinetic aspects of ion exchange in KhFek[Fe(CN)(6)](l)center dot mH(2)O compounds: A combined electrical and mass transfer functions approach

The present paper quantifies and develops the kinetic aspects involved in the mechanism of interplay between electron and ions presented elsewhere(1) for KhFek[Fe(CN)(6)](l)center dot mH(2)O (Prussian Blue) host materials. Accordingly, there are three different electrochemical processes involved in the PB host materials: H3O+, K+, and H+ insertion/extraction mechanisms which here were fully kinetically studied by means of the use of combined electronic and mass transfer functions as a tool to separate all the processes. The use of combined electronic and mass transfer functions was very important to validate and confirm the proposed mechanism. This mechanism allows the electrochemical and chemical processes involved in the KhFek[Fe(CN)(6)](l)center dot mH(2)O host and Prussian Blue derivatives to be understood. In addition, a formalism was also developed to consider superficial oxygen reduction. From the analysis of the kinetic processes involved in the model, it was possible to demonstrate that the processes associated with K+ and H+ exchanges are reversible whereas the H3O+ insertion process was shown not to present a reversible pattern. This irreversible pattern is very peculiar and was shown to be related to the catalytic proton reduction reaction. Furthermore, from the model, it was possible to calculate the number density of available sites for each intercalation/deintercalation processes and infer that they are very similar for K+ and H+. Hence, the high prominence of the K+ exchange observed in the voltammetric responses has a kinetic origin and is not related to the amount of sites available for intercalation/deintercalation of the ions.

Chemically Resolved Particle Fluxes Over Tropical and Temperate Forests

Chemically resolved submicron (PM1) particlemass fluxes were measured by eddy covariance with a high resolution time-of-flight aerosolmass spectrometer over temperate and tropical forests during the BEARPEX-07 and AMAZE-08 campaigns. Fluxes during AMAZE-08 were small and close to the detection limit (<1 ng m���2 s���1) due to low particle mass concentrations (<1 ��g m���3). During BEARPEX-07, concentrations were five times larger, with mean mid-day deposition fluxes of ���4.8 ng m���2 s���1 for total nonrefractory PM1 (Vex,PM1 = ���1 mm s���1) and emission fluxes of +2.6 ng m���2 s���1 for organic PM1 (Vex,org = +1 mm s���1). Biosphere���atmosphere fluxes of different chemical components are affected by in-canopy chemistry, vertical gradients in gas-particle partitioning due to canopy temperature gradients, emission of primary biological aerosol particles, and wet and dry deposition. As a result of these competing processes, individual chemical components had fluxes of varying magnitude and direction during both campaigns. Oxygenated organic components representing regionally aged aerosol deposited, while components of fresh secondary organic aerosol (SOA) emitted. During BEARPEX-07, rapid incanopy oxidation caused rapid SOA growth on the timescale of biosphere-atmosphere exchange. In-canopy SOA mass yields were 0.5���4%. During AMAZE-08, the net organic aerosol flux was influenced by deposition, in-canopy SOA formation, and thermal shifts in gas-particle partitioning.Wet deposition was estimated to be an order ofmagnitude larger than dry deposition during AMAZE-08. Small shifts in organic aerosol concentrations from anthropogenic sources such as urban pollution or biomass burning alters the balance between flux terms. The semivolatile nature of the Amazonian organic aerosol suggests a feedback in which warmer temperatures will partition SOA to the gas-phase, reducing their light scattering and thus potential to cool the region.

Thermal relaxation for particle systems in interaction with several bosonic heat reservoirs

The present thesis is concerned with the study of a quantum physical system composed of a small particle system (such as a spin chain) and several quantized massless boson fields (as photon gasses or phonon fields) at positive temperature. The setup serves as a simplified model for matter in interaction with thermal "radiation" from different sources. Hereby, questions concerning the dynamical and thermodynamic properties of particle-boson configurations far from thermal equilibrium are in the center of interest. We study a specific situation where the particle system is brought in contact with the boson systems (occasionally referred to as heat reservoirs) where the reservoirs are prepared close to thermal equilibrium states, each at a different temperature. We analyze the interacting time evolution of such an initial configuration and we show thermal relaxation of the system into a stationary state, i.e., we prove the existence of a time invariant state which is the unique limit state of the considered initial configurations evolving in time. As long as the reservoirs have been prepared at different temperatures, this stationary state features thermodynamic characteristics as stationary energy fluxes and a positive entropy production rate which distinguishes it from being a thermal equilibrium at any temperature. Therefore, we refer to it as non-equilibrium stationary state or simply NESS. The physical setup is phrased mathematically in the language of C*-algebras. The thesis gives an extended review of the application of operator algebraic theories to quantum statistical mechanics and introduces in detail the mathematical objects to describe matter in interaction with radiation. The C*-theory is adapted to the concrete setup. The algebraic description of the system is lifted into a Hilbert space framework. The appropriate Hilbert space representation is given by a bosonic Fock space over a suitable L2-space. The first part of the present work is concluded by the derivation of a spectral theory which connects the dynamical and thermodynamic features with spectral properties of a suitable generator, say K, of the time evolution in this Hilbert space setting. That way, the question about thermal relaxation becomes a spectral problem. The operator K is of Pauli-Fierz type. The spectral analysis of the generator K follows. This task is the core part of the work and it employs various kinds of functional analytic techniques. The operator K results from a perturbation of an operator L0 which describes the non-interacting particle-boson system. All spectral considerations are done in a perturbative regime, i.e., we assume that the strength of the coupling is sufficiently small. The extraction of dynamical features of the system from properties of K requires, in particular, the knowledge about the spectrum of K in the nearest vicinity of eigenvalues of the unperturbed operator L0. Since convergent Neumann series expansions only qualify to study the perturbed spectrum in the neighborhood of the unperturbed one on a scale of order of the coupling strength we need to apply a more refined tool, the Feshbach map. This technique allows the analysis of the spectrum on a smaller scale by transferring the analysis to a spectral subspace. The need of spectral information on arbitrary scales requires an iteration of the Feshbach map. This procedure leads to an operator-theoretic renormalization group. The reader is introduced to the Feshbach technique and the renormalization procedure based on it is discussed in full detail. Further, it is explained how the spectral information is extracted from the renormalization group flow. The present dissertation is an extension of two kinds of a recent research contribution by Jak��i�� and Pillet to a similar physical setup. Firstly, we consider the more delicate situation of bosonic heat reservoirs instead of fermionic ones, and secondly, the system can be studied uniformly for small reservoir temperatures. The adaption of the Feshbach map-based renormalization procedure by Bach, Chen, Fr��hlich, and Sigal to concrete spectral problems in quantum statistical mechanics is a further novelty of this work.

Physical long-term health problems and mental comorbidity: evidence from Vietnam

OBJECTIVE: The mental health of children living in low-income countries remains a neglected research area despite the high burden of disease. This study is one of the first that examines the effects of long-term physical health problems on child mental health disorders in a low-income country and investigates whether this association is modified by the socio-economic status of the child's family. METHODS: Community-based cross-sectional survey of 975 eight-year-old children from 20 sites in Vietnam. Long-term physical health problems were measured by a caregiver report and included conditions such as anaemia, congenital malformation, physical disability and skin problems. Child mental disorders were assessed using the strengths and difficulties questionnaire (SDQ). Generalised estimating equations models were fitted to explore the association between long-term physical health problems and child mental disorders. RESULTS: Vietnamese children who suffer from long-term physical health problems have odds 2:1 times greater than children without long-term physical health problems of having a mental disorder (95% CI 1.2 to 3.6, p = 0.006). No significant interaction with socio-economic status was found. CONCLUSIONS: This study showed a high burden of mental disorders among physically ill children, re-enforcing the idea that there is "no health without mental health". While this association needs to be explored longitudinally, children with long-term health problems may be a visible group for targeted mental-health interventions.

Introductory Mathematics for Quantum Chemistry

An elementary discussion of some of the mathematics employed in studying Quantum Chemistry in a style appropriate for persons who have not taken advanced mathematical instruction.

Towards Accurate and Efficient Description of Excited States

Thesis (Ph.D.)--University of Washington, 2016-06

An investigation of nucleation events in a coastal urban environment in the southern hemisphere

The occurrence of and conditions favourable to nucleation were investigated at an industrial and commercial coastal location in Brisbane, Australia during five different campaigns covering a total period of 13 months. To identify potential nucleation events, the difference in number concentration in the size range 14-30 nm (N14-30) between consecutive observations was calculated using first-order differencing. The data showed that nucleation events were a rare occurrence, and that in the absence of nucleation the particle number was dominated by particles in the range 30-300 nm. In many instances, total particle concentration declined during nucleation. There was no clear pattern in change in NO and NO2 concentrations during the events. SO2 concentration, in the majority of cases, declined during nucleation but there were exceptions. Most events took place in summer, followed by winter and then spring, and no events were observed for the autumn campaigns. The events were associated with sea breeze and long-range transport. Roadside emissions, in contrast, did not contribute to nucleation, probably due to the predominance of particles in the range 50-100 nm associated with these emissions.

Determination of particle concentration in the breathing zone for four different types of office ventilation systems

Many factors affect the airflow patterns, thermal comfort, contaminant removal efficiency and indoor air quality at individual workstations in office buildings. In this study, four ventilation systems were used in a test chamber designed to represent an area of a typical office building floor and reproduce the real characteristics of a modern office space. Measurements of particle concentration and thermal parameters (temperature and velocity) were carried out for each of the following types of ventilation systems: a) conventional air distribution system with ceiling supply and return; b) conventional air distribution system with ceiling supply and return near the floor; c) underfloor air distribution system; and d) split system. The measurements aimed to analyse the particle removal efficiency in the breathing zone and the impact of particle concentration on an individual at the workstation. The efficiency of the ventilation system was analysed by measuring particle size and concentration, ventilation effectiveness and the Indoor/Outdoor ratio. Each ventilation system showed different airflow patterns and the efficiency of each ventilation system in the removal of the particles in the breathing zone showed no correlation with particle size and the various methods of analyses used.

Particle and gaseous emissions from compressed natural gas and ultralow sulphur diesel-fuelled buses at four steady engine loads

Exhaust emissions from thirteen compressed natural gas (CNG) and nine ultralow sulphur diesel in-service transport buses were monitored on a chassis dynamometer. Measurements were carried out at idle and at three steady engine loads of 25%, 50% and 100% of maximum power at a fixed speed of 60 kmph. Emission factors were estimated for particle mass and number, carbon dioxide and oxides of nitrogen for two types of CNG buses (Scania and MAN, compatible with Euro 2 and 3 emission standards, respectively) and two types of diesel buses (Volvo Pre-Euro/Euro1 and Mercedez OC500 Euro3). All emission factors increased with load. The median particle mass emission factor for the CNG buses was less than 1% of that from the diesel buses at all loads. However, the particle number emission factors did not show a statistically significant difference between buses operating on the two types of fuel. In this paper, for the very first time, particle number emission factors are presented at four steady state engine loads for CNG buses. Median values ranged from the order of 1012 particles min-1 at idle to 1015 particles km-1 at full power. Most of the particles observed in the CNG emissions were in the nanoparticle size range and likely to be composed of volatile organic compounds The CO2 emission factors were about 20% to 30% greater for the diesel buses over the CNG buses, while the oxides of nitrogen emission factors did not show any difference due to the large variation between buses.

Comparison of ultrafine particle release from hardcopy devices in emission test chambers and office rooms

The release of ultrafine particles (UFP) from laser printers and office equipment was analyzed using a particle counter (FMPS; Fast Mobility Particle Sizer) with a high time resolution, as well as the appropriate mathematical models. Measurements were carried out in a 1 m�� chamber, a 24 m�� chamber and an office. The time-dependent emission rates were calculated for these environments using a deconvolution model, after which the total amount of emitted particles was calculated. The total amounts of released particles were found to be independent of the environmental parameters and therefore, in principle, they were appropriate for the comparison of different printers. On the basis of the time-dependent emission rates, ���initial burst��� emitters and constant emitters could also be distinguished. In the case of an ���initial burst��� emitter, the comparison to other devices is generally affected by strong variations between individual measurements. When conducting exposure assessments for UFP in an office, the spatial distribution of the particles also had to be considered. In this work, the spatial distribution was predicted on a case by case basis, using CFD simulation.

Environmental monitoring of airborne nanoparticles

The aim of this work was to review the existing instrumental methods to monitor airborne nanoparticle in different types of indoor and outdoor environments in order to detect their presence and to characterise their properties. Firstly the terminology and definitions used in this field are discussed, which is followed by a review of the methods to measure particle physical characteristics including number concentration, size distribution and surface area. An extensive discussion is provided on the direct methods for particle elemental composition measurements, as well as on indirect methods providing information on particle volatility and solubility, and thus in turn on volatile and semivolatile compounds of which the particle is composed. A brief summary of broader considerations related to nanoparticle monitoring in different environments concludes the paper.

High-flux ceramic membranes with a nanomesh of metal oxide nanofibers

Traditional ceramic separation membranes, which are fabricated by applying colloidal suspensions of metal hydroxides to porous supports, tend to suffer from pinholes and cracks that seriously affect their quality. Other intrinsic problems for these membranes include dramatic losses of flux when the pore sizes are reduced to enhance selectivity and dead-end pores that make no contribution to filtration. In this work, we propose a new strategy for addressing these problems by constructing a hierarchically structured separation layer on a porous substrate using large titanate nanofibers and smaller boehmite nanofibers. The nanofibers are able to divide large voids into smaller ones without forming dead-end pores and with the minimum reduction of the total void volume. The separation layer of nanofibers has a porosity of over 70% of its volume, whereas the separation layer in conventional ceramic membranes has a porosity below 36% and inevitably includes dead-end pores that make no contribution to the flux. This radical change in membrane texture greatly enhances membrane performance. The resulting membranes were able to filter out 95.3% of 60-nm particles from a 0.01 wt % latex while maintaining a relatively high flux of between 800 and 1000 L/m2��h, under a low driving pressure (20 kPa). Such flow rates are orders of magnitude greater than those of conventional membranes with equal selectivity. Moreover, the flux was stable at approximately 800 L/m2��h with a selectivity of more than 95%, even after six repeated runs of filtration and calcination. Use of different supports, either porous glass or porous alumina, had no substantial effect on the performance of the membranes; thus, it is possible to construct the membranes from a variety of supports without compromising functionality. The Darcy equation satisfactorily describes the correlation between the filtration flux and the structural parameters of the new membranes. The assembly of nanofiber meshes to combine high flux with excellent selectivity is an exciting new direction in membrane fabrication.