A comparative study on the interaction between tin(II) porphyrin and selected group 8B metals for potential application as reduction catalysts

We study the interaction between tin(II) porphyrin (SnPor) with platinum and non-precious Group 8B metals (iron, cobalt and nickel) by density functional theory and discuss the electronic properties of the resulting products. We also model the interaction of the resulting compounds with water where applicable. Our studies indicate that, SnPor-Ni possesses electronic properties similar to SnPor-Pt, suggesting that it may possess similar photocatalytic properties for reduction reactions, such as converting water to hydrogen gas.     

X-ray photoelectron spectroscopy characterization of oxidated Si particles formed by pulsed ion-beam ablation

X-ray photoelectron spectroscopy (XPS) is used to probe oxidation states of Si species in particles deposited using a pulsed ion-beam evaporation method. The effects of He ambient gas, ion beam intensity and post-treatments on the oxides composition and oxygen content have been studied. It is found that presence of He ambient gas led to a profound oxidation of Si species as compared to that prepared in vacuum at the same ion-beam ablation energy, i.e. both increase of SiO₂ component and oxygen concentration in the oxides coverage. The deposition in He also resulted in an increase of oxygen concentration even under lower ablation intensity, but a higher Si suboxides concentration. It is revealed that the reaction between Si and O was controlled by the ion beam intensity (temperature of Si plasma) and the gas ambient (collision probability of Si and O species). The difference in structure of oxide layers for samples obtained under various conditions is discussed based on the results of XPS analyses.     

溶胶-凝胶VO2薄膜转换特性研究

利用溶胶凝胶法在SiO2Si衬底上沉积高取向的V2O5薄膜,在压强低于2Pa,温度高于400℃的条件下,对V2O5薄膜进行真空烘烤,获得了电阻率变化3个数量级以上、弛豫宽度为62℃的VO2多晶薄膜.以X射线衍射(XRD)、扫描电子显微镜(SEM)图和电阻率转换特性等实验结果为依据,详细分析了溶胶凝胶薄膜在真空烘烤时从V2O5向VO2的转化,它经历了从VnO2n+1(n=2,3,4,6)到VO2的过程.实验证明,根据选择合适的成膜热处理条件和真空烘烤条件是实现溶胶凝胶V2O5结构向VO2结构成功转换的关键 关键词： 溶胶-凝胶法 氧化钒薄膜 VO2膜转换特性     

Band bending at the Si(1 1 1)–SiO2 interface induced by low-energy ion bombardment

Experiments employing photoreflectance spectroscopy have uncovered band bending due to electrically active defects at the Si(1 1 1)–SiO₂ interface after sub-keV Ar⁺ ion bombardment. The band bending of about 0.5 eV resembles that for Si(1 0 0)–SiO₂, and both interfaces exhibit two kinetic regimes for the evolution of band bending upon annealing due to defects healing. The healing takes place about an order of magnitude more quickly at the (1 1 1) interface, however, probably because of less fully saturated bonding and higher compressive stress.     

Ab initio study of sodium intercalation into metal oxides

Using the full-potential linearized augmented plane wave (FP-LAPW) method, we have studied the effect of chemistry on the average intercalation voltage (AIV) caused by the Na ions intercalating into transition metal oxides. The effect of transition metal was systematically studied by varying M=Co, Ni and Mn in NaMO₂ and fixing the α-NaFeO₂ layered structure. The effect of the guest atoms into the host material is discussed in terms of the structural and electronic properties. Comparatively to Li intercalation, a significant electron transfer towards transition metal was found. This observation suggests that the transition metal contribute to the AIV determination and confirms the common assumption that intercalated electron reduces M⁴⁺ to M³⁺.     

Superconductivity and normal state resistivity of Ba0.6K0.4BiO3: an optical phonon approach

We discuss the nature of the pairing mechanism and the physical properties associated with the normal as well as the superconducting state of cubic perovskites Ba_0.6K_0.4BiO₃using the strong coupling theory. An interaction potential which includes the Coulomb, electron–optical phonon and electron–plasmon interactions is developed to elucidate the superconducting state. A model dielectric function is constructed with these interactions fulfilling thef-sum rule. The screening parameter (μ^* = 0.26) infers the poor screening of charge carriers. The electron–optical phonon strength (λ) estimated as 0.98 is consistent with an attractive electron–electron interaction and supports the moderate to strong coupling theory. The superconducting transition temperature of Ba_0.6K_0.4BiO₃is then estimated as 32 K. Ziman's formula of resistivity is employed to analyse and compare this with the temperature-dependent resistivity of a single crystal. The estimated contribution from the electron–optical phonon together with the residual resistivity clearly infers a difference when a comparison is made with experimental data. The subtracted data infer a quadratic temperature dependence in the temperature domain (30 ≤ T ≤ 200 K). The quadratic temperature dependence of ρ [ = ρ_exp − (ρ₀ + ρ_e–ph)] is understood in terms of 3D electron–electron inelastic scattering. The presence of these el–el and el–ph interactions allows a coherent interpretation of the physical properties. Analysis reveals that a moderate to strong coupling exists in the Ba_0.6K_0.4BiO₃system and the coupling of electrons with the high-energy optical phonons of the oxygen breathing mode will be a reason for superconductivity. The implications of the above analysis are discussed.     

在Ni系ABO3和A2BO4型复合氧化物催化剂上NO吸附性能的研究

合成了具有钙钛石和类钙钛石结构的复合氧化物ＬａＮｉＯ３，Ｌａ０．１Ｓｒ０．９ＮｉＯ３，Ｌａ２ＮｉＯ４和ＬａＳｒＮｉＯ４。考察了它们对ＮＯ的吸附和ＮＯ直接分解反应的催化性能，结合比表面测定，化学分析，ＸＲＤ和ＮＯ－ＴＰＤ对催化剂的表征结果，探讨了该系列复合氧化物对ＮＯ的吸附规律。     

Theoretical study of the reaction of Sc with SCO in gas phase

In order to elucidate the mechanism of reaction M⁺ + SCO, both triplet and singlet potential energy surfaces (PESs) for the reaction of Sc⁺ + SCO have been theoretically investigated using the DFT (B3LYP/6-311+G*) level of theory. The geometries for reactants, intermediates, transition states and products were completely optimized. All the transition states were verified by the vibrational analysis and the intrinsic reaction coordinate calculations. The involving potential energy curve-crossing dramatically affects reaction mechanism, reaction rate has been discussed, and the crossing points (CPs) have been localized by the approach suggested by Yoshizawa et al. The present results show that the reaction mechanism are insertion–elimination mechanism both along the C–S and C–O bond activation branches, but the C–S bond activation is much more favorable in energy than the C–O bond activation. All theoretical results not only support the existing conclusions inferred from early experiment, but also complement the pathway and mechanism for this reaction.