Preparation of titania-based catalysts for formaldehyde photocatalytic oxidation from TiCl4 by the sol-gel method

Titania sols were prepared by acid hydrolysis of a TiCl4 precursor instead of titanium alkoxides. The effect of acid concentration on the particle size and stability of sol was investigated. Stable titania sols with mean particle size of 14 nm could be obtained when the H+/Ti molar ratio was 0.5. The titania sols were modified with Pt, SiO2, ZrO2, WO3 and MoO3 to prepare a series of modified catalysts, which were used for the photocatalytic oxidation of formaldehyde at 37 degreesC. They showed different photocatalytic activities due to the influence of the additives. Comparing with pure TiO2, the addition of silica or zirconia increased the photocatalytic activity, while the addition of Pt and MoO3 decreased the activity, and the addition Of WO3 had little effect on the activity. It is of great significance that the conversion of formaldehyde was increased up to 94% over the SiO2-TiO2 catalyst. The increased activity was partly due to higher surface area and porosity or smaller crystallite size. A comparison of our catalyst compositions with the literature in this field suggested that the difference in activity due to the addition of a second metal oxide maybe caused by the surface chemistry of the catalysts, particularly the acidity. (C) 2001 Elsevier Science B.V. All rights reserved.

Electrochemical performance of mixed ionic-electronic conducting oxides as anodes for solid oxide fuel cell

Mixed ionic-electronic conducting (MIEC) oxides, SrFeCo0.5Ox, SrCo0.8Fe0.2O3-delta and La0.6Sr0.4Fe0.8Co0.2O3-delta have been synthesized and prepared on yttria-stabilized zirconia as anodes for solid oxide fuel cells. Power output measurements show that the anodes composed of such kinds of oxides exhibit modest electrochemical activities to both H-2 and CH4 fuels, giving maximum power densities of around 0.1 W/cm(2) at 950 degrees C. Polarization and AC impedance measurements found that large activation overpotentials and ohmic resistance drops were the main causes for the relative inferior performance to the Ni-YSZ anode. While interlayered with an Ni-YSZ anode, a significant improvement in the electrochemical performance was observed. in particular, for the SrFeCo0.5Ox oxide interlayered Ni-YSZ anode, the maximum power output reaches 0.25 W/cm2 on CH,, exceeding those of both SrFeCo0.5Ox and the Ni-YSZ, as anodes alone. A synergetic effect of SrFeCo0.5Ox and the Ni-YSZ has been observed. Future work is needed to examine the long-term stability of MIEC oxide electrodes under a very reducing environment. (C) 1999 Elsevier Science B.V. All rights reserved.

Structure and impedance of ZrO2 doped with SC2O3 and CeO2

Scandia and ceria doped zirconia samples, with 10 mol% SC2O3 and different content of CeO2, were synthesized and characterized. The XRD results depict that the sintered samples have a cubic phase structure. However, Raman spectra show that besides the main cubic phase, a secondary phase is also present in the sintered samples. The addition of CeO2 can raise the content of the cubic phase, but the minor metastable tetragonal phase (t'-phase) exists even at the CeO2 content as high as 10 mol%. The near-UV Raman spectra indicate that the deformed tetragonal structure predominates at the grain boundary. The addition of CeO2 can reduce the impurity at grain boundary, and no impurity can be found by near-UV Raman spectroscopy at the grain boundary of the samples with high CeO2 content. The impedance measurements show that with the increase of CeO2 content, the impedance of grain boundary decreases and the bulk impedance increases. The low impedance of grain boundary can be attributed to the formation of a clean grain boundary upon CeO2 doping, and the increase of the bulk impedance is due to the blocking effect of the large Ce(IV) ions. (c) 2005 Elsevier B.V All rights reserved.

Energy-dependent in-situ small-angle x-ray scattering study of nano-ceramics

R Winter, D Le Messurier, CM Martin; Cryst Rev 12 (2006) 3 Sponsorship: EPSRC, CCLRC, Pilkington

Avaliação das propriedades mecânicas e microestrutura de um ionómero de vidro experimental reforçado com nano partículas

Projeto de Pós-Graduação/Dissertação apresentado à Universidade Fernando Pessoa como parte dos requisitos para obtenção do grau de Mestre em Medicina Dentária

Steam reforming of model compounds and fast pyrolysis bio-oil on supported noble metal catalysts

The production of hydrogen by steam reforming of bio-oils obtained from the fast pyrolysis of biomass requires the development of efficient catalysts able to cope with the complex chemical nature of the reactant. The present work focuses on the use of noble metal-based catalysts for the steam reforming of a few model compounds and that of an actual bio-oil. The steam reforming of the model compounds was investigated in the temperature range 650-950 degrees C over Pt, Pd and Rh supported on alumina and a ceria-zirconia sample. The model compounds used were acetic acid, phenol, acetone and ethanol. The nature of the support appeared to play a significant role in the activity of these catalysts. The use of ceria-zirconia, a redox mixed oxide, lead to higher H-2 yields as compared to the case of the alumina-supported catalysts. The supported Rh and Pt catalysts were the most active for the steam reforming of these compounds, while Pd-based catalysts poorly performed. The activity of the promising Pt and Rh catalysts was also investigated for the steam reforming of a bio-oil obtained from beech wood fast pyrolysis. Temperatures close to, or higher than, 800 degrees C were required to achieve significant conversions to COx and H-2 (e.g., H-2 yields around 70%). The ceria-zirconia materials showed a higher activity than the corresponding alumina samples. A Pt/ceria-zirconia sample used for over 9 h showed essentially constant activity, while extensive carbonaceous deposits were observed on the quartz reactor walls from early time on stream. In the present case, no benefit was observed by adding a small amount of O-2 to the steam/bio-oil feed (autothermal reforming, ATR), probably partly due to the already high concentration of oxygen in the bio-oil composition. (c) 2005 Elsevier B.V. All rights reserved.

An investigation of catalysts for the on board synthesis of NH3. A possible route to low temperature NOx reduction for lean-burn engines

Platinum group metal catalysts have been investigated for the formation of NH3 from NO + H-2 at low temperatures in the absence and presence of CO. Although CO inhibits the formation of NH3, substantial amounts are still observed with a Pt catalyst. By combining Pt with a support (ceria-zirconia) that has low temperature NOx storage characteristics it has been shown in transient experiments that NH3 can be formed and stored in situ under rich conditions, and may then be used to reduce NOx under lean burn conditions.

The preparation and properties of coprecipitated Cu-Zr-Y and Cu-Zr-La catalysts used for the steam reforming of methanol

A series of Cu-zirconia catalysts containing various additives (Y2O3, La2O3, Al2O3 and CeO2) have been prepared by coprecipitation and their activities and stabilities under operating conditions have been obtained for the steam reforming of methanol. It has been found that an yttria-promoted catalyst containing 30 mol% Cu and 20 mol% of Y2O3 is not only very active but is also very stable under reaction conditions. The yttria appears to stabilise a high copper surface area and may also have a slight promotional effect on the copper. The results obtained with this material compare very favourably with data for the best catalysts reported in the literature. (C) 2007 Published by Elsevier B.V.

Investigation of the effect of the preparation method on the activity and stability of Au/CeZrO4 catalysts for the low temperature water gas shift reaction

The impact of the preparation method on the activity and stability of gold supported on ceria-zirconia low temperature water-gas shift (WGS) catalysts have been investigated. The influence of the gold deposition method, nature of the gold precursor, nature of the washing solution, drying method, Ce: Zr ratio of the support and sulfation of the support have been evaluated. The highest activity catalysts were obtained using a support with a Ce: Zr mole ratio 1: 1, HAuCl4 as the gold precursor deposited via deposition precipitation using sodium carbonate as the precipitation agent and the catalyst washed with water or 0.1 M NH4OH solution. In addition, the drying used was found to be critical with drying under vacuum at room temperature found to be most effective.

The role of Na surface species on oxygen charge transfer in the Pt/YSZ system

The role of sodium surface species in the modification of a platinum (Pt) catalyst film supported on 8 mol% yttria-stabilised-zirconia (YSZ) was investigated under a flow of 20 kPa oxygen at 400 °C. Cyclic and linear sweep voltammetry were used to investigate the kinetics of the oxygen charge transfer reaction. The Pt/YSZ systems of both ‘clean’ and variable-coverage sodium-modified catalyst surfaces were also characterised using SEM, XPS and work function measurements using the Kelvin probe technique.

Samples with sodium coverage from 0.5 to 100% were used. It was found that sodium addition modifies the binding energy of oxygen onto the catalyst surface. Cyclic voltammetry experiments showed that higher overpotentials were required for oxygen reduction with increasing sodium coverage. In addition, sodium was found to modify oxygen storage and/or adsorption and diffusion increasing current densities at higher cathodic overpotential. Ex situ XPS measurements showed the presence of sodium hydroxide, carbonate and/or oxide species on the catalyst surface, while the Kelvin probe technique showed a decrease of approximately 250 meV in the work function of samples with more than 50% sodium coverage (compared to a nominally ‘clean’ sample).

Measuring oxygen reduction/evolution reactions on the nanoscale

The efficiency of fuel cells and metal-air batteries is significantly limited by the activation of oxygen reduction and evolution reactions. Despite the well-recognized role of oxygen reaction kinetics on the viability of energy technologies, the governing mechanisms remain elusive and until now have been addressable only by macroscopic studies. This lack of nanoscale understanding precludes optimization of material architecture. Here, we report direct measurements of oxygen reduction/evolution reactions and oxygen vacancy diffusion on oxygen-ion conductive solid surfaces with sub-10 nm resolution. In electrochemical strain microscopy, the biased scanning probe microscopy tip acts as a moving, electrocatalytically active probe exploring local electrochemical activity. The probe concentrates an electric field in a nanometre-scale volume of material, and bias-induced, picometre-level surface displacements provide information on local electrochemical processes. Systematic mapping of oxygen activity on bare and platinum-functionalized yttria-stabilized zirconia surfaces is demonstrated. This approach allows direct visualization of the oxygen reduction/evolution reaction activation process at the triple-phase boundary, and can be extended to a broad spectrum of oxygen-conductive and electrocatalytic materials.

Deactivation mechanism of a Au/CeZrO4 catalyst during a low-temperature water gas shift reaction

On-stream deactivation during a water gas shift (WGS) reaction over gold supported on a ceria-zirconia catalyst was examined. Although the fresh catalyst has very high low temperature (<200 degrees C) for WGS activity, a significant loss of CO conversion is found under steady-state operations over hours. This has been shown to be directly related to the concentration of water in the gas phase. The same catalyst also undergoes thermal deactivation above 250 degrees C, and using a combined experimental and theoretical approach, a common deactivation mechanism is proposed. In both cases, the gold nanoparticles, which are found under reaction conditions, are thought to detach from the oxide support either through hydrolysis, <200 degrees C, or thermally, > 200 degrees C. This process reduces the metal-support interaction, which is considered to be critical in determining the high activity of the catalyst.

The influence of high-temperature sintering on microstructure and mechanical properties of free-standing APS CeO-YO -ZrO coatings

In this study, ceria-yttria co-stabilized zirconia (CYSZ) free-standing coatings, deposited by air plasma spraying (APS), were isothermally annealed at 1315 °C in order to explore the effect of sintering on the microstructure and the mechanical properties (i.e., hardness and Young's modulus). To this aim, coating microstructure, before and after heat treatment, was analyzed using scanning electron microscopy, and image analysis was carried out in order to estimate porosity fraction. Moreover, Vickers microindentation and depth-sensing nanoindentation tests were performed in order to study the evolution of hardness and Young's modulus as a function of annealing time. The results showed that thermal aging of CYSZ coatings leads to noticeable microstructural modifications. Indeed, the healing of finer pores, interlamellar, and intralamellar microcracks was observed. In particular, the porosity fraction decreased from ~10 to ~5% after 50 h at 1315 °C. However, the X-ray diffraction analyses revealed that high phase stability was achieved, as no phase decomposition occurred after thermal aging. In turn, both the hardness and Young's modulus increased, in particular, the increase in stiffness (with respect to "as produced" samples) was equal to ~25%, whereas the hardness increased to up to ~60%. © 2010 Springer Science+Business Media, LLC.

Patterning and switching of nano-size ferroelectric memory cells

A "top-down" approach using a-beam lithography and a "bottom-up" one using self-assembly methods were used to fabricate ferroelelectric Pb(Zr,Ti)O-3, SrBi2Ta2O9 and BaTiO3 nanostructures with lateral sizes in the range of 30 nm to 100 nm. Switching of single sub-100 nm cells was achieved and piezoelectric hysteresis loops were recorded using a scanning force microscope working in piezoresponse mode. The piezoelectricity and its hysteresis acquired for 100 nm PZT cells demonstrate that a further decrease in lateral size under 100 nm appears to be possible and that the size effects are not fundamentally limiting on increase density of non-volatile ferroelectric memories in the Gbit range.

Re-dispersion of gold supported on a ‘mixed’ oxide support

The ability to reactivate, stabilize and increase the lifetime of gold catalysts by dispersing large, inactive gold nanoparticles to smaller nanoparticles provides an opportunity to make gold catalysts more practical for industrial applications. Previously it has been demonstrated that mild treatment with iodomethane (CH3I) (J. Am. Chem. Soc., 2009, 131, 6973; Angew. Chem. Int. Ed., 2011, 50, 8912) was able to re-disperse gold on carbon and metal oxide supports. In the current work, we show that this technique can be applied to re-disperse gold on a ‘mixed’ metal oxide, namely a mechanical mixture of ceria, zirconia and titania. Characterization was conducted to gage the impact of the iodomethane (CH3I) treatment on a previously sintered catalyst.