SrS/α-SiO~2界面的XPS研究

TFEL器件中绝缘层与发光层之间的界面对电荷的输运特性、发光特性等有着十分重要的作用。本文通过XPS的测量,分析了新结构器件中SrS/α-SiO~2界面的各成分的芯电子能谱的变化和深度分布,发现Sr^2^+向SiO~2中扩散较深并以氧化物的形态存在,介质层以SiO~x(x=1.65～1.70)的形态存在。这些丰富的界面态有可能成为TFEL器件的初电子源而对SrS:Ce发光有贡献。     

Effect of strontium substitution on the composition and microstructure of sol–gel derived calcium phosphates

Sr-doped calcium phosphates have been prepared by sol–gel chemistry. All samples exhibit two phases: hydroxyapatite (HAp) and tricalcium phosphate (β-TCP). With respect to undoped sample, the Sr-doped samples exhibit higher proportion of β-TCP phase but the quantity appears to be quite independent of the doping level. To explain the mismatch with the nominal stoichiometry, the presence of amorphous CaO and SrO compounds have been postulated and their proportions evaluated. The insertion of Sr²⁺ ions in the two crystalline phases HAp and β-TCP is almost total for low doping levels but quite incomplete for the highest doping level. The majority of the inserted Sr²⁺ ions are in the β-TCP phase. Considering the acknowledged beneficial effect of Sr²⁺ on the bone regeneration process, the effective partial substitution of Sr in biphasic calcium phosphate makes these materials very interesting for clinical applications. The Sr-substituted HAp and β-TCP cell parameters agree fairly well with the Vegard’s law and Sr²⁺ ions substitute preferentially for Ca²⁺ in the Ca2 site for hydroxyapatite and in the Ca4 site for β-TCP. The microstructural parameters confirm the previous observation and give a new evidence of clear stabilizing effect of Sr²⁺ ions towards the β-TCP structure.     

Hard and soft X-ray photoelectron spectroscopy for selective probing of surface and bulk chemical compositions in a perovskite-type Ni catalyst

Combined chemical analyses of both the surface and bulk of industrial catalysts is a significant challenge, because all microanalysis methods reveal either the surface or the bulk properties but not both. We demonstrate the combined use of hard and soft X-ray photoelectron spectroscopy (XPS) as a powerful, practical, and nondestructive tool to quantitatively analyze the chemical composition at the surfaces (~1 nm) and subsurfaces/bulk (~10 nm) for catalysts. The surface-bulk differentiation is achieved via an exchangeable anode system, where the Al (Kα, 1486.6 eV) and Cr (Kα, 5414.7 eV) for the XPS and hard X-ray photoelectron spectroscopy (HAXPES) analyses, respectively, are interchanged without affecting the X-ray beam position on the sample. As an archetypical catalyst, we study the perovskite-type material La_0.30Sr_0.55Ti_0.95Ni_0.05O_3-δ (LSTNO), which has differing chemical compositions at the surface and subsurface after reduction and oxidation reactions. We look at the relative changes in surface composition, which minimizes the error stemming from the differing relative sensitivity factors in the oxidized and reduced states. The HAXPES-XPS analysis indirectly confirms the well-known exsolution and formation of Ni nanoparticles on the surface upon reduction though following changes of Ni concentration at the surface. However, the XPS-HAXPES analysis demonstrates an increase in not only the Ni but also the Sr, which corroborates the reorganization within the perovskite lattice upon reduction. The XPS-measured intensities decrease for all the accessible peaks (La 3d, Sr 3d, lattice O 1s, and Ti 2p), which is attributed to the photon diffusion by the surface Ni nanoparticles.     

XPS study on surface modification of NiTi alloy by acidic solution immersion and subsequent heating in air

Changes in the surface chemical state of a nearly equiatomic nickel–titanium (NiTi) alloy caused by immersion in aqueous solutions of HNO₃ and H₂SO₄ as well as subsequent heating in air at 723 K were analyzed using X-ray photoelectron spectroscopy (XPS). An XPS analysis using angle-resolved technique and a mathematical deconvolution technique revealed that a passive layer formed in an ambient atmosphere contained TiO₂ as a major state and Ni(OH)₂ and NiO as minor states. The Ni(OH)₂ on the alloy remained in the region even when heated in air at 723 K. Therefore, the resulting layer became a Ti-oxide layer with Ni segregated region at the surface, which was NiO formed via dehydration of Ni(OH)₂. However, immersion in an aqueous solution of HNO₃ or H₂SO₄ enables Ni(OH)₂ state to dissolve in the passive layer of a NiTi alloy; thereby, the Ni segregated region rarely appeared in the oxide layer by heating. The Ni segregated region at the surface becomes an obstacle for the inward diffusion of oxygen; thus, the annihilation of such a segregated region results in an increase in the thickness of the oxide layer.     

One-step approach for nano-crystalline hydroxyapatite coating on titanium via micro-arc oxidation

Nano-crystalline hydroxyapatite (HAp) films were formed at the surface of Ti by a single-step micro-arc oxidation (MAO) using Ca²⁺ and P⁵⁺ ion-containing electrolytes. The HAp films were 10–25 μm thick, showing strong crystallinity dependence on the CaCl₂ concentration in the electrolytes. Also, the formation of an amorphous CaTiO₃ interlayer was identified to exist between the HAp and Ti substrates. In contrast to the previous researches using K₂HPO₄ for the electrolytes, KH₂PO₄ was used in this study, and this could allow the formation of the crystalline HAp layer. It is suggested as the most probable mechanism for the HAp formation that the high-density hydroxyl groups of TiO(OH)₂, formed by the reactions between the amorphous CaTiO₃ interlayer and the H⁺ ions from the dissolution of the KH₂PO₄, can play a key role in the nucleation and crystal growth of HAp by attracting Ca²⁺ and P⁵⁺ ions in the electrolytes.     

Untersuchungen im System SrO?SiO2?H2O

Investigation on the System SrO? SiO₂? H₂O On addition sodium silicate solutions to solutions of Sr(OH)₂, at room temperature strontium hydrogensilicates are precipitated which are always amorphous and contain silicate anions of various condensation degrees. At about 100°C at first also amorphous products are formed containing lower- and higher-molecular silicate anions. On standing of these precipitates at about 80°C under the mother liquor, however, cristallization occurs under complete degradation of the higher-molecular anions to monomeric resp. dimeric silicate anions. In dependence on the Na₂O: SiO₂ ratio of the sodium silicate solutions and on the Sr(OH)₂ concentrations the following crystalline compounds are formed: 1.25 SrO · 1 SiO₂ · 2 H₂O, 3 SrO · 2 SiO₂ · 3 H₂O and 3 SrO · 2 SiO₂ · 4 H₂O, with monomeric silicate anions; 2 SrO · 2 SiO₂ · 1.5 H₂O; 2 SrO · 2 SiO₂ · 2 H₂O, and 2 SrO · 2 SiO₂ · 3 H₂O, with dimeric anions.     

Thermoanalytical study of the formation of compounds in the PbO−MO (M=Ca,Sr, Ca+Sr) system

In order to clarify the effect of PbO addition on the formation steps of the superconducting phases in the system Bi₂O₃?SrO?CaO?CuO, a study of solid-state reactions under non-isothermal conditions, in the PbO?MO (M=Ca, Sr, Ca+Sr) system has been carried out. Results suggest that the reactivity of the components in the system containing PbO and CaO is much higher than in the system containing SrO. The Ca₂PbO₄ compound is formed first even in the system whereM=Ca+Sr. It is confirmed that Ca₂PbO₄ systems containing PbO.     

Photoelectron core levels for enargite,Cu3AsS4

The mineral chemistry of enargite surfaces and near‐surfaces prepared by fracture within an ultrahigh vacuum are investigated using XPS and synchrotron radiation XPS (SRXPS). The purpose of the study is to identify surface core‐level line positions in high‐resolution photoelectron spectra. The XPS spectra obtained using monochromatic Al Kα radiation show that there are near‐identical monosulphide line positions in S 2p spectra for the As–S and Cu–S bonds in enargite. The SRXPS spectra for sulphur are remarkably similar to the XPS spectra for sulphur, showing that there is minimal difference in the chemical environment between sulphur atoms at the surface and in the mineral matrix. The Cu 2p XPS data have only cuprous contributions and a minor surface contribution. The surface Cu contribution is observed as a high‐binding‐energy tail in the Cu 2p_3/2 spectrum. The As 3d data for both XPS and SRXPS show contributions from arsenic atoms at the surface and in the bulk mineral matrix. The surface contribution is distinct and is found 1 eV below the bulk contribution. The results of the study suggest that, following fracture, the enargite surface is reorganized in such a manner that the surface is characterized by protrusions of individual arsenic atoms. Copyright © 2004 John Wiley & Sons, Ltd.     

Electronic structure of lanthanum transition-metal oxyarsenides LaMAsO (M = Fe,Co, Ni) and LaFe1−xM′xAsO (M′ = Co,Ni) by X-ray photoelectron and absorption spectroscopy

The electronic structures of the quaternary oxyarsenides LaMAsO (M = Fe, Co, Ni) were examined with X-ray photoelectron spectroscopy (XPS) and X-ray absorption near-edge spectroscopy (XANES). Interpretation of the metal 2p_3/2 and arsenic 3d_5/2 binding energies, as well as a satellite feature in the Co 2p XPS spectrum, suggests charges that are much less extreme than expected (i.e., not M²⁺ and As^3?) because of the strong covalent character within the M–As bonds. As M is varied, the differing degrees of charge transfer from M to As atoms within these bonds are manifested by shifts in the As 3d_5/2 binding energies and changes in the As K-edge intensities. This charge transfer is isolated within the [MAs] layer and does not influence the O 1s and La 3d XPS spectra. Fitting the experimental valence band spectra of these oxyarsenides LaMAsO yielded electron populations of states that support the formal charge assignment [La³⁺O^2?][M²⁺As^3?]. The mixed-metal series LaFe_1?xM′_xAsO (M′ = Co, Ni) was examined by XANES; analysis of the metal K- and L-edges, as well as of the Co 2p XPS satellite feature, revealed that no metal–metal charge transfer takes place.     

YBCO超导体中B位元素替代的簇模型计算研究

由计算电荷分布讨论了元素的氧化态，指出ＹＢＣＯ中不存在Ｃｕ￣（３＋），计算得到Ｂ位的Ｂａ，Ｓｒ等元素有负电荷，直接解释了Ｂａ３ｄ，Ｂａ４ｄ．束缚能ＸＰＳ测定的“反常”结果。同时指出Ｂ位元素与其配位氧原子形成电子库，其容量由Ｂ位原子上负电荷大小标志，它与Ｏ＿（２ｐ）空穴相关。还讨论了Ｙ／ＢＣＯ中一些化学键的性质，它们可能与高温超导电性相关联。     

La1—xMxCoO3（M=Ca,Sr）表面状态的XPS研究

合成了一系列钙钛矿复合氧化物La_(1-x)M_(?)CoO_3(M=Ca,Sr),并用XPS研究了LaCoO_3中的La~(3+)部分被Ca~(2+)或Sr~(2+)取代后表面状态的变化。由XPS的O_(10)谱图拟合得到的吸附氧O(2)百分数与取代量x呈现规律性变化。对Ca_(2p)与Sr_(3d)谱图也进行峰拟合处理,其中结合能较高的Sr(2)、Ca(2)可指认为周围有氧离子缺位物种。Ca(2)或Sr(2)百分数与吸附氧百分数的关系可用取代后表面状态的变化来解释。     

Biomimetic fabrication of hydroxyapatite hollow spheres with polyoxyethylene chain-containing quaternary ammonium salt cationic Gemini surfactant as template

This paper reports a biomimetic fabrication of hydroxyapatite (HAp) with a hollow spherical three-dimensional architecture, using Ca(NO₃)₂ and (NH₄)₃PO₄ as the starting materials, and a polyoxyethylene chain-containing quaternary ammonium salt cationic Gemini surfactant [C₁₂C₂C₁₂ (EO)] as the template. The effects of the surfactant concentration, aging time, and temperature on the morphology and the degree of crystallinity of HAp were investigated. We also proposed a possible mechanism for the formation of hollow spherical HAp. The results showed that the cationic Gemini surfactant was the most important parameter for the formation of spherical HAp. We obtained uniform well-defined hollow spherical HAp with semidiameter about 1.5 μm, using 0.1% mass fraction of template, at 37°C for 7 days.     

Core level photoemission spectroscopy and chemical bonding in Sr2Ta2O7

Electronic parameters of constituent element core levels of strontium pyrotantalate (Sr₂Ta₂O₇) were measured with X-ray photoelectron spectroscopy (XPS). The Sr₂Ta₂O₇ powder sample was synthesized using standard solid state method. The valence electron transfer on the formation of the Sr–O and Ta–O bonds was characterized by the binding energy differences between the O 1s and cation core levels, Δ(O–Sr) = BE(O 1s) − BE(Sr 3d_5/2) and Δ(O–Ta) = BE(O 1s) − BE(Ta 4f_7/2). The chemical bonding effects were considered on the basis of our XPS results for Sr₂Ta₂O₇ and earlier published structural and XPS data for other Sr- and Ta-containing oxide compounds. The new data point for Sr₂Ta₂O₇ is consistent with the previously derived relationship for a set of Sr-bearing oxides. The binding energy difference Δ(O–Sr) was found to decrease with increasing bond distance L(Sr–O).     

X-ray photoelectron spectroscopy-based valence band spectra of passive films on titanium

Titanium (Ti) is always covered by thin passive films. Thus, valence band (VB) spectra, obtained using X-ray photoelectron spectroscopy (XPS), are superpositions of the VB spectra of passive films and that of the metallic Ti substrate. In this study, to obtain the VB spectra only of passive films, angular resolution (for eliminating the substrate Ti contribution) and argon ion sputtering (for removing passive films) were used along with XPS. The passive film on Ti was determined to consist of a very thin TiO₂layer with small amounts of Ti₂O₃, TiO, hydroxyl groups, and water with a thickness of 5.9 nm. The VB spectra of Ti were deconvoluted into four peak components: a peak at ~1 eV, attributed to the Ti metal substrate; a broad peak in the 3–10 eV range, mainly attributed to O 2p (~6 eV) and O 2p-Ti 3d hybridized states (~8 eV), owing to the π (non-bonding) and σ (bonding) orbitals in the passive oxide film; and a peak at ~13 eV, attributed to the 3σ orbital of O 2p as OH⁻or H₂O. The VB region spectrum between approximately 3 and 14 eV from Ti is originating from the passive film on Ti. In particular, characterization of VB spectrum obtained with a takeoff angle of less than 24° is effective to obtain VB spectrum only from the passive film on Ti. The property as n-type semiconductor of the passive film on Ti is probably higher than that of rutile TiO₂ceramics.     

Preparation of an experimental glass-ionomer cements and evaluation of their properties

The preparation of glass-ionomer cements based on the composition of SiO₂–Al₂O₃–CaO–SrO–F and evaluation of their properties is described. Cements were prepared via the sol–gel method and characterized by XRD, BET, SEM, and EDAX analysis. The effect of various concentrations of Sr on in vitro bioactivity of the glass speciments was investigated. In vitro bioactivity of the samples was evaluated by soaking them in simulated body fluid followed by structural characterization using SEM and atomic absorption analysis. A glass specimen with 0.5 mol of Sr exhibited appropriate bioactivity.     

High oxygen vacancy tin oxide synthesized by combustion chemical vapor deposition (CCVD)

Tin oxide nanotentacles were synthesized by combustion chemical vapor deposition in air. Their surface composition and optical properties were then investigated using X‐ray photoelectron spectroscopy (XPS) and Raman spectroscopy. XPS core level spectra indicate that these nanotentacles are of high oxygen vacancy with chemical composition of about SnO_1.6, which is also supported by the Sn Auger parameter. Besides SnO₂, the optical properties of SnO were detected in Raman spectrum. Moreover, two new Raman peaks were found for the SnO₂ phase because of the high oxygen vacancy concentration. Copyright © 2008 John Wiley & Sons, Ltd.     

固相浸渍法制备NiO/CeO2催化剂及其在CO氧化反应中的应用

采用固相浸渍法制备了一系列NiO/CeO2催化剂,并通过与常规湿浸渍法比较,考察了制备方法对催化剂和CO氧化反应性能的影响.同时结合X射线衍射(XRD),N2吸附-脱附(BET),透射电镜(TEM),氢气-程序升温还原(H2-TPR),拉曼(Raman)光谱,X射线光电子能谱(XPS)等手段对催化剂的结构和表面物种分散状态进行了表征.CO氧化活性测试结果表明,当镍负载量相同时,固相浸渍法制备的催化剂相比于湿浸渍法表现出更好的催化性能.TEM、XPS、H2-TPR结果表明,固相浸渍法更有利于加强镍铈间的相互作用和得到高分散的镍物种,从而促进镍物种的还原.Raman结果表明固相浸渍法相比于湿浸渍法能产生更多氧空位,这有利于氧气在催化剂表面的活化,使得CO氧化反应更容易进行.     

Surface characterization of Co,K/La2O3 catalysts used for the catalytic combustion of diesel soot

Catalysts of Co,K/La₂O₃ have been prepared by wet impregnation. The samples have been calcined at 400°C and 700°C and have been characterized for phase composition using x‐ray diffraction and Fourier transform infrared spectroscopy. The XPS analysis of the samples has been obtained by examination of the O 1s, K 2p, C 1s and La 3d spectral regions. The XPS data are discussed with respect to the calcination temperatures and the soot combustion performed in the spectrometer reaction chamber. Analysis of the XPS data indicates considerable carbonation of the surfaces of all samples, even after burning the soot. The K/La₂O₃ solid presents the highest content of surface carbonated species, showing the highest catalytic activity for soot combustion. Interaction of the catalysts with CO₂ is studied by temperature‐programmed desorption and microbalance experiments. Kinetic studies and surface characterization of the potassium‐containing samples suggest that an appropriate surface potassium concentration is necessary for a synergetic action between potassium and lanthanum. In the cobalt‐containing catalysts calcined at 700°C, an increase is observed in the concentration of the outer‐layer perovskite species when the potassium content increases, following the same tendency observed in the bulk. Such LaCoO₃ species would limit the reaction of lanthanum with CO₂. Copyright © 2003 John Wiley & Sons, Ltd.     

Synthesis and visible light photocatalytic activity of Ag spot-coated TiO2–60 wt% SrO composite powders

Nano-sized TiO₂–60 wt% SrO composite powders were synthesized from titanium isopropoxide and Sr(OH)₂·8H₂O by use of a sol–gel method. Ag spot-coated TiO₂–60 wt% SrO composite powders containing 3, 5, or 7 wt% Ag were synthesized by hydrothermal-assisted attachment, by use of Ag hydrosol in a high-pressure bomb at 250 °C and 450 psi. Nano-sized Ag particles approximately 5–25 nm in diameter adhered to the TiO₂–60 wt% SrO₂ composite powders. The photocatalytic activity of Ag spot-coated TiO₂–SrO powders in the degradation of phenol showed that all were highly active when irradiated with UV light. TiO₂–60 wt% SrO composite powder spot-coated with 5 wt% Ag was more photocatalytically active under visible light than TiO₂–SrO composite powder.