Preparation of TiO<Subscript>2</Subscript>-coated LiCo<Subscript>1/3</Subscript>Ni<Subscript>1/3</Subscript>Mn<Subscript>1/3</Subscript>O<Subscript>2</Subscript> by electrostatic self-assembly method and its properties

A precursor of TiO₂–LiCo_1/3Ni_1/3Mn_1/3O₂ was prepared by electrostatic self-assembly method. The final product was obtained by heating the precursor at 400–450 °C for 4–6 h in air. X-ray diffraction (XRD), scanning electron microscope (SEM), X-ray photoelectron spectroscopy (XPS), and electrochemical tests were used to examine the structural, morphology, elementary valence, and electrochemical characteristics. XRD indicated that the TiO₂-coated material can be indexed by α-NaFeO₂ layered structure, which belongs to hexagonal-type space group R3m. XPS results confirmed the existence of TiO₂ compound on the surface of the coated sample. The SEM image showed that the material had spherically porous morphology with the uniform size about 6 μm. The initial charge–discharge capacity of the TiO₂-coated LiCo_1/3Ni_1/3Mn_1/3O₂ material was 168.8/160.0 mAh/g. After 60 cycles, the discharge capacity of the TiO₂-coated LiCo_1/3Ni_1/3Mn_1/3O₂ sample was 147.0 mAh/g, and the coulombic efficiency was 94.0%. Compared with the uncoated sample, the electrochemical performance of TiO₂-coated LiCo_1/3Ni_1/3Mn_1/3O₂ was improved.     

Analysis of hydrogen bonds by the IR spectra of thymine and N<Subscript>1</Subscript>,N<Subscript>3</Subscript>-deuterothymine

Calculations of the frequencies and absolute intensities of the IR bands of plane vibrations of thymine and N₁,N₃-deuterothymine in various phase states have been carried out. It has been shown that in the polycrystalline state thymine forms hydrogen bonds C₂=O₈...HN₁ and C₂=O₈...HN₃, and in an aqueous solution the intermolecular interaction is realized by means of the hydrogen bonds O₈...HO and O...HN₁.__________Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 72, No. 1, pp. 99–105, January–February, 2005.     

Study of the third order nonlinear optical properties of Zn<Subscript>1−x</Subscript>Mg<Subscript>x</Subscript>Se and Cd<Subscript>1−x</Subscript>Mg<Subscript>x</Subscript>Se crystals

Third order nonlinear optical susceptibilities χ^<3> of ternary Zn_1−xMg_xSe and Cd_1−xMg_xSe crystals have been measured using standard degenerate four-wave mixing (DFWM) method at 532 nm. The nonlinear transmission technique has been applied to check if our crystals exhibit two-photon absorption. The studied Zn_1−xMg_xSe and Cd_1−xMg_xSe solid solutions were grown from the melt by the modified high-pressure Bridgman method. For both crystals the energy gap increases with increasing Mg content. In the case of Zn_1−xMg_xSe, it was found that the value of third order nonlinear optical susceptibility χ^<3> decreases with increasing Mg content. An explanation of this behaviour results from the dependence of optical nonlinearities on the energy band gap E_g of the studied crystals. In the case of Cd_1txMg_xSe with low content of Mg, no response was observed for the studied wavelength since the energy gap in such crystals is smaller than the photon energy of the used laser radiation. It was also found that the value of third order nonlinear optical susceptibility χ^<3> for Cd_0.70Mg_0.30Se is higher than for Zn_0.67Mg_0.33Se. This behaviour can be understood if one take into consideration that the free carrier concentration in Cd_1−xMg_xSe samples is about four orders of magnitude higher than that in Zn_1txMg_xSe ones with comparable Mg content respectively. It is commonly known that when the electric conductivity increases, the values of nonlinear optical properties increase. From the performed measurements one can conclude that the incorporation of Mg as constituent into ZnSe and CdSe crystals leads to a change of the third order nonlinear optical susceptibilities.     

Effect of Y2O3 addition on the conductivity and elastic modulus of (CeO2)1 − x(YO1.5)x

The conductivity and elastic modulus of (CeO₂)_1 − x(YO_1.5)_x for x values of 0.10, 0.15, 0.20, 0.30, and 0.40 were investigated by experiments and molecular dynamics simulations. The calculated conductivity exhibited a maximum value at approximately 15 mol% Y₂O₃; this trend agreed with that of the experimental results. In order to clarify the reason for the occurrence of the maximum conductivity, the paths for the transfer of oxygen vacancies were counted. The numerical result revealed that as the content of Y₂O₃ dopant increases, the number of paths for the transfer of oxygen vacancies decreases, whereas the number of oxygen vacancies for conductivity increases. Thus, the trade-off between the increase in the number of vacancy sites and the decrease in the vacancy transfer was considered to be the reason for the maximum conductivity occurring at the Y₂O₃ dopant content of approximately 15 mol%. The calculated elastic modulus also exhibited a minimum value at approximately 20 mol% Y₂O₃, which also agreed with the experimental results. It was shown that the Y–O–Y bonding energy increased with the increasing content of Y₂O₃ dopant. Thus, the trade-off between the increase in the number of vacancy sites and that in the Y–O–Y bonding energy was considered to be the reason for the minimum elastic modulus occurring at the Y₂O₃ dopant content of approximately 20 mol%.     

Au adsorption and Au-mediated charge transfer on the SrO-termination of SrTiO3 (0 0 1) surface

Atomic Au adsorption on the SrO-termination of SrTiO₃ (0 0 1) surface has been studied by means of the first-principles calculations based on the density functional theory (DFT). It indicates that charge polarization dominantly contributes to the bonding between Au and SrO-termination. Interfacial charge transfer induces dipole moment and changes work function. The mediating role Au played in charge transfer from electron-doped SrTiO₃:Nb to NO has been simulated. Charge transfer from SrTiO₃:Nb to Au is ascertained indicating that Au plays as an electron trapping center. SrO-termination has weak activity to NO while the molecule can be strongly adsorbed on negatively charged Au atom. It has been represented that Au mediates the charge transfer from SrTiO₃:Nb to NO. Antibonding orbital (π_2p*) of NO accommodates the charge and thus molecular bond is weakened (activated). Fukui functions demonstrate the role Au played in transiting the charge transfer from electronically excited SrTiO₃ to target species. Evidence that metal deposited on photocatalyst surface effectively separates the electron-hole pairs and improves the photocatalytic activity is presented in the current work.