Ti(IV)/BINOL-catalyzed asymmetric aldol reaction of a masked acetoacetic ester: pronounced influence of catalyst concentration on nonlinear effects

Initial concentration of enantioenriched or enantiopure catalysts proved to be an important factor for the achievement of a more pronounced amplification of ee's in the Ti(IV)/BINOL-catalyzed aldol reaction of an O-silyldienolate.     

Fundamental reactions in TiO2 nanocrystallite aqueous solutions studied by pulse radiolysis

Reactions of the hydrated electron, H atoms, 2-propanol, and methanol radicals with the TiO₂ nano-particles have been studied either directly or by competition kinetics. The radicals were produced by radiolysis of 2-propanol, t-butanol, or methanol aqueous solutions in acid pH's. The reactions involve electron injection to the conduction band. As expected, the t-butanol radical is inert towards TiO₂ under our conditions, while the other reducing radicals react with TiO₂. The reactivity decreases in the order: e_aq⁻>H>CH₃COHCH₃>CH₂OH. Two TiO₂ nanocrystallite sizes, with average diameters of 1.0 and 4.7 nm were compared. For equal concentrations (in terms of TiO₂ molecules), the rate of electron injection shows relatively little dependency on particle size. The rates of interfacial electron transfer and transfer coefficient are also reported.     

Precipitation and characterization of uniform submicrometer lead titanate particles. Part II: Reaction mechanism

The chemical mechanism of the precipitation of lead titanium peroxohydroxide particles in a solution of nitrilotriacetate (NTA) complexes of lead and titanium peroxo-hydroxide is envisioned as the interaction between cations of lead hydroxide and anions of polymeric titanium peroxo-hydroxide.     

纳米累托石-TiO2光催化剂的制备及表征

以TiCl4和累托石为主要原料，制备出纳米累托石-TiO2粉末，并用X-衍射、透射电镜等对其进行表征．结果表明：纳米累托石-TiO2粉末平均直径为17．5nm当焙烧温度从500℃升至800℃时，累托石-TiO2粉末的比表面积从65．7m^2／g下降至3．3m^2／g，单位质量吸附剂的孔体积从0．1430cm。／u降到0．0213cm^3／g；当焙烧温度从300℃上升至500℃时，孔径变化不大，属中孔范围；当焙烧温度升至800℃时，一些孔道出现坍塌，不利于纳米累托石-TiO2粉末的光催化活性．     

Density functional theory investigation of the structure of SO2 and SO3 on Cu(1 1 1) and Ni(1 1 1)

Density functional theory (DFT) slab calculations, mainly using the generalised gradient approximation, have been used to investigate the minimum energy structures of molecular SO₂ and SO₃ on Cu(1 1 1) and Ni(1 1 1) surfaces. On Ni(1 1 1) the optimal local adsorption structures are in close agreement with experimental results for both molecular species obtained using the X-ray standing wavefield technique, although for adsorbed SO₂ the energetic difference between two alternative lateral positions of the lying-down molecule on the surface is marginally significant. On Cu(1 1 1) the results for adsorbed SO₂, in particular, were sensitive to the DFT functional used in the calculations, but in all cases failed to reproduce the experimentally-established preference for adsorption with the molecular plane perpendicular to the surface. This result is discussed in the context of previously published DFT results for these species adsorbed on Cu(1 0 0). The optimal geometry found for SO₃ on Cu(1 1 1) is similar to that on Ni(1 1 1), providing agreement with experiment regarding the molecular orientation but not the adsorption site.     

The structure of monolayer SiO2 on Mo(1 1 2): A 2-D [Si-O-Si] network or isolated [SiO4] units?

In this letter, atomically resolved scanning tunneling microscopic (STM) images obtained from monolayer SiO₂/Mo(1 1 2) are presented. The results are consistent with a previously proposed structural model of isolated [SiO₄] units based on vibrational features observed by high-resolution electron energy loss spectroscopy (HREELS) and infrared reflection-absorption spectroscopy (IRAS), and oxygen species identified by ultra-violet photoemission spectroscopy (UPS). These results are inconsistent with a structural model that assumes a two-dimensional (2-D) [Si-O-Si] network. These data illustrate that a metal substrate, although coated with an oxide thin layer, can be directly imaged at the atomic-scale with STM.     

Solubility of carbon dioxide in aqueous solutions of sodium chloride: Experimental results and correlation

The solubility of carbon dioxide in aqueous solutions of sodium chloride was measured in the temperature range from 40 to 160°C, up to 6 mol-kg salt solutions and total pressures up to 10 MPa. Pitzer's⁽¹⁾ equations as well as the Chen and Evans⁽²⁾ model were used to correlate the new data. Results are reported and compared to literature data and correlations.     

Interaction of carbon dioxide with ditoluenetitanium

The interaction of ditoluenetitanium with CO{in2} has been studied. Based on hydrolysis, thermolysis, and IR spectral data, the conclusion is drawn that a low-valent titanium oxalate is formed.This study was financially supported by the Russian Foundation for Basic Research (Project No. 93-03-5538).Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 12, pp. 2241–2242, December, 1994.     

Nanocrystalline ceramic films for efficient conversion of light into electricity

Transparent nanocrystalline films of oxide semiconductors such as TiO₂ and Fe₂O₃ have been prepared on a conducting glass support employing a sol-gel procedure. The films are composed of nanometer-sized particles sintered together to allow for percolative charge carrier transport. The internal surface of these films is very high, roughness factors of the order of 1000 being readily obtained. Electric polarization was applied for forward and reverse biasing of the films and the resulting optical changes have been analyzed to derive their flat band potential. Band gap excitation of such nanocrystalline semiconductors produces electron-hole pairs which migrate through the film to be collected as electric current. Steady state photolysis and time resolved laser techniques have been applied to scrutinize the mechanism of light induced charge separation within the nanostructure. When derivatized with a suitable chromophore, TiO₂ films give extraordinary efficiencies for the conversion of incident photons into electric current, exceeding 90% for certain transition metal complexes within the wavelength range of their absorption band. The underlying physical principles of these astonishing findings will be discussed. Exploiting this discovery, we have developed a new type of photovoltaic device whose overall light to electric energy conversion yield is 10% under simulated AM 1.5 solar radiation.