Au-Cu/SBA(Ti) based catalysts for photocatalytic applications

Comunicación a congresoIn this work, it has been synthesized several Au and Au-Cu alloy photocatalysts supported on two different mesoporous supports: a non-commercial SBA-15 and a post-synthesis TiO2 modified SBA-15 (TiSBA-15), with which a high dispersion of TiO2 species have been achieved maintaining the SBA-15 structure. In addition, it has also been obtained highly dispersed Au nanoparticles confined in SBA-15 pore channels, as can be observed in Figure 1. The photocatalysts have been preliminary tested in the preferential CO oxidation in a H2-rich stream (CO-PROX) at room temperature and atmospheric pressure under simulated solar light irradiation. In spite of the very low gold and copper loading (1.5 wt% and 0.5wt% respectively), the catalysts resulted active and selective in the low temperature photo-CO-PROX.Universidad de Málaga, Campus de Excelencia Internacional Andalucía Tec

Nanoestructuras de ceria-titania para fotodegradar azul de metileno con luz solar simulada

En los últimos años la protección ambiental y el uso de fuentes de energía renovables son dos objetivos principales en la investigación química. La energía solar se puede aprovechar para la degradación fotocatalítica de moléculas orgánicas contaminantes, hormonas o medicamentos, tanto en el aire, en el agua, como en las superficies, porque la luz solar es capaz de descomponerlas [1]. A pesar de la gran cantidad de aplicaciones fotocatalíticas de la titania (TiO2), fotocatalizador no tóxico, de bajo costo y muy prometedor [2], hay algunos factores críticos que limitan su fotoactividad. El principal es el valor de su salto de energía, que limita su uso como fotocatalizador en la región UV del espectro. Con el objetivo principal de extender su uso a la región visible del espectro, en literatura se ha propuesto el depósito de metales nobles en su superficie, modificaciones superficiales, así como el dopaje con iones de metales de transición o elementos de tierras raras. En este sentido, el uso de ceria (CeO2) ha atraído una gran atención debido a propiedades como su biocompatibilidad, inercia química así como su actividad en reacciones de oxidación, relacionada con la formación vacantes de oxígeno en su superficie [3]. Se ha comprobado que el sistema oxídico mixto CeO2-TiO2 es más fotoactivo que la titania pura debido a la disminución del salto de energía y a la mejora en la movilidad de los excitones. Este trabajo tiene como objetivo desarrollar fotocatalizadores basados en nanoestructuras de titania que sean activas en el visible, dopando la matriz de titania con cerio. Principalmente se pretende evaluar tanto el papel del cerio como la morfología del nanomaterial en la respuesta fotocatalítica bajo luz UV y solar.Universidad de Málaga. Campus de Excelencia Internacional Andalucía Tech

X-ray powder diffraction quantitative analysis of anamorphous SiO2–poly(methyl methacrylate) nanocomposite

Quantification of individual phases within a multiphase amorphous material has been achieved using a newly developed technique based on X-ray powder diffraction. The quantification method was developed during a study of an amorphous silica-poly(methyl methacrylate) (SiO2-PMMA) hybrid nanocomposite. The efficiency of the method as a quantifying tool for individual phases was demonstrated for samples of SiO2-PMMA prepared either by polymerization of methyl methacrylate in the presence of amorphous SiO2 or by mechanically mixing known quantities of the individual and pre-prepared SiO2 and PMMA materials. The weight percentages of amorphous SiO2 in the nanocomposites as determined by application of the new technique were analogously found to be 29%, a result that was supported by thermogravimetric analysis and helium picnometry measurements

A qualitative and quantitative investigation of structural morphology in the neonatal ilium

Cortical and trabecular bone characteristics can be used to make predictions regarding previous loading regimes and developmental milestones which a bone has encountered. This has led to the suggestion that in the adult pelvis, bone patterning is related to the remodeling forces generated during bipedal locomotion. However, during the neonatal period the pelvic complex is non-load bearing, therefore, structural organisation of the ilium cannot reflect direct stance related forces. This study considers the cortical and trabecular bone structure in the ilium of the fetal and newborn infant, a structural configuration which until now has remained largely neglected in the literature. Only recently, with the advent of imaging modalities, has a greater insight and understanding of previously unexplored human bone structural composition and developing bone structure been made possible. In this study, multiple imaging techniques were applied to establish the optimal modality for application to the assessment of bone microstructure. Plain plate macroradiography and micro-computed tomography were identified as the gold standard imaging modalities for bone structural analysis for respective qualitative and quantitative assessment. These techniques were applied to gain a perspective of bone form from a sample of fetal and neonatal ilia selected from the Scheuer collection of juvenile remains. Initially, qualitative analysis highlighted consistent and well-defined patterns of cortical and trabecular bone organisation within the fetal and neonatal ilium, which corresponded with previously recognised regions in the adult that have been attributed directly to forces associated with bipedal locomotion. This was highly unexpected as the early developmental ilium is non-load bearing. Subsequently, quantification of the neonatal cortical and trabecular structure reinforced radiographic observations by identifying regions of significant architectural arrangement. Further investigation of this precocious patterning led to a revised proposal for the mode of growth in the human ilium during the neonatal developmental period. Analysis revealed statistically significant differences in regional trabecular characteristics and cortical thicknesses which have formed the basis of a proposed growth model for the ilium. The presence of ‘progressive growth regions’ and ‘restricted growth regions’ which appear to relate to metaphyseal and non-metaphyseal borders of the ilium have been demonstrated. Analysis of the early iliac bone pattern is important for understanding the relationship between trabecular bone patterning and cortical bone structure during the earliest stages of development in response to the specific functional forces acting during this period. It is suggested that the seemingly organised rudimentary scaffold observed in the early developmental ilium may be attributable to early ossification patterning, non-weight bearing anatomical interactions or even to a predetermined genetic blueprint. It must also be postulated that whilst the observed patterning may be indicative of a predetermined inherent template, early non-load bearing locomotive influences may subsequently be superimposed upon this scaffolding and perhaps reinforced and likely remodelled at a later age. Ultimately, the analysis of this fundamental primary pattern has core implications for understanding the earliest changes in iliac trabecular architecture and provides a baseline insight into future ontogenetic development and bipedal capabilities. Finally, the structural data and statistical analysis presented challenge the current concept of implied centrifugal ossification within the human ilium and present evidence of an alternative pattern of ossification that is largely dictated and controlled by basic anatomical principles.EThOS - Electronic Theses Online ServiceLeng TrustWenner-Gren FoundationBiotechnology and Biological Sciences Research CouncilGBUnited Kingdo

The physics, dosimetry and microdosimetry of boron neutron capture therapy

A validated experimental and numerical procedure is described detailing macroscopic and microscopic dose calculations forming the basis of a protocol for the pre-clinical biological characterisation of the University of Birmingham’s BNCT facility. Fundamental reference dosimetric measurements have been carried out at the University of Birmingham’s accelerator based NCT facility and the Massachusetts Institute of Technology (MIT) research reactor to characterise macroscopic and microscopic doses and derive correction factors for the irradiation of V79 cells incubated in boric acid and irradiated as monolayers. On and off-axis thermal neutron, fast neutron and photon doses have been measured and calculated with standard macroscopic dosimetry techniques (foils and ion chambers) from which normalised MCNPX calculations are used to derive perturbation factors and off-axis corrections for cell flask irradiations. Microdosimetric correction factors are calculated for the boron dose component using Monte Carlo methods to simulate lithium ion and alpha particle tracks in semi-stochastic geometries representative of cell monolayer irradiations, incubated in a medium with 50ppm boric acid. Further simulations of recoil protons from nitrogen capture reactions allow for the calculation of correction factors for the non-uniform distribution of the nitrogen dose at the cellular level.EThOS - Electronic Theses Online ServiceGBUnited Kingdo

Ceria–zirconia-copper oxide catalysts for CO removal from H2-rich streams under PEMFC operating conditions

On-board hydrogen production from hydrocarbons or alcohols has been proposed as the most efficient process to obtain hydrogen for feeding proton-exchange membrane fuel cells (PEMFCs). However, the gas produced after reforming and water gas-shift processes still presents in most cases a relatively high CO concentration, that disallows efficient handling of the fuel by the Pt anode usually employed in the PEMFCs. Preferential oxidation of carbon monoxide (CO-PROX) has been recognized as one of the most straightforward and cost-effective methods to achieve acceptable CO concentrations (<10 ppm). Among different types of catalysts for the PROX reaction, those based on Ce-Zr-Cu oxides 1-3 have shown promising properties in terms of activity, selectivity and resistance to CO2 and H2O. In this work, a series of Ce–Zr–Cu mixed oxide systems, with different atomic ratios among cations, were prepared by slow co-precipitation with the aim to investigate the influence of the presence of very small amounts of zirconium on the performances of these three-component catalysts. The activity of these materials was evaluated in the CO preferential oxidation in hydrogen-rich gas stream (1.2% CO, 1.2% O2, 50% H2, He balance) in the absence and presence of CO2 and H2O, in the 40-190°C temperature range. Correlations between catalytic activity and physico-chemical properties of the materials were made by X-ray Powder Diffraction (XRPD), N2 physisorption, Temperature-Programmed Reduction (H2-TPR), X-ray Photoelectron Spectroscopy (XPS)

Scanning probe microscopy of poly-atomic molecules

This thesis presents studies on the adsorption of chlorobenzene using STS, non-local desorption of chlorobenzene and the atomic manipulation of the PCB molecule using STM. The atomic manipulation of the mucin molecule on HOPG surfaces under different conditions has also been investigated. Chlorobenzene adsorbate on the Si(111)-(7×7) surface has been investigated using STS. The missing rest atom state at -0.8 V confirmed the rest atom involvement in the bonding geometry. Two adsorbate states located at -1.3 V and +1 to +2 V have been identified. The effect of the surface step and the temperature on the non-local chlorobenzene desorption process has been investigated. Different reactions generated by STM of the PCB molecule on the Si(111)-(7×7) surface have been studied. While molecular desorption is maximized by electron injection into the chemisorbed molecular ring at low voltage, injection into the physisorbed molecular ring at high voltage favours the reconfiguration of the bonding. The mucin molecule has been studied by AFM and STM. An unraveling manipulation has been achieved over a folded mucin polymer on the bare HOPG surface. Enhanced mucin-substrate binding has also been achieved in the liquid state on the size-selected Au55 cluster-decorated HOPG surface.EThOS - Electronic Theses Online ServiceGBUnited Kingdo

Mesoporous silica nanoparticles with tunable pore size for tailored gold nanoparticles

The aim of this paper was to verify a possible correlation between the pore-size of meso- porous silica nanoparticles (MSNs) and the sizes of gold nanoparticles (AuNPs) obtained by an impreg- nation of gold(III) chloride hydrate solution in the MSNs, followed by a specific thermal treatment. Mesoporous silica nanoparticles with tunable pore diameter were synthesized via a surfactant-assisted method. Tetraethoxysilane as silica precursor, cetyl- trimethylammonium bromide (CTAB) as surfactant and toluene as swelling agent were used. By varying the CTAB–toluene molar ratio, the average dimension of the pores could be tuned from 2.8 to 5.5 nm. Successively, thiol groups were grafted on the surface of the MSNs. Finally, the thermal evolution of the gold salt, followed by ‘‘in situ’’ X-ray powder diffraction (XRPD) and thermogravimetric analysis (TGA), revealed an evident correlation among the degradation of the thiol groups, the pore dimension of the MSNs and the size of the AuNPs. The samples were characterized by means of nitrogen adsorption– desorption, transmission electron microscopy, small- angle X-ray scattering, XRPD ‘‘in situ’’ by synchro- tron radiation, and ‘‘ex situ’’ by conventional tech- niques, diffuse reflectance infrared Fourier transform spectroscopy, and TGA