XPS and XAES analysis of copper,arsenic and sulfur chemical state in enargites

Enargite, a copper arsenic sulfide with the formula Cu₃AsS₄ is of environmental concern due to its potential to release toxic arsenic species. The oxidation and dissolution of enargite are governed by the composition and chemical state of the outermost surface layer. Qualitative and quantitative analysis of the enargite surface can be initially obtained on the basis of X‐ray photoelectron spectroscopy (XPS) binding energy and intensity data. However, a more precise determination of the chemical state of the principal elements of enargite (copper, arsenic and sulfur) in the altered surface layer and in the bulk of the mineral requires a combined analysis based on XPS photoelectron lines and the corresponding X‐ray excited Auger lines. On the basis of results obtained on natural and synthetic enargite samples and on standards of sulfides and oxides, the Auger parameter α′ of different compounds was calculated and the Wagner chemical state plots were drawn for arsenic, copper and sulfur. Arsenic in enargite is found to be in a chemical environment similar to that of arsenides or elemental arsenic, whereas copper in enargite is in a chemical state that corresponds to copper sulfide, Cu₂S, for all samples irrespective of surface treatment (natural or freshly cleaved). Only sulfur changed from a chemical state similar to that of copper or iron sulfide in freshly cleaved samples to another state in natural enargite in the as‐received state. Thus, it is the sulfur atom at the surface of enargite that is most susceptible to changes in the enargite surface state and composition. A more detailed interpretation of this behavior, based on differences in the initial and final state effects, is proposed here. The concept of Auger parameter and chemical state plot, used here for the first time for investigating enargite, has proved to be a method to unambiguously assign the chemical state of the principal elements copper, arsenic and sulfur in these minerals. Copyright © 2006 John Wiley & Sons, Ltd.     

K-Pb-Tl-O复合氧化物的合成和电子结构的XPS研究

用熔盐阳极电沉积法合成了导电的复合氧化物K-Pb-Tl-O晶体.这些晶体具有纳米尺寸层状结构.用XPS对其进行了表征,并与相关的化合物进行了比较.实验表明,氧化物中的Pb和Tl都以高价态的单一价态存在,但电子结合能比相应的非导电低价化合物的低.该文用原子外弛豫效应解释了复合氧化物中的Pb和Tl的结合能的反常现象.讨论了它们的价电子结构与导电性的关系.     

溶剂化金属原子浸渍法制备的Ni-Ag/γ-Al2O3催化剂的结构表征

应用溶剂化金属原子浸渍法和普通浸渍法制备了三种不同摩尔比的γ－Ａｌ２Ｏ３负载Ｎｉ－Ａｇ双金属催化剂。ＸＲＤ和磁测定结果表明ＳＭＡＩ催化剂中Ｎｉ和Ａｇ的粒度均小于金属相同的ＣＩ催化剂。ＳＭＡＩ催化剂中Ｎｉ和Ａｇ未形成合金，而ＣＩ催化剂中Ｎｉ和Ａｇ形成了合金。     

XPS study of interactions between linear carbon chains and colloidal Au nanoparticles

1. Download : Download high-res image (158KB)
2. Download : Download full-size image

     

Titanium‐implanted CaTiO3 films and their changes in Hanks' solution

Titanium‐implanted CaTiO₃ film was prepared and then characterized by x‐ray photoelectron spectroscopy (XPS) and Rutherford backscattering spectrometry (RBS) before and after immersion in Hanks' solution for 7 days. An as‐prepared specimen contained a small amount of Ar implanted during sputtering, although the pressure was as low as 10^?4 Torr. Even though Ar convolution increased with an increase in the relative Ti ion dose, most of the convoluted Ar was not from the Ar gas used for Ti ion production but rather was from the Ar gas used for sputtering the CaTiO₃. During Ti implantation, the CaTiO₃ films were ion‐etched by Ti ions. The composition of the CaTiO₃ film was not changed to any great degree by the Ti implantation, however its properties changed considerably. After immersion in Hanks' solution, the thickness of the specimen not implanted with Ti decreased the most whereas the [Ca]/[P] ratio, which was nearly unity before exposure, decreased significantly, becoming 0.23 on the Ti‐implanted specimen prepared at 200 W and 0.13 on the Ti‐implanted specimen prepared at 50 W. It was also observed by XPS that the ratio [Ca]/[P] was ～1.9 for all Ti‐implanted specimens after immersion in Hanks' solution for 7 days. Judging from the binding energies of Ca 2p_3/2 and P 2p electrons and the [Ca]/[P] ratio, it was suggested that a hydroxyapatite‐like substance had formed on the surfaces of the Ti‐implanted specimens after immersion in Hanks' solution. Copyright © 2003 John Wiley & Sons, Ltd.     

Bi-Sr-Ca-Cu-O超导体与氧化物衬底材料的反应性估计

测定了一系列氧化物的电子结合能，显示了铋系超导体与二元氧化物衬底材料的化学反应性可以用固态酸碱反应理论来描述，其反应性大小除了可以用衬底氧化物的酸碱参数估计以外，还可以用衬底氧化物氧离子的内层电子结合能估计．     

Perfluorinated polymer surfaces comprising SF5-terminated long-chain perfluoroacrylate

A new perfluorinated acrylate monomer containing the SF₅(CF₂)₆-perfluorinated side chain was synthesized and polymerized into films. Bulk monomer characterization is consistent with the molecular structure based on FTIR, mass spectrometry and NMR analyses. The surface properties of polymer coatings were studied with aqueous wetting (contact angle) and X-ray photoelectron spectroscopy (XPS) methods. The surface composition is shown to be highly enriched in the terminal side chain SF₅-chemistry and exhibits properties consistent with a highly apolar, non-wetting perfluorinated polymer surface. Depth-dependent XPS studies using angular-resolved methods (ADXPS) confirmed a non-stoichiometric enrichment of sulfur and fluorine at the film ambient interface, consistent with a surface presence of the terminal SF₅-group and possibly film structural anisotropy in the surface zone. Time-of-flight (TOF) secondary ion mass spectrometry (SIMS) analysis supplements the XPS data by showing the presence of all expected SF₅-acrylate chemistry components in the outer 15 Å of the film surface.     

Eu1—xTbxBa2Cu3O7—δ中Tb离子价态的研究

研究了BaTbO_3、Tb_4O_7、TbFeO_3的Tb_(4d)XPS谱,找到了表征Tb~(3+)、Tb~(4+)的特征峰,得出的高、低结合能峰强之比与Tb~(4+)/Tb含量间的依赖关系,可用于确定Eu_(1-x)Tb_xBa_2Cu_3O_(7-δ)中“123”相的Tb离子混合价态,用常压高温烧结法,未能获得纯“123”单相,也不易获得纯利Tb~(3+)价态样品.在Eu_(1-x)Tb_xBa_2Cu_3O_(7-δ)中的Tb以Tb~(3+)、Tb~(4+)混合价态存在;当x=0.3时,Tb~(4+)/Tb=0.61.引入Tb~(4+)后“123”主相Cu(2)-O(2)平面上的O_(2p)空穴数降低,这是Tb~(4+)破坏超导电性的一种可能原因。     

XPS analysis of the effect of Pt addition to Pd catalysts for complete benzene oxidation

Pt-Pd bimetallic catalysts were prepared in order to develop and investigate catalysts having excellent activity and stability for benzene destruction. The effect of Pt addition to Pd catalysts is studied by XPS analysis. This revised version was published online in August 2006 with corrections to the Cover Date.     

A comparative study between inductively and capacitively coupled plasma deposited polystyrene films: chemical and morphological characterizations

Thin polystyrene films were deposited on stainless steel substrates by capacitively and inductively coupled radio frequency glow discharge plasma, in order to compare their chemical and morphological properties. The films were characterized by Fourier‐transform infrared spectroscopy (FTIR), X‐Ray photoelectron spectroscopy (XPS), time‐of‐flight secondary ion mass spectrometry (ToF‐SIMS), atomic force microscopy (AFM) and scanning electron microscope (SEM). Wettability properties were also determined by contact angle measurements. Ageing effect was studied by analysing films aged for 15 min and for 1 week. Results from both capacitively and inductively plasma polymerized polystyrene (pPS) films aged for 15 min showed that the chemical structure of the bulk, chemical composition of the surface (depth < 10 nm) and wettability properties were rather similar. Only their microstructures were very different: the pPS_capa film's microstructure showed homogeneous distribution of spherical particles of about 100 nm in diameter but the pPS_ind film's microstructure seemed to be mainly influenced by the surface of the metallic substrate: orientated ‘lamellae‐like layers’ of polymers were observed on each metallic grain. Ageing for 1 week in ambient air induced low oxygen uptake in the surface of both pPS films. The pPS_ind topmost surface (depth < 3 nm) was more oxidized than that of pPS_capa but no modification of the chemical structure of the bulk or of the morphology was noticed after ageing. Copyright © 2006 John Wiley & Sons, Ltd.