Aida V. Rudakova

Light-Controlled ZrO2 Surface Hydrophilicity.

In recent years many works are aimed at finding a method of controllable switching between hydrophilicity and hydrophobicity of a surface. The hydrophilic surface state is generally determined by its energy. Change in the surface energy can be realized in several different ways. Here we report the ability to control the surface wettability of zirconium dioxide nano-coatings by changing the composition of actinic light. Such unique photoinduced hydrophilic behavior of ZrO2 surface is ascribed to the formation of different active surface states under photoexcitation in intrinsic and extrinsic ZrO2 absorption regions. The sequential effect of different actinic lights on the surface hydrophilicity of zirconia is found to be repeatable and reversibly switchable from a highly hydrophilic state to a more hydrophobic state. The observed light-controllable reversible and reproducible switching of hydrophilicity opens new possible ways for the application of ZrO2 based materials.

IR Spectroscopic Testing of Surfaces in Water Ice and in Icy Mixtures with Prussic Acid or Ammonia

An experimental technique is developed for spectral studies of ice films deposited at 77 K onto the ZnSe inner windows of a cell, so that the spectra could be registered in the presence of gaseous adsorbate. Pure H2O or D2O ice as well as HCN/D2O and ND3/D2O mixed icy films with different dopant/water ratios (1:10, 1:5, and 1:1) were investigated. The surface area of ice deposited at 77 K H2O estimated from adsorption measurements was about 160 m2/g. Bands of dangling hydroxyl groups disappear on raising the temperature up to 130-160 K when the changes of bulk absorption provide evidence for a phase transition from amorphous to polycrystalline ice. Surface properties of icy films were characterized by low-temperature adsorption of CO and CHF3. Insertion of small doses of HCN or ammonia does not change the acid/base strength of dangling hydroxyl groups or coordinately unsaturated surface oxygen atoms, but it changes the proportion between the concentrations of these sites as compared with pure water ice. For high dopant concentrations, the dangling hydroxyls were not observed, and the dominant adsorption sites for CO are likely to be the unsaturated oxygen atoms, while serious structural changes occur in the bulk of ices.

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.

IR Spectroscopic Study of Surface Properties of Amorphous Water Ice

The state of the surface of amorphous ice with a specific surface area of about 160 m2/g obtained by the condensation of water vapor at 77 K is studied by IR spectroscopy. As the temperature increases to 130–160 K, absorption bands of surface hydroxyl groups vanish, whereas changes in bands characteristic of hydroxyl groups in the bulk of ice are indicative of a phase transition of ice from amorphous to the polycrystalline structure. The surface sites of amorphous ice are characterized with low-temperature adsorption of carbon monoxide. It is shown that there are two types of CO adsorption sites, free hydroxyl groups and oxygen atoms of surface coordinately unsaturated water molecules. Upon adsorption of nitrogen, methane, and carbon monoxide, in addition to the perturbation of surface OH groups, reversible changes in the spectrum are observed in the region of vibrations of bulk hydroxyls, which indicate that the strength of hydrogen bonds between water molecules in the surface layer of icy particles increases approaching the strength of these bonds in the crystal and that the ice surface becomes less amorphous. These results indicate that the properties of the ice surface layer substantially depend on the presence of adsorbed molecules.

Spectroscopic study of zeolite Na-ETS-10 and ethylene photopolymerization reaction on its surface

Zeolite Na-ETS-10 is studied by the Raman and IR spectroscopy methods. The ethylene polymerization reaction on this zeolite under UV irradiation is studied by IR spectroscopy. It is found that this reaction proceeds at room temperature yielding polyethylene. The experimental data are analyzed using 2D correlation spectroscopy.

Spectroscopic studies of ozone in cryosolutions: FT-IR spectra of 16 O 3 in liquid nitrogen, oxygen, argon and krypton

We have measured and interpreted the IR spectra of ozone dissolved in liquid nitrogen, oxygen, argon, and krypton in the 650-4700cm-1 spectral region at 79-117K. Frequency shifts, band intensities and bandshapes of 22 spectral features of soluted ozone were analyzed. The bands of the А1 symmetry have a complex contour and possess an excess intensity with respect to the value of the purely vibrational transition moment. It was found that this effect is related to the manifestation of the Coriolis interaction. The bandshape distortion manifests itself as an additional intensity from the side of the В1 symmetry band being an intensity source in the case of the Coriolis interaction.