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.

Gold in Ophiolites

Ophiolites, as a class, have been currently under-estimated as potential gold targets, although they have been the subject of major scientific research. Their resources have also attracted investors producing Cr, Cu (massive sulphides), Co, Ni (laterites), industrial rocks and minerals (serpentinites, emeralds), etc. They are also potential PGE sources.

Geología de las ultramafitas pre-andinas de Tapo y Acobamba, Tarma, en la Cordillera Oriental de Perú

Ultramafic rocks occur scattered along a 300 km long NNW-SSE trending belt, parallel to the central Peruvian Andes in the Cordillera Oriental, from Tarma (Junín Dept.) to Huancapallac and Tingo María (Huánuco Dept.). The Tarma occurrences (Tapo and Acobamba) are dealt with here, as the first step of a broader research. The Tapo massif comprises strongly tectonised serpentinites with scarce peridotitic relics, amphibolites and podiform chromitites. It was overthrust on early Carboniferous metasedimentary rocks of the Andean basement (Ambo Group), and it shows evidences of a pre-Andean deformational history, not observed in the Ambo Group; the basal thrust plane is folded by the Andean tectonics. The two smaller Acobamba occurrences are also allochtonous and show similar tectonic features. Major and trace element composition of amphibolites point to a tholeiitic basalt (to picrobasalt) protolith, compatible with an ocean-ridge or ocean-island environment. Small podiform chromitite lenses and chromite disseminations also occur; they are strongly deformed, metamorphosed and overprinted by hydrothermal alteration related to deformation, and were the subject of small scale mining. The ores comprise mainly chromite, ferritchromite, spinel, magnetite, ilmenite and scarce sulphides, as well as the secondary minerals stichtite and nimite. Results of this work exclude current interpretations of the Tarma ultramafites as autochtonous igneous intrusives, and point to a new interpretation for their emplacement.