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.

Enhancing the thermomechanical behaviour of poly(phenylene sulphide) based composites via incorporation of covalently grafted carbon nanotubes

The thermal and thermomechanical properties of poly(phenylene sulphide) (PPS) based nanocomposites incorporating a polymer derivative covalently anchored onto single-walled carbon nanotubes (SWCNTs) were investigated. The grafted fillers acted as nucleating agents, increasing the crystallization temperature and degree of crystallinity of the matrix. They also enhanced its thermal stability, flame retardancy, glass transition (Tg) and heat deflection temperatures while reduced the coefficient of thermal expansion at temperatures below Tg. A strong rise in the thermal conductivity, Young?s modulus and tensile strength was found with increasing filler loading both in the glassy and rubbery states. All these outstanding improvements are ascribed to strong matrix-filler interfacial interactions combined with a compatibilization effect that results in very homogeneous SWCNT dispersion. The results herein offer useful insights towards the development of engineering thermoplastic/CNT nanocomposites for high-temperature applications.

Inorganic Nanoparticle-Modified Poly(Phenylene Sulphide)/ Carbon Fiber Laminates: Thermomechanical Behaviour

Carbon fiber (CF)-reinforced high-temperature thermoplastics such as poly(phenylene sulphide) (PPS) are widely used in structural composites for aerospace and automotive applications. The porosity of CF-reinforced polymers is a very important topic for practical applications since there is a direct correlation between void content and mechanical properties. In this study, inorganic fullerene-like tungsten disulphide (IF-WS2) lubricant nanoparticles were used to manufacture PPS/IF-WS2/CF laminates via melt-blending and hot-press processing, and the effect of IF-WS2 loading on the quality, thermal and mechanical behaviour of the hybrid composites was investigated. The addition of IF-WS2 improved fiber impregnation, resulting in lower degree of porosity and increased delamination resistance, compression and flexural properties; their reinforcement effect was greater at temperatures above the glass transition (Tg). IF-WS2 contents higher than 0.5 wt % increased Tg and the heat deflection temperature while reduced the coefficient of thermal expansion. The multiscale laminates exhibited higher ignition point and notably reduced peak heat release rate compared to PPS/CF. The coexistence of micro- and nano-scale fillers resulted in synergistic effects that enhanced the stiffness, strength, thermal conductivity and flame retardancy of the matrix. The results presented herein demonstrate that the IF-WS2 are very promising nanofillers to improve the thermomechanical properties of conventional thermoplastic/CF composites.

Integrated Pb- and S-isotope investigation of sulphide minerals from the early Archaean of southwest Greenland

We present high-spatial resolution secondary ion mass spectrometry (SIMS) measurements of Pb and S isotopes in sulphides from early Archaean samples at two localities in southwest Greenland. Secondary pyrite from a 3.71 Ga sample of magnetite-quartz banded iron formation in the Isua Greenstone Belt, which has previously yielded unradiogenic Pb consistent with its ancient origin, contains sulphur with a mass independently fractionated (MIF) isotope signature (Delta(33)S =+3.3 parts per thousand). This reflects the secondary mineralization of remobilized sedimentary S carrying a component modified by photochemical reactions in the early Archaean atmosphere. It further represents one of the most extreme positive excursions so far known from the early Archaean rock record. Sulphides from a quartz-pyroxene rock and an ultramafic boudin from the island of Akilia, in the Godth (a) over circle bsfjord, have heterogeneous and generally radiogenic Pb isotopic compositions that we interpret to represent partial re-equilibration of Pb between the sulphides and whole rocks during tectonothermal events at 3.6, 2.7 and 1.6 Ga. Both these samples have Delta(33)S=0 (within analytical error) and therefore show no evidence for MIF sulphur. These data are consistent with previous interpretations that the rock cannot be proven to have a sedimentary origin. Our study illustrates that SIMS S-isotope measurements in ancient rocks can be used to elucidate early atmospheric parameters because of the ability to obtain combined S and Pb-isotope data, but caution must be applied when using such data to infer protolith. When information from geological context, petrography and chronology (i.e. by Pb isotopes) is combined and fully evaluated, Delta(33)S signatures from sulphides and their geological significance can be interpreted with a higher degree of confidence. (c) 2005 Elsevier B.V All rights reserved.

A study of field emission from cadmium sulphide

It was decided to investigate field emission from cadmium sulphide because many workers have found that the agreement between theory and experiment for this material, and other semiconductors, is poor. An electron energy analyser, similar to those used in most of the previously reported experiments, was, therefore, built. The performance of the analyser was thoroughly investigated both theoretically and practically and the results of these investigations were used in conjunction with a tungsten emitter. Excellent agreement was obtained between the usually accepted total energy distribution for tungsten and the corresponding .distribution measured with the present analyser. A method of obtaining reliable cadmium sulphide emitter was developed. These emitters were then used in the analyser and it was found that the agreement between theory and experiment was poor. Previous explanations of the lack of agreement are considered and are found to be doubtful. The theory of field emission from semiconductors is reviewed and possible reasons for the discrepancy between theory and experiment are proposed. Finally, further experiments are described which should prove or disprove the conclusions arrived at in this work.

Sulphide ore minerals:surface chemical properties

The surfaces of iron-containing sulphide minerals were oxidised by a range of inorganic oxidants, and the resultant surface alteration products studied using various spectroscopic techniques. The characterisation of surface oxidation is relevant to the alteration of ores in nature and their behaviour during flotation and leaching, of importance to the metallurgical industry. The sulphides investigated included pyrite (FeS2), hexagonal pyrrhotine (Fe9S10), monoclinic pyrrhotine (Fe7Se), violarite (FeNi2S4), pentlandite ((FeiNi)9Se), chalcopyrite (CuFeS2) and arsenopyrite (FeAsS). The surfaces were oxidised by various methods including acid (sulphuric), alkali (ammonium hydroxide), hydrogen peroxide, steam, electrochemical and air/oxygen (in a low-temperature (150ºC) furnace), The surfaces were examined using surface sensitive chemical spectroscopic methods including x-ray photoelectron spectroscopy (ms), Auger electron spectroscopy (LES) and conversion electron Mössbauer spectroscopy (CEKS). Physical characterisation of the surfaces was undertaken using scanning electron microscopy (SM), spectral reflectance measurements and optical microscopy. Bulk characterisation of the sulphide minerals was undertaken using x-ray diffraction and electron microprobe techniques. Observed phases suggested to form in most of the sulphide surfaces include Fe204, Fe1-x0, Fe202, Fe00H, Fe(OH)3, with iron II & III oxy-sulphates. The iron sulphides show variable extents of oxidation, indicating pyrite to be the most stable. Violarite shows stability to oxidation, suggested to result from both its stable spinel crystal structure, and from the rapid formation of sulphur at the surface protecting the sub-surface from further oxidation. The phenomenon of sub-surface enrichment (in metals), forming secondary sulphides, is exhibited by pentlandite and chalcopyrite, forming violarite and copper sulphides respectively. The consequences of this enrichment with regard to processing and leaching are discussed. Arsenopyrite, often a hindrance in ore processing, exhibits the formation of arsenic compounds at the surface, the dissolution of which is discussed in view of the possible environmental hazard caused by the local pollution of water systems. The results obtained allow a characterisation of the sulphides in terms of their relative stability to oxidation, and an order of stability of the sulphide surfaces is proposed. Models were constructed to explain the chemical compositions of the surfaces, and the inter-relationships between the phases determined at the surface and in the sub-surface. These were compared to the thermo-chemically predicted phases shown in Eh/pH and partial pressure diagrams! The results are discussed, both in terms of the mineralogy and geochemistry of natural ores, and the implications for extraction and processing of these ore minerals.

Effects of hydrogen sulphide on the isolated perfused rat heart

Objectives: Hydrogen sulphide has been identified as a gas signalling molecule in the body, and has previously been shown to have vasorelaxant properties. The aim of the study was to investigate the effects of sodium hydrosulphide (NaHS), a hydrogen sulphide donor, on heart rate (HR), left ventricular developed pressure (LVDP) and coronary flow (CF) in the isolated perfused rat heart. Methods: A Langendorff isolated heart preparation was used to investigate the effect of a dose range of sodium hydrosulphide, in the presence and absence of inhibitors, on heart rate, left ventricular developed pressure and coronary flow. Results: Sodium hydrosulphide caused a significant decrease in heart rate at a concentration of 10-3 M (P <0.001). This decrease was partially inhibited by glibenclamide, a K ATP channel blocker (P <0.05); L-NAME, a nitric oxide synthase inhibitor (P <0.001), and methylene blue (P <0.001), but not by H-89, a protein kinase A inhibitor. Sodium hydrosulphide significantly increased coronary flow at concentrations of 10-4 - 10-3M (P <0.05). This response was significantly increased in the presence of L-NAME (P <0.001) and methylene blue (P <0.001), whereas H-89 inhibited the increase in coronary flow due to sodium hydrosulphide (P <0.001). Sodium hydrosulphide significantly decreased LVDP at all concentrations (P <0.001). In the presence of glibenclamide and H-89, the time period of the decrease in LVDP due to sodium hydrosulphide was extended (P <0.001), whereas methylene blue and L-NAME caused a significant reduction in the response to sodium hydrosulphide (P <0.05, P <0.01 respectively). Conclusion: Sodium hydrosulphide reduced heart rate and LVDP, and increased coronary flow in the isolated perfused rat heart; however, the mechanisms of action could not be fully elucidated.