Photoinduced oxygen adsorption of AgBr crystals at 77 K

Photoinduced adsorption (PIA) of oxygen molecules on AgBr films at 77 K has been experimentally observed and investigated. Lifetimes of PIA centers and desorption activation energies of O₂ molecules have been determined. The process is suggested to compete with the ionic step of AgBr photolysis.

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- () - AgBr 77 K. - O₂. , , - AgBr.

     

Dogmas and misconceptions in heterogeneous photocatalysis. Some enlightened reflections

In a recent article, Ollis analyzed heretofore reported photocatalyst kinetics of surface photochemical reactions that take place in heterogeneous systems and that rely heavily on the Langmuir-Hinshelwood (LH) kinetic model to interpret the experimental observations. This model assumes a fast adsorption/desorption equilibrium step and a subsequent slow surface step. His interesting analysis of the experimental results reported in 2000 by Emeline and co-workers, Xu and Langford, and Martyanov and Savinov prompted our reexamination of the LH kinetic model along with several other dogmas that continue to propagate in the heterogeneous photocatalytic landscape. This short article discusses some of these issues and reexamines certain misinterpretations. Specifically, we reexamine (1) the a priori assumed validity of the LH kinetic model in heterogeneous photocatalysis, (2) the recombination of photogenerated free charge carriers on the solid (metal oxide) photocatalyst by the band-to-band recombination pathway, and (3) the mistaken assertion that the kinetics of a heterogeneous photoreaction are either only first-order dependent or half-order dependent on photon flow (i.e., light irradiance).     

A macrokinetic theory of sample vaporization in electrothermal atomic absorption spectrometry

A macrokinetic theory of the vaporization of a substance based on a consideration of the discrete distribution of a sample and of surface diffusion in the condensed phase has been developed. An analysis of mathematical models describing the vaporization process for the cases of a sample distributed in a porous bulk and over the vaporizer surface revealed several regions. The vaporization rate in these regions depends in different ways on the vaporization rate constant and the diffusion coefficient of the sample in the condensed phase. This offers an opportunity of explaining the appearance of breaks and inflections in the Arrhenius plots as well as of finding the relationship between the activation energies of vaporization in the different regions. The theoretical conclusions are in good agreement with the available and recently obtained data. The macrokinetic theory provided a better understanding of the mechanism of atomization for many elements in the graphite furnace. The macrokinetic theory offers an explanation for many aspects of electrothermal atomic absorption spectrometry associated with the effects of the furnace material and the wall structure, as well as of sample distribution in the furnace on the process of vaporization and, in particular, on the signal shape, sensitivity and matrix interferences.     

Cascade Synthesis of Pyrroles from Nitroarenes with Benign Reductants Using a Heterogeneous Cobalt Catalyst

A bifunctional 3d-metal catalyst for the cascade synthesis of diverse pyrroles from nitroarenes is presented. The optimal catalytic system Co/NGr-C@SiO₂-L is obtained by pyrolysis of a cobalt-impregnated composite followed by subsequent selective leaching. In the presence of this material, (transfer) hydrogenation of easily available nitroarenes and subsequent Paal–Knorr/Clauson-Kass condensation provides >40 pyrroles in good to high yields using dihydrogen, formic acid, or a CO/H₂O mixture (WGSR conditions) as reductant. In addition to the favorable step economy, this straightforward domino process does not require any solvents or external co-catalysts. The general synthetic utility of this methodology was demonstrated on a variety of functionalized substrates including the preparation of biologically active and pharmaceutically relevant compounds, for example, (+)-Isamoltane.     

Photoinduced radical processes on the spinel (MgAl2O4) surface involving methane, ammonia, and methane/ammonia

The present study explored photoinduced radical processes caused by interaction of CH(4) and NH(3) with a photoexcited surface of a complex metal oxide: magnesium-aluminum spinel (MgAl(2)O(4); MAS). UV irradiation of MAS in vacuo yielded V-type color centers as evidenced by the 360 nm band in difference diffuse reflectance spectra. Interaction of these H-bearing molecules with photogenerated surface-active hole states (O(S)(-)?) yielded radical species which on recombination produced more complex molecules (including heteroatomic species) relative to the initial molecules. For the MAS/CH(4) system, photoinduced dissociative adsorption of CH(4) on surface-active hole centers produced ?CH(3) radicals that recombined to yield CH(3)CH(3). For MAS/NH(3), a similar dissociative adsorption process led to formation of ?NH(2) radicals with formation of NH(2)NH(2) as an intermediate product; continued UV irradiation ultimately yielded N(2). For the mixed MAS/CH(4)/NH(3) system, however, interaction of adsorbed NH(3) and CH(4) on the UV-activated surface of MAS yielded ?NH(2) and ?CH(3) radicals, respectively, which produced CH(3)-NH(2) followed by loss of the remaining hydrogens to form a surface-adsorbed cyanide, CN(S), species. Recombination of photochemically produced radicals released sufficient energy to re-excite the solid spinel, generating new surface-active sites and a flash luminescence (emission decay time at 520 nm, τ ~ 6 s for the MAS/NH(3) case) referred to as the PhICL effect.     

Relativistic Nonlinear Optical Phenomena in the Field of Subterawatt Laser Pulses

Experiments on the generation of high optical harmonics demonstrating that relativistic regimes of interaction of radiation with matter can be implemented in the field of mid-infrared laser pulses with a peak power of 0.3 TW have been reported. The observation of relativistic phenomena at such extraordinary low peak powers of the laser field becomes possible because of the formation of a high-quality space-time mode of the laser field with an exactly specified polarization state. Such a field structure ensures a high intensity of radiation in the focus of the beam and the effective acceleration of electrons by a low-frequency electromagnetic field of a high-contrast laser pulse with an exactly specified polarization at the extremely sharp vacuum-solid interface.

     

Few-body Studies at Nuclotron-JINR

Recent results on the deuteron analyzing powers in dp- elastic scattering obtained at Nuclotron (JINR, Dubna) are compared with the calculations performed within relativistic multiple scattering model. The data demonstrate strong deviation form the predictions at large angles in the cms. The preliminary data on the energy dependence of the cross section in the dp → ppn reaction at 150–250 MeV/nucleon for different configurations and dp elastic scattering up to 1 GeV obtained at internal target station at Nuclotron are reported. The prospects of the further few-body studies at JINR are discussed.     

Correlation Equations for Predicting the Temperature Depression in Boiling of Aqueous Solutions of Nonvolatile Substances

Three-constant correlation equations describing the boiling point of aqueous solutions of non-volatile substances and temperature depression in boiling of the solutions under normal and arbitrary pressures are considered. The three constants appearing in the correlation equations are tabulated for aqueous solutions of 19 nonvolatile substances, and formulas for determining these constants for other aqueous solutions of nonvolatile substances from experimental data are presented.     

Photoinduced adsorption of hydrogen and methane on gamma-alumina. the photoinduced chesorluminescence (PhICL) effect

Adsorption of hydrogen and methane on a preirradiated surface of gamma-Al2O3 produces an afterglow, which has been described as a photoinduced chesorluminescence (PhICL), whose spectral features identify with the intrinsic photoluminescence of alumina. The emission spectrum consists of at least four overlapping single emission bands. For methane adsorption, the PhICL phenomenon is seen only if the solid is preirradiated in the presence of oxygen. Emission decay kinetics of the PhICL effect for gamma-Al2O3 reveal two wavelength regimes: a short wavelength regime at lambda = 300-370 nm (decay time tau = 1.1 +/- 0.2 s; signal width = 2.8 s), and a longer wavelength regime at lambda = 380-700 nm (decay time tau = 2.1 +/- 0.1 s; signal width = 4.3 s). A model is proposed in which there exist two different emission centers and, thus, two different pathways for emission decay. In the first, emission originates with electron trapping by such deep energy traps as anion vacancies {e- + Va --> F+ + hv1} to yield electron F-type color centers, whereas in the second, emission originates from electron/trapped hole recombination {e- + Os*- --> Os2- + hv2}. The first common step of the pathways is homolytic dissociative chemisorption of hydrogen and methane upon interaction with surface-active hole centers Os*-, produced upon preirradiation of alumina, to give atomic hydrogen H* and methyl radicals CH3*. Thermoprogrammed desorption spectra of photoadsorbed or postsorbed oxygen show that adsorbed oxygen interacts with atomic hydrogen and methyl radicals. The products of thermodesorption were H2O for hydrogen and H2O, CO2, and CH3CH3 for methane. The Solonitsyn memory effect coefficient was also evaluated for oxygen photoadsorption.