Some recent studies mainly addressing the preparation and the modification of nanostructured thin films based on WO(3) and their application to photoelectrolysis of aqueous electrolytes are reviewed with the aim of rationalizing the main factors at the basis of an efficient photoanodic response. WO(3) represents one of the few materials which can achieve efficient water photo-oxidation under visible illumination, stably operating under strongly oxidizing conditions; thus the discussion of the structure-related photoelectrochemical properties of WO(3) thin films and their optimization for achieving almost quantitative photon to electron conversion constitutes the core of this contribution.
The oxidation state of Cu species dispersed in a Cu-ZSM-5 zeolite obtained by a nonconventional gas-phase CuCl exchange, and nominally containing only Cu(I) species, was studied by x-ray photoelectron spectroscopy (XPS) and x-ray absorption near edge structure (XANES) analyses. The oxidation of Cu(I) species to Cu(II) by simple exposure to the atmosphere and subsequent reduction by thermal activation in vacuo was monitored. The quantitative and energetic aspects of the formation of carbonyl-like and amino-complexes at the metallic sites was studied by means of adsorption microcalorimetry. CO and NH3 were used as probe molecules in order to assess the coordinative unsaturation of the Cu(I) cations. Adsorption heats comprised in the 130–40 kJ mol−1 interval were obtained for the formation of both type of complexes. The perturbation induced on the Cu centers and/or on the zeolite matrix by the adsorption of the probe molecules was monitored by parallel experiments of XPS, IR, and XANES. A significant fraction of CO and NH3 molecules are irreversibly held on Cu(I) sites even after outgassing at room temperature (RT) at a final dynamic vacuum of 10−5 Torr. On the contrary, no evidence of Cu(I)/CO or of Cu(I)/NH3 complexes was observed by XPS, indicating that such adducts are totally destroyed upon outgassing at 10−9 Torr. This fact implies a reconsideration of what was previously considered as a “stable adduct.” XPS allowed to reveal the existence of ammonia adsorbed on defective Al(III) species, and to explain the chemical nature of species formed at the earliest stages of NH3 dosage and characterized by a heat of adsorption as high as 180 kJ mol−1. By comparing the quantitative XPS and volumetric-calorimetric data it was inferred that a significant gradient of defects amount is present in the system. Finally, from the whole set of XPS measurements here reported and from parallel blank experiments on the ZSM-5 zeolite before Cu-exchange, a calibration scale for the N(1s) peak of various nitrogen species in the different zeolite samples is proposed.
We report the observation of visible-light emission at room temperature from high fluence (0.3–3×1017 cm−2) Si+ implanted thermal SiO2 layers grown on silicon substrates. Significant blue-light emission and an intense broad luminescent band with a peak beyond 750 nm are observed after annealing at high temperature (T≥1000 °C). The red-light emission, present only in the highest fluence implant, is attributed to the luminescence emitted from silicon nanocrystals produced by silicon precipitation. The presence of silicon nanocrystals is confirmed by transmission electron microscopy. Significant blue-light emission is visible after thermal annealing in the 1×1017 cm−2 fluence implant. The peak position shifts from 490 to 540 nm by increasing the annealing cycles temperature.
The potentiostatic anodization of metallic tungsten has been investigated in different solvent/electrolyte compositions with the aim of improving the water oxidation ability of the tungsten oxide layer. In the NMF/H(2)O/NH(4)F solvent mixture, the anodization leads to highly efficient WO(3) photoanodes, which, combining spectral sensitivity, an electrochemically active surface, and improved charge-transfer kinetics, outperform, under simulated solar illumination, most of the reported nanocrystalline substrates produced by anodization in aqueous electrolytes and by sol-gel methods. The use of such electrodes results in high water electrolysis yields of between 70 and 90% in 1 M H(2)SO(4) under a potential bias of 1 V versus SCE and close to 100% in the presence of methanol.
Several aluminum nanopowders were examined and compared with the final goal to evaluate their application in solid rocket propulsion. A detailed investigation of pre-burning properties by the Brunauer-Emmet-Teller method, electron microscopy, X-ray diffraction, and X-ray photoelectron spectroscopy was carried out. Ballistic properties and the combustion mechanism of several aluminized propellant formulations were investigated. In particular, aggregation and agglomeration of metal particles at and near the burning surface were analyzed by high-speed high-resolution color digital video recordings. All tested nano-powders are of Russian production; their physical characterization was carried out at the Istituto Donegani (Novara, Italy); ballistic studies were performed at the Solid Propulsion Laboratory (Milano, Italy) using laboratory and, for comparison, industrial composite propellants based on ammonium perchlorate as an oxidizer. Results obtained under a fair variety of operating conditions typical of rocket propulsion indicate, for increasing nano-Al mass fraction or decreasing nano-Al size, larger steady burning rates with essentially the same pressure sensitivity. While aggregation and agglomeration phenomena still occur, their significance may be reduced by using nano-Al instead of micro-Al.
Anodically grown WO3 photoelectrodes prepared in an N-methylformamide (NMF) electrolyte have been investigated with the aim of exploring the effects induced by anodization time and water concentration in the electrochemical bath on the properties of the resulting photoanodes. An n-type WO3 semiconductor is one of the most promising photoanodes for hydrogen production from water splitting and the electrochemical anodization of tungsten allows very good photoelectrodes, which are characterized by a low charge-transfer resistance and an increased spectral response in the visible region, to be obtained. These photoanodes were investigated by a combination of steady state and transient photoelectrochemical techniques and a correlation between photocurrent produced, morphology, and charge transport has been evaluated
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