Nonlinear optical properties of (B3O7)(5-) and (B3O6)(3-) groups

From the chemical bond viewpoint, LiB3O5 (LBO) crystal has been studied by using the bond valence theory of complex crystals. Chemical bond parameters and linear and nonlinear optical (NLO) properties of each type of constituent chemical bonds are quantitatively determined. Because of the different crystal structure characteristics of LBO from those of beta-BaB2O4 (BBO), the two anionic groups, (B3O7)(5-) in LBO and (B3O6)(3-) in BBO, play different roles in contributions to their own total NLO tensor coefficients of LBO and BBO, respectively. By comparison, we find that planar (B3O6)(3-) groups are the ideal structure model, leading to little cancellation of contributions of each kind of bond in these groups, and this gives us a useful guide to design new NLO materials in the future.

Single crystal growth and spectroscopic properties of KZnF3:Eu3+

Single crystal of KZnF3 : Eu3+ has been grown by means of Bridgman-Stockbarger technique in Ar atmosphere, The emission and excitation spectra of europium ion were measured, The results show that a small amount of Eu2+ exists in the crystal, The existence of Eu2+ ions was also confirmed by ESR data, The valence change of Eu ions during the crystal growth is due to unequivalent substitution of Eu3+ ions for the lattice ions. The sites possibly occupied by Eu ions in this crystal were also discussed.

Comparison of non-linear optical susceptibilities of KNbO3 and LiNbO3

From the chemical bond viewpoint, second-order non-linear optical (NLO) tenser coefficients of KNbO3 and LiNbO3 crystals have been calculated. By using the bond-valence theory of complex crystals and the modified bond-charge model, we were able to determine contributions of each type of constituent chemical bond to the total second-order NLO susceptibility. The tenser values thus calculated are in good agreement with experimental data. From the comparison of NLO tenser coefficients of these two crystals, we found that the major NLO contributors are KO12 groups and LiO6 octahedra not the distorted NbO6 octahedra. The difference between their NLO properties arises from their different structural characters, and the high coordination number of constituent elements in KNbO3 makes its valence electrons become more delocalised compared with those of LiNbO3. (C) 1997 Elsevier Science Ltd. All rights reserved.

Characterization and catalytic behavior of La2-x(Sr,Th)(x)CuO4+/-lambda in reaction NO+CO

Two mixed oxide systems La2-xSrxCuO4+/-lambda(0.0 less than or equal to x less than or equal to 1.0) and La2+xThxCuO4+/-lambda(0.0 less than or equal to x less than or equal to 0.4) with K2NiF4 structure were prepared by varying re values; Their crystal structures were studied by means of XRD and IR spectra. The average valence of Cu ion at B site, nonstoichiometric oxygen (A) and the chemical composition in the bulk and on the surface of the catalysts were measured by means of chemical analysis and XPS. The catalytic behavior in reaction CO + NO was investigated under the regular change of average valence of Cu ion at B site and nonstoichiometric oxygen (lambda). Meanwhile, the adsorption and activation of the small molecules NO and the mixture of NO + CO over the mixed oxide catalysts were studied by means of MS-TPD. The catalytic mechanism of reaction NO + CO over these oxide catalysts were proposed; and it has been found that, at lower temperatures the activation of NO is the rate determining step and the catalytic activity is related to the lower valent metallic ion and its concentration, while at higher temperatures the adsorption of NO is the rate determining step and the catalytic activity is related to the oxygen vacancy and its concentration.

Catalysis of the rare earth containing mixed oxides Ln(2)CuO(4) in phenol hydroxylation

Mixed oxides Ln(2)CuO(4+/-lambda)(Ln = La, Pr, Nd, Sm, Gd) with K2NiF4 structure were prepared. Their crystal structures were studied with XRD and IR spectra. Meanwhile, the average valence of Cu ions and nonstoichiometric oxygen (lambda) were determined through chemical analyses. Catalysis of the above-mentioned mixed oxides in the phenol hydroxylation was investigated. Results show that the catalysis of these mixed oxides has close relation with their structures and composition. Substitution of A site atom in Ln(2)CuO(4+/-lambda) has a great influence on their catalysis in the phenol hydroxylation.

The origin of nonlinearities in K[B5O6(OH)(4)]center dot 2H(2)O crystal

In this paper the origin of nonlinearities of the K[B5O6(OH)(4)].2H(2)O(KB5) crystal has been investigated from a comprehensive view-point by using the bond-valence theory of complex crystals. The results of the calculation (d(31) = -1.18 X 10(-10) esu, d(32) = 0.20 X 10(-10) and d(33) = -1.03 X 10(-9) esu) are in good agreement with experimental data. For the first time we pointed out that its nonlinearities come from the H(2)-O(2) bonds and the [B5O6(OH)(4)](-) group, and estimated its larger nonlinear optical (NLO) coefficient d(33).

A study of the electrochemical characteristics of the Co(salen)-Nafion modified electrode

A Co(salen)-Nafion modified electrode was prepared by immersing a glassy carbon electrode coated with the Nafion film into the aqueous solution with saturated Co(salen), The modified electrode showed a stable electrochemical reaction of Co(salen) at about 0 V(vs, SCE), The result of XPS indicated the valence of cobalt in Co(salen) changes from +2 before to +3 after Co(salen) enters the Nafion film, It is due to forming axis coordination of cobalt with sulfonic group in Nafion film, It was found that the mode of electron transfer in Co(salen)-Nafion modified electrode was controlled by physical diffusion and electron hopping, It was also found that the modified electrode could catalyze the reduction of O-2 to H2O2. The real catalyst may be the adduct of Co-I(salen) and O-2.

Luminescent properties of Ba-3(PO4)(2):Eu, Tb phosphors

Luminescence of europium (III), europium(II) and terbium(III) has been observed in Ba-3(PO4)(2):Eu, Tb phosphors which are synthesized in air atmosphere. The valence state of europium is influenced by amount of terbium. It is notable that the relative intensity of the emission spectra peaks corresponding to Eu2+ is increased if the amount of Tb3+ is increased. These phenomena can be explained by an electron transfer mechanism. We predict a new kind of two-rare-earth codoped trichromatic phosphors in Ba-3(PO4)(2) matrix.

The spectral properties of BaB8O13:Eu,Tb phosphors

The luminescence properties of BaB8O13:xEu,yTb phosphors which were synthesized in air atmosphere have been studied. The emissions of europium(III), terbium(III) and europium(II) have been observed in BaB8O13:xEu, yTb phosphors. Electron paramagnetic resonance (EPR) studies were carried out. The intensities of EPR peaks of europium(II) are increased if terbium(III) is increased in BaB8O13:Eu3+,yTb(3+) phosphors. So the valence state of europium is influenced by terbium(III). These phenomena can be explained by an electron transfer mechanism. We found a new kind of method to prepare trichromatic phosphor that two rare earth ions activated in a BaB8O13 matrix.

Nonlinearity of the complex crystals with O-H bond

A systematic and quantitative research on the structure-property correlation has been carried out in KH2PO4 (KDP), NH4H2PO4 (ADP) and HIO3, based on the dielectric theory of complex crystals and the Levine bond charge model. We, for the first time, successfully solve the problems in the calculation of the nonlinearities of the complex inorganic nonlinear optical (NLO) crystals, which have O-H bonds in their crystal structures. We do this by introducing the bond-valence equation we have set up, calculating the nonlinear optical tensor coefficients d(ijk) of these three compounds, quantitatively determining the contributions of each type of bond to the total second-order NLO tensor coefficient (d(ijk)) of the crystal, and presenting the bond parameters and the linear properties of each kind of bond. For the first time, the NLO coefficient d(36) for ADP was calculated. All calculated results are in good agreement with experimental data. We found that O-H bonds also play an important role in these crystals, except for in the important anionic groups (PO4 groups and IO3 groups). All the results thus calculated show that our method is useful in evaluating the NLO coefficients of the inorganic NLO crystals containing O-H bonds in their structures, and should be a useful tool toward the future research into new nonlinear optical materials of this kind.

Synthesis and characterization of a new double-cubane Mo-Fe-S cluster compound, [NEt(4)](3)[Mo2Fe6S8(mu-OMe)(3)(SPh)(3)Cl-3]

The new double-cubane cluster compound [NEt(4)](3)[Mo2Fe6S8(mu-OMe)(3)(SPh)(3)Cl-3] is synthesized from (NH4)(2)MoS4, FeCl3, Fe powder, S powder, NaSPh and NEt(4)Br in MeOH-DMF, its crystal structure is determined by X-ray crystallography, and results of XPS indicate a valence state of +4 for Mo.

Electron transfer between Eu and Tb in MMgF(4) systems

Emission of europium(II) and europium(III) have been observed in SrMgF4 : xEu, yTb phosphors which are synthesized in Ar or Ar/H-2 flow. The valence state of Eu is influenced by terbium. It is notable that the intensities of the ESR peaks corresponding to EU(2+) are regularly changed when terbium ion is incorporated. The typical Tb3d XPS spectrum belonging to Tb4+ is also found when Eu is codoped. This phenomena can be explained by electron transfer mechanism Eu3+ + Tb3+-->EU(2+) + Tb4+. And its equilibrium constant is studied by ESR technique.

Studies on the adsorption property of NO on the Ni-based mixed oxide catalysts with Perovskite-like (ABO(3) and A(2)BO(4)) structure

The mixed oxides LaNiO3, La0.1Sr0.9NiO3, La2NiO4 and LaSrNiO4 with perovskite (ABO(3)) and related(A(2)BO(4)) structures were prepared and the adsorption property for NO and the catalytic activity for NO decomposition over these oxidse were also tested. The catalysts were characterized by means of BET surface measurement, chemical analysis, NO-TPD etc.. It was shown that the adsorption amount of NO is correlated with the concentration of oxygen vacancy formed and the adsorption type and strength of NO are related to the valence of metallic ion. Generally there are three kinds of adsorption species, NO-, NO+ and NO on the mixed oxides, among them the negative adsorpion species (NO-) are active for NO decomposition. The weaker the adsorption of oxygen on the catalyst is, the faster the mobility of oxygen is and the easier the redox process takes place in reproducing the active sites in which the oxygen species (O-, O2-) would participate.

Luminescence properties of SrB4O7: Eu, Tb phosphors

In this paper, the luminescence properties of SrB4O7: xEu, yTb phosphors were investigated. The SrB4O7: xEu, yTb phosphors were first synthesized in air atmosphere, and the emission spectra of Eu2+, Eu3+ and Tb3+ ions have been observed in phosphors. We found that the relative intensity of the emission of Eu2+ ion in the same matrix are increased when Tb3+ is incorporated in SrB4O7:Eu phosphor. So the valence state of europium is influenced by terbium. These phenomena can be explained using an electron transfer theory.

Relationship between the structure and catalytic activity of La2-xSrxNiO4-lambda(0<=x<=1) mixed oxides for NH3 oxidation

A series of samples having the composition of La2-xSrxNiO4(0 less than or equal to x less than or equal to 1) were prepared and used as catalysts for NH3 oxidation. It was found that the La and oxygen vacancies exist in the La2-xSrxNiO4-lambda(0 less than or equal to x less than or equal to 1). The unit cell volume decreases with the increase of x. For bath c and a parameters there appeared a turning point at x = 0.5. Doping with a lower valence cation Sr2+ in the case of La2NiO4 resulted in an increase of Ni3+, consequently the formation of oxygen vacancies, the increase of reducing ability and the increase of catalytic activity. In the oxygen TPD of La2-xSrxNiO4(0 less than or equal to x less than or equal to 1) appeared three peaks, the alpha' peak at about 400K was attributed to the surplus oxygen desorption, the a peak at 700K which approaches to a maxium at x = 0.6 was attributed to the oxygen adsorbed at oxygen vacancies. The beta peak at about 1000K which depends closely on the x and favors the catalytic activity was attributed to the reduction of Ni3+. The catalytic activity of La-2-x SrxNiO4 mixed oxides in the NH3 oxidation in general could be attributed to the extent of the redox reaction: 2Ni(2+) + O-2 + V-0(..) reversible arrow 2Ni(3+) + 20(-) where V-0(..) representes the oxygen vacancies and O- the oxygen species adsorbed at the vacancies.