Resonant Raman scattering in ultrafine CdSxSe1−x colloidal particles

Vibrational spectra of ultrafine (～1.8 nm) CdS _x Se_1?x colloidal nanoparticles (NPs) are studied by resonant Raman scattering (RRS). The detected difference of the shape and spectral position of the longitudinal optical vibration band in comparison with the spectrum of slightly larger NPs (≥ 2 nm) is explained by the dominance of surface atoms as their fraction increases above 50%. The correlation of experimental results with ab initio calculated vibrational spectra and with vibration anharmonicity enhancement as the NP size decreases is discussed.     

Effects of metal ions on the ethylene/ethane ratio in the oxidative conversion of methane

Modified forms of natural mordenites containing transition-metal ions catalyze the oxidative conversion of methane. The ethane-ethylene ratio in the C₂ hydrocarbon fraction is correlated with the metal ion hydrogenating and dehydrogenating capacity.Translated from Teoreticheskaya i Éksperimental'naya Khimiya, Vol. 28, No. 4, pp. 368–371, July–August, 1992.     

Structural and optical characterization of colloidal Se nanoparticles prepared via the acidic decomposition of sodium selenosulfate

Colloidal selenium nanoparticles (NPs) were synthesized via acidic decomposition of sodium selenosulfate. The effects of synthesis and post-synthesis treatment conditions on the size, structure and size distribution of the Se nanoparticles are discussed. It is shown that the decomposition of sodium selenosulfate with non-oxidative acids (e.g., HCl) in aqueous solutions of polymers (sodium polyphosphate, gelatin, polyvinyl alcohol, polyethyleneglycole) and surfactants (sodium dodecylsulfonate, cetylpyridinium chloride) results in the formation of amorphous 25–200 nm Se nanoparticles converting upon ageing at 90 °C into trigonal 150–250 nm Se nanocrystals. Optical properties (absorption and Raman spectra) of freshly prepared and aged Se nanoparticles both in colloidal solutions and in polymeric (polyvinyl alcohol) films are analyzed.     

Photocatalytic production of hydrogen from water–alcohol media with the participation of mesoporous TiO<Subscript>2</Subscript>

Samples of mesoporous TiO₂ containing 80-85% of anatase and 15-20% of rutile with average particle and pore sizes of ∼10 nm and specific surface areas of 70 m²/g were obtained. The nanohetero structures TiO₂/Cu formed during photocatalytic reduction of Cu^II exhibit photocatalytic activity in the release of hydrogen from water–ethanol mixtures. The quantum yield with respect to atomic hydrogen amounts to 1.5.     

Quantum-sized effects and the nature of the primary photoprocesses in copper(I) and copper(II) sulfide nanoparticles

The spectral and semiconductor properties of copper(I) and copper(II) sulfides in aqueous solution were studied. The colloids studied display quantum-sized effects. Two types of optical transitions, namely, indirect band-band and intraband transitions, are responsible for light absorption by the nanoparticles in the visible range. L. V. Pisarzhevskii Institute of Physical Chemistry, National Academy of Sciences of Ukraine, 31 Prospekt Nauki, Kiev 252039, Ukraine. Translated from Teoreticheskaya i éksperimental'naya Khimiya, Vol. 35, No. 2, pp.92–98, March–April, 1999.     

Photocatalytic Reduction of Zn(II) with Participation of ZnS Nanoparticles

We have studied the photochemical processes occurring in colloidal ZnS solutions containing zinc chloride and sodium sulfite as additives. Irradiation of such systems leads to reduction of Zn(II), the rate of which increases as the size of the ZnS nanoparticles decreases. Based on analysis of the kinetic curves for the reaction, we hypothesize that photoreduction of Zn(II) is a two-electron process. __________ Translated from Teoreticheskaya i Eksperimental'naya Khimiya, Vol. 41, No. 4, pp. 231–235, July–August, 2005.     

Optical Characteristics of Colloidal Nanoparticles of CdS Stabilized with Sodium Polyphosphate and Their Behavior during Pulse Photoexcitation

The optical and photophysical characteristics of quantum-dimensional particles of CdS stabilized in water (the oscillator force of the first exciton transition, the forbidden band width, the conduction and valence band potentials) were determined. It was established that pulse excitation of CdS nanoparticles gives rise to nonstationary bleaching of the colloid, due to the accumulation of excess electrons in the conduction band. Their amount and their consumption rate are determined by the nature and concentration of the electron donors and acceptors present in the system.     

Photoinduced variations in the size of nanoparticles of CdS in colloidal solutions

The possibility of decreasing the size of colloidal nanoparticles of CdS in the oxidative photocorrosion reaction in the presence of methylviologen and of increasing their size during photocatalytic reduction of sulfur in ethanol in the presence of cadmium acetate. A dependence of the quantum yield of the latter reaction on the initial size of CdS nanoparticles was observed, which was interpreted as a result of quantum size effects. __________ Translated from Teoreticheskaya i éksperimental’naya Khimiya, Vol. 43, No. 3, pp. 170–175, May–June, 2007.     

Photopolymerization of water-soluble acrylic monomers induced by colloidal CdS and Cd x Zn1 − x S nanoparticles

Photocatalytic activity of CdS and Cd _x Zn_1−x S nanoparticles in the polymerization of acrylamide and acrylic acid in aqueous solutions has been found. It has been shown that the most probable way of the photogeneration of primary radicals is the reduction of an adsorbed monomer by the conduction band electrons of the semiconductor nanoparticles, a monomer oxidation by the valence band holes and atomic hydrogen addition to a monomer being complementary photoinitiation routes. A correlation between the composition of Cd_xZn_1-xS nanoparticles and their photocatalytic activity in the acrylamide polymerization has been established. It has been shown that an increase in the quantum yield of the photopolymerization in a sequence СdS < Cd_0.75Zn_0.25S < CdS_0.5Zn_0.5S < Cd_0.3Zn_0.7S originates from a concurrent increase of the conduction band potential of the semiconductor nanoparticles. A kinetic equation of the photocatalytic acrylamide polymerization has been derived. Quantum yields of the photoinitiation have been found to be as small as 10⁻⁴ to 10⁻³.