Effect of valence of copper in La2-xThxCuO4 on NO decomposition reaction

NO decomposition reaction was investigated over La2-xThxCuO4, in which the valence of copper was controlled by Th substitution and was characterized by XPS measurement. A close correlation between the valence of copper and the activity was observed. The activity increased with the decrease of the average oxidation number of copper, and increased with the increase of Cu+ content, suggesting that the transition metal with low valence (Cu+) is active for the reaction in the present cases.

Alkali metal ions transfer across a water/1,2-dichloroethane interface facilitated by a novel monoaza-B15C5 derivative

In this paper, a novel monoaza-B15C5 derivative, N-(2-tosylamino)-isopentyl-monoaza-15-crown-5 (L), is used as an ionophore to facilitate alkali metal cations transfer across a water/1,2-dichloroethane (W/DCE) interface. Well-defined voltammetric behaviors are observed at the polarized W/DCE interfaces supported at micro- and nano-pipets except Cs+. The diffusion coefficient of this ionophore in the DCE phase is calculated to be equal to (3.3+/-0.2) x 10(-6) cm(2) s(-1). The experimental results indicate that a 1:1 (metal: ionophore) complex is formed at the interface with a TIC/TID mechanism. The selectivity of this ionophore towards alkali ions follows the sequence Na+ > Li+ > K+ > Rb+ > Cs+. The logarithm of the association constants (log beta(1)(0)) of the LiL+, NaL+, KL+ and RbL+ complexes in the DCE phase are calculated to be 10.6, 11.6, 9.0 and 7.1, respectively. The kinetic parameters are determined by steady-state voltammograms using nanopipets. The standard rate constants (k(0)) for Li+, Na+, K+ and Rb+ transfers facilitated by L are 0.54+/-0.05, 0.63+/-0.09, 0.51+/-0.04 and 0.46+/-0.06 cm s(-1), respectively. The pH values of aqueous solution have little effect on the electrochemical behaviors of these facilitated processes. The results predicate that this new type of ionophore might be useful to fabricate electrochemical sensor of sodium ion.

Measurement of the single-color three-photon resonant ionization spectrum of atomic uranium under the "equivalent wavelength effect laser" interaction

Using Nd: YAG laser (532 nm) pumped mixed-dye laser. we obtained the output of this dye enhanced at the wavelength interval equivalent to that given by the copper vapor laser pumped dye laser. This measure favored is with the measurement of single-color three-photon resonant ionization spectrum of atomic uranium in the range of 562-586 nm,which is otherwise not efficiently covered by Nd: YAG laser pumped dye laser with any single dye. Thus 140 U I energy levels were obtained and the peaks of interest 575.814 nm and 575.836 rim were well resolved and their relative intensity determined.

The effect of KSCN on the partition of proteins in polyethylene glycol/(NH4)(2)SO4 aqueous two-phase system

The effect of potassium thiocyanate on the partitioning of lysozyme and BSA in polyethylene glycol 2000/ammonium sulfate aqueous two-phase system has been investigated. As a result of the addition of potassium thiocyanate to the PEG/ammonium sulfate system, the PEG/mixed salts aqueous two-phase system was formed. It was found that the potassium thiocyanate could alter the pH difference between the two phases, and, thus, influence the partition coefficients of the differently charged proteins. The relationship between partition coefficient of the proteins and pH difference between two phases has been discussed. It was proposed that the pH difference between two phases could be employed as the measurement of electrostatic driving force for the partitioning of charged proteins in polyethylene glycol 2000/ammonium sulfate aqueous two-phase system.

Study of physicochemical properties and active oxygen in structures of layered mixed La4BaCu5-xMxO13+lambda (M = Mn, Co)

Two series of layered mixed oxides La4BaCu5-xMxO13+lambda(M = Mn, Co, x = 0 similar to 5) were prepared and characterized by means of XRD, XPS, O-2-TPD and chemical analysis. The results show that their structures are 5-layered ABO(3) perovskite, and the XPS and O-2-TPD investigation confirms that there exists synergistic effect between Cu ion and M when M ion is doped into the lattice of La4BaCu5O13+lambda,, and the synergistic effect between Mn and Cu is stronger than that of Cu-Co.

Physico-chemical properties and catalytic behavior of LnSrNiO(4) mixed oxides for NO decomposition

A series of LnSrNiO(4)(A(2)BO(4), Ln = La, Pr, Nd, Sm, Gd) mixed oxides with K2NiF4 structure, in which A-site(Sr) was partly substituted by individual light rare earth element, was prepared. The solid state physico-chemical properties including crystal structure, defect structure, IR spectrum, valence state of H-site ion, nonstoichiometric oxygen, oxygenous species, the properties of oxidation and reduction etc. as well as the catalytic behavior for NO decomposition on these mixed oxides were investigated. The results show that all of these mixed oxide catalysts have high activity for the direct decomposition of NO(at 900 degrees C the conversion of NO is more than 90%). The effect of the substitution of light rare earth elements at A-site on catalytic behavior for NO decomposition was elucidated.

Superconductor mixed oxides La2-xSrxCuO4+/-lambda for catalytic hydroxylation of phenol in the liquid-solid phase

Superconductor mixed oxides are often used as catalysts at high temperature in gas-solid phase oxidations and considered not suitable for lower temperature reactions in the liquid-solid phase; here the catalysis of La2-xSrxCuO4+/-lambda (x = 0, 0.1, 0.7, 1) mixed oxides in phenol hydroxylation at lower temperatures are studied, and we find that the value of x has a significant effect on catalytic activity: the lower its value, the higher the catalytic activity; a mechanism is proposed to explain the experimental phenomena.

Effect of water on the electrochemical oxidation process of biliverdin in dimethylformamide

A systematic study has been made for the electrochemical oxidation reaction of biliverdin (BV) in pure dimethylformamide (DMF) and in DMF - H2O mixed solvent by in situ time resolved spectroelectrochemical and cyclic voltametric techniques. The experiments show that not only the oxidation of BV is promoted, the reaction mechanism is also changed from a ECEC to a ECCECC process by the introduction of water into DMF.

STUDIES ON THE PEROVSKITE-TYPE MIXED CATALYSTS OF TITANIUM SYSTEM FOR OXIDATIVE COUPLING OF METHANE - THE INFLUENCE OF CALCINATION TEMPERATURE

The correlations of the calcination temperature, structure and catalytic activity for the oxidative coupling of methane on the LiLa0.5Ti0.5O2+lambda catalysts whose main phase and major active phase is Perovskite-type ternary complex oxide LaTi1-yLiyO3-lambda have been studied. The surface and bulk structures of the catalysts were characterized by means of XRD, XPS, IR, BET and so on, The results cleary indicated that the effect of calcination temperature on the activity for the oxidative coupling of methane is twofold. On one hand, it is favorable for Li+ substitution for Ti3+ to enter into the lattice of LaTiO3 and produce more oxygen vacancies in which active oxygens are formed; however, excessively high calcination temperature make the amount of Li+ substitution for Ti3+ lower, due to a little change of structure or phases for the catalyst. On the other hand, the conversion of CH4 drops because of the decrease of surface area, when the calcination temperature is raised.

SYNTHESIS OF ALKALI-METAL HYDRIDES USING LANTHANIDE TRICHLORIDE-NAPHTHALENE AS CATALYST UNDER MILD CONDITIONS

The hydrogenation of alkali metals using lanthanide trichloride and naphthalene as catalyst has been studied. LnCl3(Ln = La, Nd, Sm, Dy, Yb) and naphthalene can catalyze the hydrogenation of sodium under atmospheric pressure and 40-degrees-C to form sodium hydride. The activities of lanthanide trichlorides are in the following order: LaCl3 > NdCl3 > SmCl3 > DyCl3 > YbCl3. Although lithium proceeds in the same catalytic reaction, the kinetic curve of the lithium hydrogenation is different from that of sodium. Lanthanide trichlorides display no catalytic effect on the hydrogenation of potassium in presence of naphthalene. The mechanism of this reaction has been studied and it is suggested that the anion-radical of alkali metal naphthalene complexes may be the intermediate for the hydrogenation of alkali metals and the function of LnCl3 is to catalyze the hydrogenation of the intermediate. The products are porous solids with high specific surface area (83 m2/g for NaH) and pyrophoric in air. They are far more active than the commercial alkali metal hydrides. The combination of these hydrides with some transition metal complexes exhibits high catalytic activity for the hydrogenation of olefins.

Enrichment and hydrogen production by marine anaerobic hydrogen-producing microflora

Acid, alkali, heat-shock, KNO3 and control pretreatment methods applied to anaerobic sludge were evaluated for their ability to selectively enrich the marine hydrogen-producing mixed microflora. Seawater culture medium was used as the substrate. The hydrogen yield of pretreated microflora was higher than that of the un-pretreated control (P < 0.05). Among the pretreatment methods studied, heat-shock pretreatment yielded the greatest hydrogen production, which was 14.6 times that of the control. When the effect of initial pH on hydrogen production of heat-shock pretreated samples was studied, hydrogen was produced over the entire pH range (pH 4-10). The hydrogen yield peaked at initial pH 8 (79 mL/g sucrose) and then steadily decreased as the initial pH increased. Sucrose consumption was high at neutral initial pH. During the process of hydrogen production, pH decreased gradually, which indicated that the acquired microflora consisted of acidogenic bacteria.

Effect of heavy metals (Cd, Cu) on the gametophytes of Laminaria japonica Aresch

Effects of various concentrations of two heavy metals, namely Cd and Cu, on gametophytes of Laminaria japonica Aresch were determined by recording morphological changes of gametophytes, determining pH values and the heavy metal content of the culture solution, calculating the germination rate of sporophytes, and observing heavy metal (Cd) distribution using a fluorescence microscope. The results showed that heavy metals damaged the gametophytes, and were even lethal, and that the higher the concentration of heavy metal ions, the greater the injury to gametophytes. Gametophytes could not survive in culture solutions containing more than 100 mg/L Cd and 50 mg/L Cu and were only able to survive in culture solution containing a mixture of Cd and Cu tip to a concentration of 10 mg/L, which indicates that gametophytes have a higher tolerance to Cd than Cu and that multiple heavy metal ions in solution markedly aggravate the damage to gametophytes compared with individual heavy metal ions. With increases in the concentration of the heavy metal, the burgeoning rate of sporophytes decreased acutely, and solutions containing multiple heavy metal ions caused even more marked harm to sporophytes than solutions containing a single heavy metal ion, because most sporophytes died in mixed solutions. The pH value of the culture medium dropped immediately at the beginning (the first day) of treatment, increased over the following days, and then decreased again. The pH of culture media containing multiple heavy metal ions showed greater variation than media containing a single heavy metal ion, with the extent of the decrease in pH of culture media containing multiple ions being greatest during the last period of the experiment. With increases in the concentration of heavy metals, the capacity of gametophytes to accumulate these ions increased. The blue fluorescent light emitted by the Cd- and Cd-binding protein complex existing in gametophytes in media containing different concentrations of Cd showed clearly the distribution of the ion in gametophytes and the results obtained were consistent with distribution determined using other methods. All results of the present study showed that gametophytes of L. japonica play a remarkable role as heavy metal decontaminators, especially with regard to Cd.

Simulation of the ocean surface mixed layer under the wave breaking

A one-dimensional mixed-layer model, including a Mellor-Yamada level 2.5 turbulence closure scheme, was implemented to investigate the dynamical and thermal structures of the ocean surface mixed layer in the northern South China Sea. The turbulent kinetic energy released through wave breaking was incorporated into the model as a source of energy at the ocean surface, and the influence of the breaking waves on the mixed layer was studied. The numerical simulations show that the simulated SST is overestimated in summer without the breaking waves. However, the cooler SST is simulated when the effect of the breaking waves is considered, the corresponding discrepancy with the observed data decreases up to 20% and the MLD calculated averagely deepens 3.8 m. Owing to the wave-enhanced turbulence mixing in the summertime, the stratification at the bottom of the mixed layer was modified and the temperature gradient spread throughout the whole thermocline compared with the concentrated distribution without wave breaking.

Effect of Stokes drift on upper ocean mixing

Stokes drift is the main source of vertical vorticity in the ocean mixed layer. In the ways of Coriolis - Stokes forcing and Langmuir circulations, Stokes drift can substantially affect the whole mixed layer. A modified Mellor-Yamada 2.5 level turbulence closure model is used to parameterize its effect on upper ocean mixing conventionally. Results show that comparing surface heating with wave breaking, Stokes drift plays the most important role in the entire ocean mixed layer, especially in the subsurface layer. As expected, Stokes drift elevates both the dissipation rate and the turbulence energy in the upper ocean mixing. Also, influence of the surface heating, wave breaking and wind speed on Stokes drift is investigated respectively. Research shows that it is significant and important to assessing the Stokes drift into ocean mixed layer studying. The laboratory observations are supporting numerical experiments quantitatively.

Wave breaking on turbulent energy budget in the ocean surface mixed layer

As an important physical process at the air-sea interface, wave movement and breaking have a significant effect on the ocean surface mixed layer (OSML). When breaking waves occur at the ocean surface, turbulent kinetic energy (TKE) is input downwards, and a sublayer is formed near the surface and turbulence vertical mixing is intensively enhanced. A one-dimensional ocean model including the Mellor-Yamada level 2.5 turbulence closure equations was employed in our research on variations in turbulent energy budget within OSML. The influence of wave breaking could be introduced into the model by modifying an existing surface boundary condition of the TKE equation and specifying its input. The vertical diffusion and dissipation of TKE were effectively enhanced in the sublayer when wave breaking was considered. Turbulent energy dissipated in the sublayer was about 92.0% of the total depth-integrated dissipated TKE, which is twice higher than that of non-wave breaking. The shear production of TKE decreased by 3.5% because the mean flow fields tended to be uniform due to wave-enhanced turbulent mixing. As a result, a new local equilibrium between diffusion and dissipation of TKE was reached in the wave-enhanced layer. Below the sublayer, the local equilibrium between shear production and dissipation of TKE agreed with the conclusion drawn from the classical law-of-the-wall (Craig and Banner, 1994).