Among solution-processed nanocrystals containing environmentally benign elements, bismuth sulfi de (Bi 2 S 3 ) is a very promising n-type semiconductor for solar energy conversion. Despite the prompt success in the fabrication of optoelectronic devices deploying Bi 2 S 3 nanocrystals, the limited understanding of electronic properties represents a hurdle for further materials developments. Here, two key materials science issues for light-energy conversion are addressed: bandgap tunability via the quantum size effect, and photocarrier trapping. Nanocrystals are synthesized with controlled sizes varying from 3 to 30 nm. In this size range, bandgap tunability is found to be very small, a few tens of meV. First principles calculations show that a useful blueshift, in the range of hundreds of meV, is achieved in ultra-small nanocrystals, below 1.5 nm in size. Similar conclusions are envisaged for the class of pnictide chalcogenides with a ribbon-like structure [Pn 4 Ch 6 ] n (Pn = Bi, Sb; Ch = S, Se). Time-resolved differential transmission spectroscopy demonstrates that only photoexcited holes are quickly captured by intragap states. Photoexcitation dynamics are consistent with the scenario emerging in other metal-chalcogenide nanocrystals: traps are created in metal-rich nanocrystal surfaces by incomplete passivation by long fatty acid ligands. In large nanocrystals, a lower bound to surface trap density of one trap every sixteen Bi 2 S 3 units is found.
Zinc oxide/ and iron oxide/SBA-15 composites were synthesized using the innovative Two-Solvents procedure and tested as sorbents for the mid-temperature (300 C) removal of hydrogen sulphide, and then compared with a commercial unsupported ZnO sorbent. The sulphur retention capacity results showed the superior performance of the iron oxide/SBA-15 composite (401 mg S g1 Fe2O3) in comparison with the zinc oxide/SBA-15 composite (53 mg S g1 ZnO), both these sorbents being much more efficient than the commercial sorbent (6 mg S g1 ZnO). The different sorption behaviour was discussed in terms of the nature of the nanocomposites where: (i) the mesostructure of the support was retained with a high surface area and pore volume; (ii) the zinc oxide phase was incorporated inside the SBA-15 channels as a thin amorphous homogeneous layer while the iron oxide was dispersed in form of small maghemite crystallites; and (iii) significant interactions occurred between the silica matrix and the zinc oxide phase. Remarkable differences in the regeneration behaviour of the exhaust sorbents were revealed by temperature-programmed experiments under an oxidizing atmosphere. After regeneration, the sorption properties of the zinc oxide/SBA-15 composite appeared to be enhanced compared to the commercial sorbent. Incomplete recovery of the sorption activity was observed for the regenerated iron oxide/SBA-15 sorbent, whose performance remained far better than that of the ZnO-based one, either fresh or regenerated. In view of its higher sulphur retention capacity and appropriate regeneration temperature (T # 350 C), the iron oxide/SBA-15 composite is a promising material for the design of advanced sorbents for a thermally efficient H2S removal process from hot gas streams
In order to limit global warming to around 1.5–2.0 °C by the end of the 21st century, there is the need to drastically limit the emissions of CO2. This goal can be pursued by promoting the diffusion of advanced technologies for power generation from renewable energy sources. In this field, biomass can play a very important role since, differently from solar and wind, it can be considered a programmable source. This paper reports a techno-economic analysis on the possible commercial application of gasification technologies for small-scale (2 MWe) power generation from biomass. The analysis is based on the preliminary experimental performance of a 500 kWth pilot-scale air-blown bubbling fluidized-bed (BFB) gasification plant, recently installed at the Sotacarbo Research Centre (Italy) and commissioned in December 2017. The analysis confirms that air-blown BFB biomass gasification can be profitable for the applications with low-cost biomass, such as agricultural waste, with a net present value up to about 6 M€ as long as the biomass is provided for free; on the contrary, the technology is not competitive for high-quality biomass (wood chips, as those used for the preliminary experimental tests). In parallel, an analysis of the financial risk was carried out, in order to estimate the probability of a profitable investment if a variation of the key financial parameters occurs. In particular, the analysis shows a probability of 90% of a NPV at 15 years between 1.4 and 5.1 M€ and an IRR between 11.6% and 23.7%.
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