New Intermediate band sulphide nanoparticles acting in the full visible light range spectra as an active photocatalyst

Nowadays one of the challenges of materials science is to find new technologies that will be able to make the most of renewable energies. An example of new proposals in this field are the intermediate-band (IB) materials, which promise higher efficiencies in photovoltaic applications (through the intermediate band solar cells), or in heterogeneous photocatalysis (using nanoparticles of them, for the light-induced degradation of pollutants or for the efficient photoevolution of hydrogen from water). An IB material consists in a semiconductor in which gap a new level is introduced [1], the intermediate band (IB), which should be partially filled by electrons and completely separated of the valence band (VB) and of the conduction band (CB). This scheme (figure 1) allows an electron from the VB to be promoted to the IB, and from the latter to the CB, upon absorption of photons with energy below the band gap Eg, so that energy can be absorbed in a wider range of the solar spectrum and a higher current can be obtained without sacrificing the photovoltage (or the chemical driving force) corresponding to the full bandgap Eg, thus increasing the overall efficiency. This concept, applied to photocatalysis, would allow using photons of a wider visible range while keeping the same redox capacity. It is important to note that this concept differs from the classic photocatalyst doping principle, which essentially tries just to decrease the bandgap. This new type of materials would keep the full bandgap potential but would use also lower energy photons. In our group several IB materials have been proposed, mainly for the photovoltaic application, based on extensively doping known semiconductors with transition metals [2], examining with DFT calculations their electronic structures. Here we refer to In2S3 and SnS2, which contain octahedral cations; when doped with Ti or V an IB is formed according to quantum calculations (see e.g. figure 2). We have used a solvotermal synthesis method to prepare in nanocrystalline form the In2S3 thiospinel and the layered compound SnS2 (which when undoped have bandgaps of 2.0 and 2.2 eV respectively) where the cation is substituted by vanadium at a ?10% level. This substitution has been studied, characterizing the materials by different physical and chemical techniques (TXRF, XRD, HR-TEM/EDS) (see e.g. figure 3) and verifying with UV spectrometry that this substitution introduces in the spectrum the sub-bandgap features predicted by the calculations (figure 4). For both sulphide type nanoparticles (doped and undoped) the photocatalytic activity was studied by following at room temperature the oxidation of formic acid in aqueous suspension, a simple reaction which is easily monitored by UV-Vis spectroscopy. The spectral response of the process is measured using a collection of band pass filters that allow only some wavelengths into the reaction system. Thanks to this method the spectral range in which the materials are active in the photodecomposition (which coincides with the band gap for the undoped samples) can be checked, proving that for the vanadium substituted samples this range is increased, making possible to cover all the visible light range. Furthermore it is checked that these new materials are more photocorrosion resistant than the toxic CdS witch is a well know compound frequently used in tests of visible light photocatalysis. These materials are thus promising not only for degradation of pollutants (or for photovoltaic cells) but also for efficient photoevolution of hydrogen from water; work in this direction is now being pursued.

On the charged particle drag acting on LAGEOS

A recent study by the authors points to Charged Particle Drag (CPD) as a contributor to revisit in the LAGEOS non-gravitational perturbations problem. Such perturbations must account for dynamical contributions in the order of pms−2 . The simulated effect takes into account: (i) spatial and temporal variations of the plasmatic parameters (temperature and concentration of the species), (ii) spacecraft potential variations caused by both the eclipse passages and variations in the parameters mentioned above, and (iii) solar and geomagnetic conditions. Furthermore, recent theoretical improvements concerning scattering drag overcome previous limitations allowing for a complete formulation of this effect. For each satellite the lifetime CPD instantaneous acceleration is computed. The plasmatic parameters have been obtained fromthe Sheffield Coupled Thermosphere-Ionosphere-Plasmasphere (SCTIP) semi-empirical model (up to the polar region), as well as alytical/empirical approximations based on spacecraft measurements for the auroral and polar regions. Results show that maximum amplitudes for LAGEOSI are larger than those for LAGEOS-II: −85 pms−2 and −70 pms−2 respectively. This is due to the almost (magnetically) polar orbit configuration of the first, producing larger combinations of plasmatic parameter values. High solar activity has a huge impact in the resulting LAGEOS accelerations: it yields a perfect modulation of the resulting acceleration with maximum amplitudes up to a factor of 10 when comparing low and high activity periods. On the other hand, the impact of the geomagnetic activity results into a reduction of the effect itself, probably due to a decrease in the hydrogen concentration for high energy input periods. The acceleration results will be used in a refined orbit computation in a subsequent investigation.