Adsorption of H3PW12O40 by porous carbon materials

Adsorption of H₃PW₁₂O₄₀ from water and organic oxygen-containing solvents (AcOH, Me₂CO, MeOH) by carbon mesoporous materials, viz., Sibunit and catalytic filamentous carbons (CFC), was studied. The amount of irreversibly sorbed heteropolyacid is 50—100 mg g^–1 of support and decreases in the series of solvents: H₂O > Me₂CO > AcOH > MeOH. The adsorption capacity of CFC depends on the specific surface, total pore volume, and microstructure of the CFC fiber.     

The Structure of o-Hydroxyaryloxy-bis-(o-arylenedioxy)-phosphoranes and their Acid-Base Properties

Abstract

The crystalline phosphoranes have been obtained. IR-, UV- and NMR spectra of phosphoranes (Ia,b) and their interaction products with nitrogen bases have been investigated. It was determined that phosphoranes have structure (I) with pentacoordinate phosphorus and phenolic hydroxy group, while their products of interactions with nitrogen bases have the ionic structure (II) with hexacoordinate phosphorus (II). The X-ray difraction approves the structure (I) for phosphorane Ib.     

Q-switched Yb 3+ :YVO 4 laser with Raman self-conversion

We report the efficient continuous-wave (CW) and Q-switched laser operation of a diode-pumped Yb:YVO₄ laser. A CW output power of 1 W with a slope efficiency of 59% with respect to absorbed pump power was demonstrated. Passively Q-switched with a Cr⁴⁺:YAG saturable absorber, a Yb:YVO₄ laser with Raman conversion was demonstrated. Q-switched 18.7- J pulses with a pulse duration of 17 ns and a peak power up to 1 kW were obtained at 1018-nm fundamental wavelength and 3.6- J pulses with a pulse duration of 6 ns and a peak power of about 0.6 kW were obtained at 1119.5-nm first-Stokes wavelength.This revised version was published online in March 2005. In the previous version, the published online date was missing     

Yb3+-doped YVO4 crystal for efficient Kerr-lens mode locking in solid-state lasers

We report the first demonstration, to our knowledge, of soft-aperture Kerr-lens mode locking in a diode-pumped femtosecond Yb3+:YVO4 laser. Near-transform-limited pulses as short as 61 fs are generated around a center wavelength of 1050 nm with an output power of 54 mW and a pulse repetition frequency of 104.5 MHz. This is, to our knowledge, the shortest pulse generated directly from an Yb laser having a crystalline host material. The femtosecond operation has a mode-locking threshold at an absorbed pump power of 190 mW. The nonlinear refractive indexes of the Yb3+:YVO4 crystal have been measured to be 19 x 10(-16) cm2/W and 15 x 10(-16) cm2/W for the sigma and pi polarizations, respectively, at 1080 nm.     

Spectroscopy and continuous-wave diode-pumped laser action of Yb3+:YVO4

The growth, spectroscopic properties, and laser performance of Yb:YVO4 crystal with laser diode pumping are reported. A peak absorption cross section of 7.4 x 10(-20) cm2 at 985 nm, a radiative lifetime of 0.25 ms, and a stimulated-emission cross section of 1.25 x 10(-20) cm2 at 1008 nm for pi polarization were determined for the Yb3+ ions in YVO4. Continuous-wave laser action of Yb:YVO4 at 1020-1027 nm was demonstrated with an output power of 610 mW and a slope efficiency of 49%.     

Anisotropy of nonlinear absorption in Co<Superscript>2+</Superscript>:MgAl<Subscript>2</Subscript>O<Subscript>4</Subscript> crystal

Anisotropy of the nonlinear absorption of Co²⁺ ions in MgAl₂O₄ single crystal at the wavelengths of 1.35 and 1.54 μm has been experimentally demonstrated. The experimental data are analyzed in the framework of a phenomenological model when the Co²⁺ ions are described as three sets of linear dipoles oriented along the crystallographic axes. Ground-state and excited state absorption cross-sections at 1.35 and 1.54 μm are evaluated to be σ_gsa=(4.0±0.3)×10^-19, σ_esa=(3.6±0.4)×10^-20 cm² and σ_gsa=(5.1±0.3)×10^-19, σ_esa=(4.6±0.4)×10^-20 cm², respectively. PACS 42.55.Rz; 71.20.Be     

A Study of the Acid Properties of Structurally and Compositionally Different Heteropoly Acids in Acetic Acid

The acid properties of heteropoly acids of the following three structure types were studied by conductometry in acetic acid: Keggin (H₃PW₁₂O₄₀, H₃PMo₁₂O₄₀, H₄SiW₁₂O₄₀, H₃PW₁₁ThO₃₉; and H₅PW₁₁XO₄₀, where X(IV) = Ti or Zr), Dawson (-H₆P₂W₁₈O₆₂and -H₆P₂Mo₁₈O₆₂), and H₆P₂W₂₁O₇₁(H₂O)₃. These compounds are electrolytes that dissociate in only the first step of this solvent. The thermodynamic dissociation constants of the heteropoly acids were calculated by the Fuoss–Kraus method. The Hammett acidity functions H ₀of the solutions of H₅PW₁₁XO₄₀, H₃PW₁₂O₄₀, H₄SiW₁₂O₄₀, and H₆P₂W₂₁O₇₁(H₂O)₃in 85% acetic acid at 25°C were determined by the indicator method. All of the test heteropoly acids were found to be strong acids.     

Esterification of n-Butanol with Acetic Acid in the Presence of Heteropoly Acids with Different Structures and Compositions

The esterification reaction of n-butanol with acetic acid ([BuOH] : [HOAc] = 1 : 15 mol/mol; 55°C, 5% H₂O) was studied in the presence of tungsten heteropoly acids of the Keggin (H₃PW₁₂O₄₀, H₄SiW₁₂O₄₀, H₅PW₁₁TiO₄₀, H₅PW₁₁ZrO₄₀, and H₃PW₁₁ThO₃₉) and Dawson structure (-H₆P₂W₁₈O₆₂, H₆P₂W₂₁O₇₁(H₂O)₃, H₆As₂W₂₁O₆₉(H₂O), and H₂₁B₃W₃₉O₁₃₂). The reaction orders with respect to H₆P₂W₂₁O₇₁(H₂O)₃, H₃PW₁₂O₄₀, and H₆P₂W₁₈O₆₉are equal to 0.78, 1.00, and 0.97, respectively. It was found that the reaction rate depends on the acidity, as well as on the structure and composition of heteropoly acids. The H₂₁B₃W₃₉O₁₃₂heteropoly acid is most active, whereas the Keggin-structure heteropoly acids exhibit the lowest activities. Of the Keggin structure heteropoly acids, H₅PW₁₁ZrO₄₀exhibits the highest activity because of the presence of a Lewis acid site in its structure.