Vanadium-Doped In and Sn Sulphides: Photocatalysts able to use the whole visible light spectrum

Using photocatalysis for energy applications depends, more than for environmental purposes or selective chemical synthesis, on converting as much of the solar spectrum as possible; the best photocatalyst, titania, is far from this. Many efforts are pursued to use better that spectrum in photocatalysis, by doping titania or using other materials (mainly oxides, nitrides and sulphides) to obtain a lower bandgap, even if this means decreasing the chemical potential of the electron-hole pairs. Here we introduce an alternative scheme, using an idea recently proposed for photovoltaics: the intermediate band (IB) materials. It consists in introducing in the gap of a semiconductor an intermediate level which, acting like a stepstone, allows an electron jumping from the valence band to the conduction band in two steps, each one absorbing one sub-bandgap photon. For this the IB must be partially filled, to allow both sub-bandgap transitions to proceed at comparable rates; must be made of delocalized states to minimize nonradiative recombination; and should not communicate electronically with the outer world. For photovoltaic use the optimum efficiency so achievable, over 1.5 times that given by a normal semiconductor, is obtained with an overall bandgap around 2.0 eV (which would be near-optimal also for water phtosplitting). Note that this scheme differs from the doping principle usually considered in photocatalysis, which just tries to decrease the bandgap; its aim is to keep the full bandgap chemical potential but using also lower energy photons. In the past we have proposed several IB materials based on extensively doping known semiconductors with light transition metals, checking first of all with quantum calculations that the desired IB structure results. Subsequently we have synthesized in powder form two of them: the thiospinel In2S3 and the layered compound SnS2 (having bandgaps of 2.0 and 2.2 eV respectively) where the octahedral cation is substituted at a â?10% level with vanadium, and we have verified that this substitution introduces in the absorption spectrum the sub-bandgap features predicted by the calculations. With these materials we have verified, using a simple reaction (formic acid oxidation), that the photocatalytic spectral response is indeed extended to longer wavelengths, being able to use even 700 nm photons, without largely degrading the response for above-bandgap photons (i.e. strong recombination is not induced) [3b, 4]. These materials are thus promising for efficient photoevolution of hydrogen from water; work on this is being pursued, the results of which will be presented.

Sewage sludge gasification. Dolomite performance under different operating conditions

Gasification is a technology that can replace traditional management alternatives used up to date to deal with this waste (landfilling, composting and incineration) and which fulfils the social, environmental and legislative requirements. The main products of sewage sludge gasification are permanent gases (useful to generate energy or to be used as raw material in chemical synthesis processes), liquids (tars) and char. One of the main problems to be solved in gasification is tar production. Tars are organic impurities which can condense at relatively high temperatures making impossible to use the produced gases for most applications. This work deals with the effect of some primary tar removal processes (performed inside the gasifier) on sewage sludge gasification products. For this purpose, analysis of the gas composition, tar production, cold gas efficiency and carbon conversion were carried out. The tests were performed with air in a laboratory scale plant consisting mainly of a bubbling bed gasifier. No catalyzed and catalyzed (10% wt of dolomite in the bed and in the feeding) tests were carried out at different temperatures (750ºC, 800ºC and 850ºC) in order to know the effect of these parameters in the gasification products. As far as tars were concerned, qualitative and quantitative tar composition was determined. In all tests the Equivalence Ratio (ER) was kept at 0.3. Temperature is one of the most influential variables in sewage sludge gasification. Higher temperatures favoured hydrogen and CO production while CO2 content decreased, which might be partially explained by the effect of the cracking, Boudouard and CO2 reforming reactions. At 850ºC, cold gas efficiency and carbon conversion reached 49% and 76%, respectively. The presence of dolomite as catalyst increased the production of H2 reaching contents of 15.5% by volume at 850 °C. Similar behaviour was found for CO whereas CO2 and CnHm (light hydrocarbons) production decreased. In the presence of dolomite, a tar reduction of up to 51% was reached in comparison with no catalyzed tests, as well as improvements on cold gas efficiency and carbon conversion. Several assays were developed in order to test catalyst performance under more rough gasification conditions. For this purpose, the throughput value (TR), defined as kg sludge “as received” fed to the gasifier per hour and per m2 of cross sectional area of the gasifier, was modified. Specifically, the TR values used were 110 (reference value), 215 and 322 kg/h·m2. When TR increased, the H2, CO and CH4 production decreased while the CO2 and the CnHm production increased. Tar production increased drastically with TR during no catalysed tests what is related to the lower residence time of the gas inside the reactor. Nevertheless, even at TR=322 kg/h·m2, tar production decreased by nearly 50% with in-bed use of dolomite in comparison with no catalyzed assays under the same operating conditions. Regarding relative tar composition, there was an increase in benzene and naphthalene content when temperature increased while the content of the rest of compounds decreased. The dolomite seemed to be effective all over the range of molecular weight studied showing tar removal efficiencies between 35-55% in most cases. High values of the TR caused a significant increase in tar production but a slight effect on tar composition.

Photovoltaic LiNbO3particles: Applications to Biomedicine/Biophotonics

Recently, a novel method to trap and pattern ensembles of nanoparticles has been proposed and tested. It relies on the photovoltaic (PV) properties of certain ferroelectric crystals such as LiNbO3 [1,2]. These crystals, when suitably doped, develop very high electric fields in response to illumination with light of suitable wavelength. The PV effect lies in the asymmetrical excitation of electrons giving rise to PV currents and associated space-charge fields (photorefractive effect). The field generated in the bulk of the sample propagates to the surrounding medium as evanescent fields. When dielectric or metal nanoparticles are deposited on the surface of the sample the evanescent fields give rise to either electrophoretic or dielectrophoretic forces, depending on the charge state of the particles, that induce the trapping and patterning effects [3,4]. The purpose of this work has been to explore the effects of such PV fields in the biology and biomedical areas. A first work was able to show the necrotic effects induced by such fields on He-La tumour cells grown on the surface of an illuminated iron-doped LiNbO3 crystal [5]. In principle, it is conceived that LiNbO3 nanoparticles may be advantageously used for such biomedical purposes considering the possibility of such nanoparticles being incorporated into the cells. Previous experiments using microparticles have been performed [5] with similar results to those achieved with the substrate. Therefore, the purpose of this work has been to fabricate and characterize the LiNbO3 nanoparticles and assess their necrotic effects when they are incorporated on a culture of tumour cells. Two different preparation methods have been used: 1) mechanical grinding from crystals, and 2) bottom-up sol-gel chemical synthesis from metal-ethoxide precursors. This later method leads to a more uniform size distribution of smaller particles (down to around 50 nm). Fig. 1(a) and 1(b) shows SEM images of the nanoparticles obtained with both method. An ad hoc software taking into account the physical properties of the crystal, particullarly donor and aceptor concentrations has been developped in order to estimate the electric field generated in noparticles. In a first stage simulations of the electric current of nanoparticles, in a conductive media, due to the PV effect have been carried out by MonteCarlo simulations using the Kutharev 1-centre transport model equations [6] . Special attention has been paid to the dependence on particle size and [Fe2+]/[Fe3+]. First results on cubic particles shows large dispersion for small sizes due to the random number of donors and its effective concentration (Fig 2). The necrotic (toxicity) effect of nanoparticles incorporated into a tumour cell culture subjected to 30 min. illumination with a blue LED is shown in Fig.3. For each type of nanoparticle the percent of cell survival in dark and illumination conditions has been plot as a function of the particle dilution factor. Fig. 1a corresponds to mechanical grinding particles whereas 1b and 1c refer to chemically synthesized particles with two oxidation states. The light effect is larger with mechanical grinding nanoparticles, but dark toxicity is also higher. For chemically synthesized nanoparticles dark toxicity is low but only in oxidized samples, where the PV effect is known to be larger, the light effect is appreciable. These preliminary results demonstrate that Fe:LiNbO· nanoparticles have a biological damaging effect on cells, although there are many points that should be clarified and much space for PV nanoparticles optimization. In particular, it appears necessary to determine the fraction of nanoparticles that become incorporated into the cells and the possible existence of threshold size effects. This work has been supported by MINECO under grant MAT2011-28379-C03.