Influence of oxidation time on semiconductive behaviour of thermally grown oxide films on AISI 304L

The oxide films formed on AISI 304L stainless steel at 300 °C in the oxidation time range between 2 and 4 h have been studied by photoelectrochemistry. Photocurrents were investigated as a function of the wavelength of the incident light and the electrode potential. The investigation allowed the determination of the semiconductive properties of the oxides. The oxide films showed n-type behaviour. A duplex structure of the oxide films has been suggested on the basis of the photocurrent spectra, with an internal oxide layer having an optical gap (E_g2 = 2.16-2.3 eV) depending on the applied potential and oxidation time, higher to that of the external oxide layer (E_g1 ≈ 1.9 eV). Significant variations in the amplitude of the photocurrent were detected as a function of the applied potential and the oxidation time.     

Ring expansion of 5- to 6-member zirconacycles by carbenoid insertion

A wide range of carbenoids (1-lithio-1-halo species), including those with α-SiR₃, OEt, SPh, SO₂Ph, P(O)(OEt)₂, and CN substituents, insert into 5-member zirconacycles (saturated and unsaturated, mono- and bi-cyclic) to afford functionalized 6-member zirconacycles. 1-Lithio-1-haloalkenes insert to afford 6-member zirconacycles with an alkylidene substituent next to the metal. Unexpected double insertion of some carbenoids, and evidence for endocylic β-hydride transfer processes provide additional mechanistic interest.     

无催化纳米氧化锌的制备及其光学性质研究

本文采用无催化剂直接蒸发高纯Zn粉,在800℃氧气氛条件下,在Si(111)衬底上生长得到以四角状为主的纳米ZnO(T-ZnO)。T-ZnO纳米线每个角约互成110°,长度约为1.5μm,直径100nm左右;Raman分析表明E2(H)普遍存在于各形态的ZnO;光致发光光谱表明,T-ZnO纳米线的光致发光除了与材料性质有关,还与杂质缺陷有关,蓝绿光带是ZnO的缺陷产生的。     

Lewis acid promoted reactions of γ,γ-dialkoxyallylic zirconium species with various carbonyl compounds

The reactions of γ,γ-dialkoxyallylic zirconium species with carbonyl compounds in the presence of Lewis acid are reported. The reactivity of γ,γ-dialkoxyallylic zirconium species and reaction pathway were strongly dependent on the structure and electrostatic nature of the carbonyl compounds.     

LaB6-ZrB2共晶复合材料的组织特征及控制

用电弧炉和电子束悬浮区熔炉法制备了ＬａＢ６ＺｒＢ２共晶复合材料，并用ＳＥＭ和ＴＥＭ方法对其显微组织进行了研究。结果表明，ＬａＢ６ＺｒＢ２形成纤维状共晶组织，控制凝固条件可得到定向排列的组织，ＬａＢ６基体上均匀分布着直径为０２～１２μｍ的ＺｒＢ２纤维，纤维长度可达１００μｍ以上。对于固液界面为平面生长的试样，其结晶学取向关系为［００１］ＬａＢ６∥［００１］ＺｒＢ２，（１１０）ＬａＢ６∥（０１０）ＺｒＢ２。     

Effect of Ba and Bi doping on the synthesis and sintering of Ge-based apatite phases

Recently, high oxide ion conduction has been observed in the apatite-type systems La_9.33+x(Si/Ge)₆O_26+x/2, with conductivities approaching and even exceeding that of yttria-stabilized zirconia. The Ge-based phases have been reported to suffer from Ge loss and undergo irreversible structural changes on sintering at the high temperatures required to obtain dense pellets. In this paper we discuss doping studies (Ba, Bi for La) aimed at stabilizing the hexagonal apatite lattice to high temperature, and/or lowering the synthesis and sintering temperatures. The results show that doping with Ba helps to stabilize the hexagonal lattice at high temperatures, although Ge loss appears to still be a problem. Conductivity data show that, as previously reported for the Si-based systems, non-stoichiometry in the form of cation vacancies and/or oxygen excess is required to achieve high oxide ion conduction in these Ge-based systems. Neutron diffraction structural data for the fully stoichiometric phase La₈Ba₂Ge₆O₂₆ shows that the channel oxygen atoms show little anisotropy in their thermal displacement parameters, consistent with the low oxide ion conductivity of this phase. Bi doping is shown to lower the synthesis and sintering temperatures, although the presence of Bi means that these samples are not stable at high temperatures under reducing conditions.Presented at the OSSEP Workshop Ionic and Mixed Conductors: Methods and Processes, Aveiro, Portugal, April 10–12, 2003     

RuO2 electrode surface effects in electrocatalytic oxidation of glucose

We have studied the electrocatalytic activity of RuO₂-PVC film electrodes, fabricated using RuO₂ powders prepared at five different temperatures, viz., 300, 400, 500, 600 and 700°C, for the oxidation of glucose in high alkaline media, 1 to 3 M NaOH. The RuO₂-PVC film electrodes have been first characterized in 1 to 3 M NaOH solution by cyclic voltammetry (CV) and rotating disc electrode (RDE) techniques in a wide potential range −1,100 to 450 mV (SCE), and three redox pairs representing Ru(IV)/Ru(III), Ru(VI)/Ru(IV) and Ru(VII)/Ru(VI) transitions have been identified. The voltammetric peaks at low sweep rates have been analyzed using surface activity theory formulated for interacting electroactive adsorption sites, and interaction terms have been evaluated. The total voltammetric surface charges have been analyzed as per Trassatti’s formalism with respect to their dependence on potential sweep rate, and charges associated with less accessible and more accessible surface sites have been calculated. For glucose oxidation, the results have indicated that RuO₂ (700°C)-PVC electrode shows two oxidation peaks in contrast to RuO₂ (300°C)-PVC electrode. Also, RuO₂ (700°C)-PVC electrode exhibits higher intrinsic electrocatalytic activity than the 300°C electrode, although the former possesses lower electrochemically active surface area. Additionally, kinetic analyses made from RDE results with reference to Michealis–Menten (MM) enzyme catalysis has shown that RuO₂ (700°C) electrode possesses extended glucose-sensing range in terms of MM kinetic constant, K _M , compared to other electrodes. Possible reasons for such differences in the behavior of the electrodes of different temperatures towards glucose oxidation are identified from studies on oxidation of glucose in solutions of different pH, oxidation of different glucose derivatives, and also from physicochemical results from BET, XRD, SEM, DTGA, XPS analysis of RuO₂ powder samples.     

Synthesis and structural characterization of [SiMe2(C5H4)2][(C5Me5) Zr(μ-S)]2. a dinuclear zirconocenophane complex with a skewed dimethylsilyl-bridged bis(cyclopentadienyl) ligand

The reaction of [SiMe₂(C₅H₄)₂][(C₅Me₅)ZrMe₂]₂ with H₂S at 110°C proceeds with the formation of [SiMe₂(C₅H₄)₂][(C₅Me₅)Zr(-S)]₂]₂. The molecular structure of this dinuclear zirconocenophane compound features a non-planar four-membered Zr₂(-S)_{2 2} ring with two symmetrically-bridging sulfido groups. The bridging dimethylsilyl-bridged bis(cyclopentadienyl) ligand adopts a skewed orientation to accommodate the long Zr ... Zr separation of 3.611(1) Å. This compound crystallizes in the centrosymmetric space group P1 with refined lattice parameters ofa = 10.905(1) Å,b = 10.939(2) Å,c = 14.621(2) Å, = 106.32(1)°, = 91.25(1)°, = 111.25(1)°,V = 1545.1(8) ų, _calc. = 1.512g/cm³,Z=2. Full-matrix refinement converged with final discrepancy indices of R(F _o = 0.045 andR(F _o) = 0.079 with GOF= 1.60 for 4403 data withF _o > 3(F _o).This paper is dedicated to Professor Larry Dahl, a valued friend and mentor, on the occasion of his 65th birthday and in recognition of his significant fundamental contributions to the field of metal cluster chemistry. May the Goddess Fortuna continue to bring distinction and honor to him and his research endeavors.     

Preparation and properties of rare-earth containing oxide fluoride glasses

The preparation of the rare earth containing oxide fluoride glasses LnF₃ (Ln; Y through Lu)-BaF₂-AlF₃-GeO₂ in which the nominal content of LnF₃ reached 60 mol% in maximum and their basic properties such as density, refractive index and glass transition temperature were investigated and summarized in detail. Especially, in order to discuss the local structure around the rare earth ion in the glass, the Judd-Ofelt analysis (discussion with Ω parameters) of the HoF₃-BaF₂-AlF₃-GeO₂ glasses was carried out. The unique fluorescent behavior and the magnetic properties of LnF₃-BaF₂-AlF₃-GeO₂ glasses (Ln = Tb and/or Sm) were also studied.     

The Effects of M2O3 on Stabilizing Monocopper over the Surface of Cu-ZnO-M2O3 Catalysts for Mathanol Synthesis

The effects of M₃O₃ (M = Al, Sc etc.) in Cu-ZnO-M₂O₃ catalysts on methanol synthesis at low pressure were studied with ESR, XPS and TPR spectroscopy. The results of ESR showed that the generation of monovalent cationic defects was because the valence state and electronic charge on the ZnO lattice lost their balance as M³⁺ doped into ZnO. The induced effect by Sc³⁺ is stronger than that by Al³⁺. The results of XPS and TPR indicated that the amount and stabilization of Cu⁺ on the surface of reduced copper-based catalyst and its catalytic activity were affected by the monovalent cationic defects on the surface of ZnO.