A hybrid photocatalytic system, which is based on a mixed-phase cadmium sulfide matrix composed of nanoparticulate cubic-phase CdS (c-CdS) with average particle diameters of 13 nm and a bandgap energy of 2.6 eV, is coupled with bulk-phase hexagonal CdS (hex-CdS) that has a bandgap energy of 2.3 eV and is interlinked with elemental platinum deposits. The resulting hybrid nanocomposite catalysts are photocatalytically efficient with respect to hydrogen gas production from water with visible light irradiation at λ > 420 nm. Rates of H 2 production approaching 1.0 mmol-H 2 g -1 h -1 are obtained with a c-CdS/Pt/hex-CdS composite photocatalyst, in the presence of a mixed sodium sulfide and sodium sulfite background electrolyte system at pH 14. In contrast, the same composite produces H 2 a rate of 0.15 mmol g -1 h -1 at pH 7 in a water-isopropanol solvent system. The relative order of reactivity for the synthesized hybrid catalysts was found to be c-CdS/ Pt/hex-CdS > Pt/c-CdS/hex-CdS > Pt/hex-CdS > hex-CdS > c-CdS/hex-CdS > quantum-sized c-CdS. A mechanism involving enhanced lifetimes of electron-hole trapping states that are dependent on the surface chemistry of hydrated CdS involving surface hydroxyl (>CdOH) and sulfhydryl groups (>CdSH) are invoked.
The presence of carbonyl compounds (CCs) in wines has sparked the interest of researchers in several countries. The quantification of some of these compounds has been used as a parameter of quality for many fermented beverages. Although present in minute quantities (except for acetaldehyde), they have a strong olfactory impact. In addition, the CCs found in wines have a strong affinity for bisulfite and can form stable adducts, which will also interfere in the characteristics of aroma. The greatest challenge, however, is to predict which CCs have the strongest affinity for S(IV) and what conditions favor this interaction. To better understand the reaction of CC-bisulfite adduct formation (HASA), this study has evaluated the profile of 22 CCs in a "synthetic wine" containing bisulfite and in 10 real samples of different wines from the São Francisco Valley, northeastern Brazil. On the basis of principal component analysis (PCA) and dissociation constants, the results revealed that aliphatic aldehydes form adducts with S(IV), whereas ketones, cyclic aldehydes, and trans-alkenes interact weakly and are found predominantly in their free form. These results revealed also that pH 10 and 11 were defined as the most appropriate for CC-SO 2 adduct dissociation, and the total CCs were quantified reliably.
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