The chloroform / TBP / aqueous nitric acid interfacial system: a molecular dynamics investigation

We report MD studies on a chloroform / nitric acid water interface, either neat, or saturated by TBP molecules. Two extreme models are compared, where the acid is either neutral HNO₃ or dissociated to NO₃⁻ and H₃O⁺. The latter species are found to be “repelled” by the neat interface, while the neutral HNO₃ molecules are surface active. When the neat interface is saturated by TBP molecules, the latter form highly disordered arrangements instead of a regular monolayer, and water is dragged to the organic phase as 1:1, 1:2 and 2:2 hydrates of TBP. Simulations with the neutral HNO₃ model lead to extraction of acid to the organic phase, hydrogen bonded to the phosphoryl oxygen of TBP, forming HNO₃:TBP adducts of 1:1 and 2:1 types. Simulations with the ionic model lead to H₃O⁺:TBP adducts of 1:1, 1:2 and 1:3 types in the organic phase and significant mixing of the chloroform, TBP and water liquids in the interfacial region.     

超短超强激光与薄膜靶相互作用中不同价态碳离子的来源

研究了超短超强激光与不同厚度薄膜Al靶相互作用中靶背法线方向碳离子的最初来源. 通过对比分析碰撞电离率和场致电离率所起的作用, 发现C⁴⁺ 及更低价态的碳离子主要由场致电离产生, 而高价态的C⁵⁺和C⁶⁺ 离子主要来自于超热电子与靶表面的碰撞电离. 关键词： 超短超强激光与等离子体相互作用 离子加速 场致电离 碰撞电离     

Evolution of morphologic properties on the preparation of Ir/Al2O3 catalysts with high metallic contents

Ir/Al₂O₃ catalysts with high metallic contents are applied on satellite thruster to decompose hydrazine. The present work has as principal aim the study of the morphologic evolution of Ir/Al₂O₃ catalysts with metallic contents from 12 to 30 wt.%. The catalysts were prepared through consecutive impregnations from the H₂IrCl₆ precursor, using three different types of aluminas. The specific surface area, volume and distribution of pore size, specific metallic area and metallic particles average diameter, as well as the mechanical resistance were determined. Results show that the Ir addition leads to a decrease of the specific surface area and the pores volumes, while increases the mechanical resistance. Values for average diameter of metallic particles are comprised between 1.4 and 2.4 nm when the metallic content increases from 12 to 30 wt.%. Catalysts containing 30 wt.% of Ir presents specific metallic areas around 30 m²/g, although pores volumes and distributions of pore size were considerably different for the three supports. Their metallic particles dispersion and size values are very close to those of a commercial catalyst Shell 405, even though the preparation methods were different. These results show that there is a strong interaction between the alumina and the iridium precursor.     

Direct decomposition of nitrogen monoxide over a K-deposited Co(0 0 0 1) surface: Comparison to K-doped cobalt oxide catalysts

The influence of deposited potassium on the oxidation and NO reactivity of a Co(0 0 0 1) surface was studied using X-ray photoelectron spectroscopy. The formation of surface CoO was observed when the clean Co(0 0 0 1) surface was exposed to O₂ at 500 K. In contrast, the Co atoms on the K-deposited Co(0 0 0 1) surface remained at a lower oxidation state, CoO_x (0 < x < 1). No adsorption or dissociation of NO occurred on the CoO/Co(0 0 0 1) surface at 320 K, whereas a NO₂⁻ species formed on the oxidized K/Co(0 0 0 1) surface. This species is considered to be an intermediate in NO decomposition. It was concluded that the role of potassium was (i) to form the NO₂⁻ intermediate, and (ii) to keep the Co surface partially oxidized (CoO_x) as the active site for the dissociation of the NO₂⁻ species.     

Argon ion stimulated conversion between CFx (x = 0–3) chemical states and fluorine depletion in fluorocarbon films studied by X-ray photoelectron spectroscopy

Surface chemical composition of fluorocarbon films deposited onto indium-tin-oxide (ITO) substrates was modified by 2.0 keV Ar⁺ irradiation with doses of up to 2.6×10¹³ ions/cm². The effect of ion irradiation on the chemical composition and bonding configuration of the upper-surface and sub-surface regions were monitored by high-resolution angle-resolved X-ray photoelectron spectroscopy (AR-XPS). It was found that the as-deposited films compose of a distribution of CF, CF₂, CF₃ and C–C chemical states. C 1s line-shape analysis of XPS spectra measured at grazing and normal emission angles shows that as a result of the irradiation, the population of the CF₃ and CF₂ chemical states were preferentially depleted from the film’s surface resulting in an increased population of the CF and C–C chemical states in the upper-surface region of the film. It is suggested that low energy ion irradiation can be used to chemically modify the surface of fluorocarbon films.     

Investigation of the role of oxygen in NO reduction by C2H4 on the surface of stepped Pt(3 3 2)

The influence of pre-dosed oxygen on NO–C₂H₄ interactions on the surface of stepped Pt(3 3 2) has been investigated using Fourier transform infrared reflection–absorption spectroscopy (FTIR-RAS) and thermal desorption spectroscopy (TDS). The presence of oxygen significantly suppresses the adsorption of NO on the steps of Pt(3 3 2), leading to a very specific adsorption state for NO molecules when oxygen–NO co-adlayers are annealed to 350 K (assigned as atop NO on step edges). An oxygen-exchange reaction also takes place between these two kinds of adsorbed molecules, but there appears to be no other chemical reaction, which can result in the formation of higher-valence NOx.

C₂H₄ molecules which are post-dosed at 250 K to adlayers consisting of ¹⁸O and NO do not have strong interactions with either the NO or the ¹⁸O atoms. In particular, interactions which may result in the formation of new surface species that are intermediates for N₂ production appear to be absent. However, C₂H₄ is oxidized to C¹⁸O₂ by ¹⁸O atoms at higher annealing temperature. This reaction scavenges surface ¹⁸O atoms quickly, and the adsorption of NO molecules on step sites is therefore quickly restored. As a consequence, NO dissociation on steps proceeds very effectively, giving rise to N₂ desorption which closely resembles that following only NO exposure on a clean Pt(3 3 2), both in peak intensity and desorption temperature. It is concluded that the presence of ¹⁸O₂ in the selective catalytic reduction (SCR) of NO with C₂H₄ on the surface of Pt(3 3 2) does not play a role of activating reactants.     

Outer curvature and conformal geometry of an imbedding

The differential geometry of an imbedded (e.g. string or membrane world sheet) surface in a higher-dimensional background is shown to be conveniently describable (except in the null limit case) in terms of what are designated as its first, second, and third fundamental tensors, which will have the respective symmetry properties η_μν = η_(μν) as a trivial algebraic identity, K_μν^ρ = K_(μν)^ρ as the “generalised Weingarten identity”, which is the (Frobenius type) integrability condition for the imbedding, and Ξ_λμν^ρ = Ξ_(λμν)^ρ as a “generalised Codazzi equation”, which depends on the background geometry being flat or of constant curvature, needing replacement by a more complicated expression for a generic value of the background curvature B_κλ^μ_ν. The “generalised Gauss equation” expressing the dependence on this background curvature of the internal curvature tensor R_κλ^μ_ν of the imbedded surface is converted into terms of the first and second fundamental tensors, and it is thereby demonstrated that the vanishing of the (conformally invariant) “conformation tensor”, i.e. the trace free part C_μν^ρ of the second fundamental tensor K_μv^ρ, is a sufficient condition for conformal flatness of the imbedded surface (and thus in particular for the vanishing of its (Weyl type) conformal curvature tensor C_κλ^μ_ν) provided the background is itself conformally flat. In a trio of which the first two members are the generalised Gauss and Codazzi equations, the “third” member is shown to give an expression in terms of C_μν^ρ for the (trace free, conformally invariant) “outer curvature” tensor Ω_κλ^μ_ν whose vanishing is the condition for feasibility of the natural generalisation of the Walker frame transportation ansatz. The vanishing of C_μν^ρ is shown to be sufficient in a conformally flat background for the vanishing also of Ω_κλ^μ_ν.     

氟哌酸1HNMR的测定及过渡金属离子对其影响

氟哌酸^*[即1-乙基-6-氟-4-氧-7-(1-哌嗪)-3-(1,4-二氢化喹啉甲酸]是一种广谱、安全、有效、可供口服的抗感染药。我们测定了它的¹H自旋-晶格弛豫时间T₁及其在Cr³⁺、Mn²⁺、和Fe³⁺等过渡金属离子存在下的T₁值。实验结果表明,在加入过渡金属离子前后,氟哌酸不同位¹H的T₁值发生了一定的变化。据此可揭示过渡金属离子和氟哌酸形成配合物的配位点,从而可确定所形成配合物的结构。     

Nanoparticle-induced multi-functionalization of silicon: A plug and play approach

Here, we demonstrate a “plug and play” approach to achieve multi-functionalization of Si. In this approach, externally synthesized functional nanoparticles are introduced onto device quality Si wafers and the surface chemical bonds are manipulated. Sonochemically synthesized Fe₂O₃ nanoparticles are introduced onto Si from an alcohol suspension. On annealing this sample in ultra-high vacuum, the oxygen atoms change the bonding partner from Fe to Si and desorb as SiO at 750 °C. This results in the formation of nanoparticles of Fe on the surface and exhibits ferromagnetic behavior. Deposition of a thin layer (2 nm) of Si onto the sample containing the metallic Fe nanoparticles followed by annealing at 560 °C leads to optically active Si. Photoluminescence measurements show that this sample emits light at three different wavelengths, namely 1.57, 1.61 and 1.63 μm, when excited by He–Ne or Ar lasers. Oxidation of this material results in the formation of a selective capping layer of SiO₂. Thus we obtain multi-functional Si in an “all in one” form and we believe that this approach is universal.     

Towards the preparation of realistic model Ziegler-Natta catalysts: XPS study of the MgCl2/TiCl4 interaction with flat SiO2/Si(1 0 0)

Despite of the wide use of supported Ti based Ziegler-Natta catalysts in the olefin polymerization industry, questions concerning the role of each one of the catalyst components in the polymerization process, have not found a satisfactory answer yet. This is mainly because of the high sensitivity of these systems to oxygen and atmospheric moisture that makes their study in an atomic level rather complicated. Realistic surface science models of the pre-activated SiO₂ supported MgCl₂/TiCl₄ and TiCl₄ Ziegler-Natta catalysts were prepared by spin coating on flat conductive SiO₂/Si(1 0 0) supports under inert atmosphere. This preparation technique resembles the wet chemical impregnation which is the industrial method of the catalyst preparation. XPS analysis showed that the catalyst precursor anchors on the silica surface through bonding of the Ti atoms with surface silanes or siloxanes, while Mg is attached to the Ti through chlorine bridges. Thermal treatment of the catalysts at 723 K leads to total Cl desorption when MgCl₂ is not present while a significant amount of the Ti atoms is reduced to the Ti³⁺ state.     

Adsorption of NO on Au atoms and dimers supported on MgO(1 0 0): DFT studies

The adsorption of NO on single gold atoms and Au₂ dimers deposited on regular O²⁻ sites and neutral oxygen vacancies (F_s sites) of the MgO(1 0 0) surface have been studied by means of DFT calculations. For Au₁/MgO the adsorption of NO is stronger when the Au atom is supported on an anionic site than when it is on a F_s site, with adsorption binding energies of 1.1 and 0.5 eV, respectively. In the first case the spin density is mainly concentrated on the metal atom and protruding from the surface. In such a way, an active site against radicals such as NO is generated. On the F_s site, the presence of the vacancy delocalizes the spin into the substrate, weakening its coupling with NO. For Au₂/MgO, as this system has a closed-shell configuration, the NO molecules bonds weakly with Au₂. Regarding the N–O stretching frequencies, a very strong shift of 340–400 cm⁻¹ to lower frequencies is observed for Au₁/MgO in comparison with free NO.     

Localized corrosion effects and modifications of acidic and alkaline slurries on copper chemical mechanical polishing

This study demonstrates the CMP performance can be enhanced by modifying the corrosion effects of acidic and alkaline slurries on copper. A corrosion test-cell with a polishing platform is connected with the potentiostat to investigate the corrosion behaviors of copper CMP in various alumina slurries. Experiments show that the slurry needs to be maintained in acidic pH<4.56 or alkaline pH>9.05 surroundings and thus better dispersion of alumina particles and less residual contaminant on copper surface can be obtained. The surface defects after copper CMP using acidic and alkaline slurries are described by pitting corrosion mechanisms, and these mechanisms can be regarded as a basis to modify their corrosion effects. Experimental results indicate that it is necessary to modify the dissolution of HNO₃ and oxidization of NH₄OH for copper CMP slurries. Consequently, the slurries of 5 wt.% HNO₃ by adding 0.1 wt.% BTA or 5 wt.% KNO₃ by adding 1 wt.% NH₄OH achieve good CMP performance for copper with higher CMP efficiency factor (CMPEF), 1460 and 486, and lower surface roughness (R_q), 4.019 and 3.971 nm, respectively. It is found that AFM micrographs can support the effectiveness of corrosion modifications for copper CMP in various slurry chemistries.     

Formation of Mo and MoSx nanoparticles on Au(1 1 1) from Mo(CO)6 and S2 precursors: electronic and chemical properties

Mo(CO)₆ can be useful as a precursor for the preparation of Mo and MoS_x nanoparticles on a Au(1 1 1) substrate. On this surface the carbonyl adsorbs intact at 100 K and desorbs at temperatures lower than 300 K. Under these conditions, the dissociation of the Mo(CO)₆ molecule is negligible and a desorption channel clearly dominates. An efficient dissociation channel was found after dosing Mo(CO)₆ at high temperatures (>400 K). The decomposition of Mo(CO)₆ yields the small coverages of pure Mo that are necessary for the formation of Mo nanoclusters on the Au(1 1 1) substrate. At large coverages of Mo (>0.15 ML), the dissociation of Mo(CO)₆ produces also C and O adatoms. Mo nanoclusters bonded to Au(1 1 1) exhibit a surprising low reactivity towards CO. Mo/Au(1 1 1) surfaces with Mo coverages below 0.1 ML adsorb the CO molecule weakly (desorption temperature<400 K) and do not induce C–O bond cleavage. These systems, however, are able to induce the dissociation of thiophene at temperatures below 300 K and react with sulfur probably to form MoS_x nanoparticles. The formed MoS_x species are more reactive towards thiophene than extended MoS₂(0 0 0 2) surfaces, MoS_x films or MoS_x/Al₂O₃ catalysts. This could be a consequence of special adsorption sites and/or distinctive electronic properties that favor bonding interactions with sulfur-containing molecules.     

Nb/Au/(1 1 0)YBa2Cu3O7−δ Josephson junctions: evidence against atomic scaled “corner junctions”

We report on I–V characteristics for in situ formed Nb/Au/(1 1 0)YBa₂Cu₃O_7−δ (YBCO) Josephson junction, where the homoepitaxial (1 1 0)YBCO film shows ultra-smooth surface morphology. The field dependence of critical supercurrent I_c shows anisotropic large junction behavior with normal Fraunhofer patterns expected from BCS model of d_x²−y² wave superconductors. This strongly suggests that the Nb/Au/(1 1 0)YBCO junctions cannot be regarded as atomic scaled corner junctions, in contrast with (0 0 1)/(1 1 0)YBCO grain boundary junctions to show “π-junction” with a pronounced dip near zero fields in field modulation of I_c.     

Spin-polarized ion scattering spectroscopy of CCl4 adsorption on Fe(0 0 1) surfaces

The interaction of CCl₄ molecules with Fe(0 0 1) surfaces was investigated by spin-polarized ion scattering spectroscopy (SP-ISS). It was observed that CCl₄ molecules adsorb dissociatively on the surface at ambient temperature (290 K), and consequently, iron and chlorine were major surface constituents. It was found that the chlorine adatoms are located atop of iron atoms of the second surface layer (hollow sites of the surface). It is indicated that the spin state of iron atoms at the surface is not affected by exposure to a CCl₄ atmosphere, while almost no spin is induced in the chlorine adatoms. Similar behavior is observed in the spin states of iron and chlorine on an oxygen preadsorbed-Fe(0 0 1) surface. The difference in the spin states of iron and chlorine clarifies the local property of the incidence ion neutralization and element selectivity of SP-ISS in this CCl₄/Fe system.     

Relationship between electronic and crystal structure in Cu–Ni–Co–Mn–O spinels: Part B: Binding energy anomaly in Cu photoemission spectrum

In very rare circumstances, X-ray photoemission spectra of copper in spinel oxides exhibit a “negative binding energy shift”. The origin of such an anomalous XPS chemical shift was investigated. A metastable Ni_0.48Co_0.24Cu_0.6+xMn_1.68−xO₄ (0 < x < 0.6) spinel was fabricated at 600 °C using a low-temperature solution technique. The binding energy of the 2p_3/2 level of copper (930.8 eV) is found 1.9 eV lower than that of Cu⁰ (932.7 eV). XPS and EXAFS studies revealed that the post-thermal annealing between 600 and 800 °C undergoes an irreversible cubic-to-tetragonal phase transformation through oxidation–reduction reaction Cu¹⁺ + Mn⁴⁺  Cu²⁺ + Mn³⁺, and only tetrahedral Cu¹⁺ species in the cubic spinel shows this anomalous chemical shift. The negative shift of the core levels was correlated to an equal shift of the Cu 3d valence band levels. XPS valence bands from the samples annealed at different temperatures were compared to DOS calculations. The DOS computations were performed with FEFF-8.1 code using experimental crystal parameters established by the EXAFS analysis. It was found that the tetrahedral Cu¹⁺ in the 600 °C annealed sample exhibits localization of the 3d orbitals showing behavior characteristic to zinc. The completely filled and isolated 3d electron shell appears as a false valence band edge in the XPS spectrum. The position of the Cu 3d, and other core levels, is established by oxygen pinning the Cu valence band levels and by the fixed value of the p–d gap characteristic to the tetrahedral copper environment in this spinel.     

Fluorination of the silicon dioxide surface during reactive ion and plasma etching in halocarbon plasmas

Surface sensitive spectroscopies were employed to investigate the surface modifications which occur on SiO₂ during actual reactive ion and plasma etching in CF₄ and CF₄/O₂ plasmas. Photoemission and electron energy loss spectroscopies were used to characterize the composition and bonding in the modified layer. Core level photoemission measurements indicated a reaction layer 10–15 Å thick with a mean composition of SiOF₂. Photoemission and EELS studies of the valence bands identified several features due to Si---F bonding. Comparisons with the SiO₂ valence bands and implications for bonding are discussed. Electron energy loss spectra were also used to determine if ion induced “defect” species formed during reactive etching persist in the reaction layer. A comparison of reactive ion etching samples with those exposed to plasma etching conditions (negligible ion bombardment) indicated that the ion bombarded surfaces exhibit a reduced level of fluorination during steady state etching. Low energy ion scattering was used to determine the composition of the outermost atomic layer. These measurements indicated a fluorine terminated surface with virtually no remaining surface oxygen.     

微通道板离子壁垒膜粒子阻透特性的蒙特卡罗模拟

在三代微光像管中,微通道板(MCP)输入面上覆盖一层超薄离子壁垒膜(IBF),目的是保护光电阴极,延长像管使用寿命.为了深入研究离子壁垒膜的特性,本文对Al2O3和SiO2两种离子壁垒膜的粒子阻透能力进行了蒙特卡罗模拟,结果表明:5 nm厚Al2O3和SiO2离子壁垒膜的死电压分别为230 ～240 V和220～230...     

Effect of Ag promoter on redox properties and catalytic performance of Ag-Mo-P-O catalysts for oxidative dehydrogenation of propane

The influence of addition of sliver ions on the redox properties and catalytic performance of molybdenum-phosphate catalyst in oxidative dehydrogenation (ODH) of propane has been investigated. MoO₃ and AgMoO₂PO₄ have been detected in Ag-doped Mo-P-O catalysts. The redox properties have been characterized by H₂-temperature-programmed reduction (TPR), electronic paramagnetic resonance (EPR) and X-ray photoelectron spectroscopy (XPS). The catalytic performance of MoO₃, Ag₂O, AgMoO₂PO₄ and Ag-doped Mo-P-O catalysts has also been examined. The incorporation of Ag improved the number of Mo⁵⁺ species and the reducibility of the catalysts. The Ag-doped catalysts favor activity and selectivity in ODH of propane higher than the undoped catalyst. The best catalyst was obtained with Ag/Mo ratio of 0.3 and MoO₃/AgMoO₂PO₄ ratio of 1.1. The influence of promoter Ag⁺ on redox properties and catalytic performance is due to forming redox couple “Ag⁰+Mo⁶⁺Ag⁺+Mo⁵⁺” and the synergetic effect originating from “coherent interface” between MoO₃ and AgMoO₂PO₄.     

高能脉冲C~(6+)离子束激发Ni靶的K壳层X射线

精确测量离子与原子碰撞引起的靶原子内壳层电离截面,对研究原子内壳层过程以及建立合适的理论模型具有重要的意义.现有的实验数据和理论模型大都集中在中低能区,高能区由于受到实验条件的限制,几乎没有相关实验数据的报道,哪种理论更适合描述高能重离子入射的靶原子内壳层电离截面,还需要进行深入的实验研究.采用电子冷却存储环提供能量分别为165,300,350,430 MeV/u的C~(6+)离子束轰击Ni靶,测量Ni的K壳层X射线.分析了实验中探测到的Ni的K_β和K_α射线强度比,发现入射粒子能量的变化对该强度比影响不明显.分别应用两体碰撞近似(BEA)、平面波玻恩近似(PWBA)和ECPSSR理论对Ni的K壳层X射线的产生截面进行理论计算,并将理论结果与实验结果进行比较.