X-ray photoelectron spectroscopic studies of the oxidation of aluminium by liquid water monitored in an anaerobic cell

The oxidation of clean polycrystalline aluminium foil was performed in a previously described anaerobic cell and studied by core level and valence band X-ray photoelectron spectroscopy. Oxide free sample surfaces were exposed under inert atmosphere at room temperature to increasingly oxidative environments of water vapor and liquid water beginning with an oxide free metal foil each time. Minor oxidative environments were found to produce a film of boehmite with a thinner outer film of gibbsite. Harsher oxidation in liquid water resulted in an oxide film much thicker than that found on the as received sample which contained an inner composition of gamma alumina with an outer film of gibbsite. As expected, the oxide film observed for ultra high purity polycrystalline aluminiurm foil in the as received state was gibbsite. The valence band of the cleaned metal is discussed in terms of residual surface species. The evaluation and determination of these residual surface species is evaluated following an analysis of two different band structure calculations which use different d orbital exponents. It is found that while the density of states is almost unaltered by changes in the d exponent, the predicted spectrum is substantially changed. The work makes extensive use of valence band X-ray photoelectron spectroscopy.     

X-ray photoelectron spectroscopic studies of the oxidation of aluminium by liquid water monitored in an anaerobic cell

The oxidation of clean polycrystalline aluminium foil was performed in a previously described anaerobic cell and studied by core level and valence band X-ray photoelectron spectroscopy. Oxide free sample surfaces were exposed under inert atmosphere at room temperature to increasingly oxidative environments of water vapor and liquid water beginning with an oxide free metal foil each time. Minor oxidative environments were found to produce a film of boehmite with a thinner outer film of gibbsite. Harsher oxidation in liquid water resulted in an oxide film much thicker than that found on the as received sample which contained an inner composition of gamma alumina with an outer film of gibbsite. As expected, the oxide film observed for ultra high purity polycrystalline aluminium foil in the as received state was gibbsite. The valence band of the cleaned metal is discussed in terms of residual surface species. The evaluation and determination of these residual surface species is evaluated following an analysis of two different band structure calculations which use different d orbital exponents. It is found that while the density of states is almost unaltered by changes in the d exponent, the predicted spectrum is substantially changed. The work makes extensive use of valence band X-ray photoelectron spectroscopy.     

Surface modification of surface sol-gel derived titanium oxide films by self-assembled monolayers (SAMs) and non-specific protein adsorption studies

Biological events occurring at the implant-host interface, including protein adsorption are mainly influenced by surface properties of the implant. Titanium alloys, one of the most widely used implants, has shown good biocompatibility primarily through its surface oxide. In this study, a surface sol-gel process based on the surface reaction of metal alkoxides with a hydroxylated surface was used to prepare ultrathin titanium oxide (TiOx) coatings on silicon wafers. The oxide deposited on the surface was then modified by self-assembled monolayers (SAMs) of silanes with different functional groups. Interesting surface morphology trends and protein adhesion properties of the modified titanium oxide surfaces were observed as studied by non-specific protein binding of serum albumin. The surface properties were investigated systematically using water contact angle, ellipsometry, X-ray photoelectron spectroscopy (XPS), and atomic force microscopy (AFM) measurements. Results showed that the surface sol-gel process predominantly formed homogeneous, but rough and porous titanium oxide layers. The protein adsorption was dependent primarily on the silane chemistry, packing of the alkyl chains (extent of van der Waals interaction), morphology (porosity and roughness), and wettability of the sol-gel oxide. Comparison was made with a thermally evaporated TiOx-Ti/Si-wafer substrate (control). This method further extends the functionalization of surface sol-gel derived TiOx layers for possible titanium alloy bioimplant surface modification.     

Antimony(III) Oxide Film on a Cellulose Fiber Surface: Preparation and Characterization of the Composite

Cellulose/antimony(III) oxide composites, Cel/Sb(2)O(3), with oxide loadings of 1.7, 5.4, and 9.2 wt% were prepared by reacting the precursor SbCl(3) reagent with cellulose in dry ethanol solution. The reaction of the Lewis acid and the cellulose fibers occurred at the~amorphous domains of the biopolymer, increasing the crystallinity degree of the composite compared with that of the untreated cellulose. The scanning electron microscopy images and metal mapping for all samples showed that the oxide film layer uniformly covered the fiber surfaces with no detectable agglomerates of the oxide particles. The synchrotron X-ray diffraction patterns indicated that the antimony oxide film was obtained as a crystalline phase with orthorombic structure. The atomic ratios of O/Sb, determined by X-ray photoelectron spectroscopy, indicated that, for Cel/Sb(2)O(3) samples with 9.3 wt% loading, the fiber surface is nearly saturated by the oxide layer. The thermal stability of Cel/Sb(2)O(3) compared to that of untreated cellulose is practically unaffected. Copyright 2000 Academic Press.     

Mixed Co/Fe oxide nanoparticles in block copolymer micelles

Small iron oxide and Co-doped iron oxide nanoparticles (NPs) were synthesized in a commercial amphiphilic block copolymer, poly(ethylene oxide)-b-poly(methacrylic acid) (PEO 68-b-PMAA8), in aqueous solutions. The structure and composition of the micelles containing guest molecules (metal salts) or NPs (metal oxides) were studied using transmission electron microscopy, dynamic light scattering, X-ray photoelectron spectroscopy, and X-ray powder diffraction. The enlarged micelle cores after incorporation of metal salts are believed to be formed by both PMAA blocks containing metal species and penetrating PEO chains. The nanoparticle size distributions in PEO 68-b-PMAA8 were determined using small-angle X-ray scattering (SAXS) in bulk. Two independent methods for SAXS data interpretation for comprehensive analysis of volume distributions of metal oxide NPs showed presence of both small particles and larger entities containing metal species which are ascribed to organization of block copolymer micelles in bulk. The magnetometry measurements revealed that the NPs are superparamagnetic and their characteristics depend on the method of the NP synthesis. The important advantage of the PEO 68-b-PMAA8 stabilized magnetic nanoparticles described in this paper is their remarkable solubility and stability in water and buffers.     

Protein-associated water and secondary structure effect removal of blood proteins from metallic substrates

Removing adsorbed protein from metals has significant health and industrial consequences. There are numerous protein-adsorption studies using model self-assembled monolayers or polymeric substrates but hardly any high-resolution measurements of adsorption and removal of proteins on industrially relevant transition metals. Surgeons and ship owners desire clean metal surfaces to reduce transmission of disease via surgical instruments and minimize surface fouling (to reduce friction and corrosion), respectively. A major finding of this work is that, besides hydrophobic interaction adhesion energy, water content in an adsorbed protein layer and secondary structure of proteins determined the access and hence ability to remove adsorbed proteins from metal surfaces with a strong alkaline-surfactant solution (NaOH and 5 mg/mL SDS in PBS at pH 11). This is demonstrated with three blood proteins (bovine serum albumin, immunoglobulin, and fibrinogen) and four transition metal substrates and stainless steel (platinum (Pt), gold (Au), tungsten (W), titanium (Ti), and 316 grade stainless steel (SS)). All the metallic substrates were checked for chemical contaminations like carbon and sulfur and were characterized using X-ray photoelectron spectroscopy (XPS). While Pt and Au surfaces were oxide-free (fairly inert elements), W, Ti, and SS substrates were associated with native oxide. Difference measurements between a quartz crystal microbalance with dissipation (QCM-D) and surface plasmon resonance spectroscopy (SPR) provided a measure of the water content in the protein-adsorbed layers. Hydrophobic adhesion forces, obtained with atomic force microscopy, between the proteins and the metals correlated with the amount of the adsorbed protein-water complex. Thus, the amount of protein adsorbed decreased with Pt, Au, W, Ti and SS, in this order. Neither sessile contact angle nor surface roughness of the metal substrates was useful as predictors here. All three globular proteins behaved similarly on addition of the alkaline-surfactant cleaning solution, in that platinum and gold exhibited an increase, while tungsten, titanium, and stainless steel showed a decrease in weight. According to dissipation measurements with the QCM-D, the adsorbed layer for platinum and gold was rigid, while that for the tungsten, titanium, and stainless steel was much more flexible. The removal efficiency of adsorbed-protein by alkaline solution of SDS depended on the water content of the adsorbed layers for W, Ti, and SS, while for Pt and Au, it depended on secondary structural content. When protein adsorption was high (Pt, Au), protein-protein interactions and protein-surface interactions were dominant and the removal of protein layers was limited. Water content of the adsorbed protein layer was the determining factor for how efficiently the layer was removed by alkaline SDS when protein adsorption was low. Hence, protein-protein and protein-surface interactions were minimal and protein structure was less perturbed in comparison with those for high protein adsorption. Secondary structural content determined the efficient removal of adsorbed protein for high adsorbed amount.     

Photochemical grafting and patterning of organic monolayers on indium tin oxide substrates

Covalently attached organic layers on indium tin oxide (ITO) surfaces were prepared by the photochemical grafting with 1-alkenes. The surface modification was monitored with static water contact angle, X-ray photoelectron spectroscopy (XPS), and atomic force microscopy (AFM) measurements. Hydrophobic methyl-terminated ITO surfaces can be obtained via the grafting of tetradec-1-ene, whereas the attachment of ω-functionalized 1-alkenes leads to functionalized ITO surfaces. The use of a C≡C-Ge(CH(3))(3) terminus allows for facile tagging of the surface with an azido group via a one-pot deprotection/click reaction, resulting in bio/electronically active interfaces. The combination of nonaggressive chemicals (alkenes), mild reaction conditions (room temperature), and a light-induced grafting that facilitates the direct patterning of organic layers makes this simple approach highly promising for the development of ITO-based (bio)electronic devices.     

Helium atom scattering from oxide surfaces.

Many experimental methods of surface science employ electrons or photons of considerable incident energy as probe particles. However, insulating surfaces or delicate physisorbed layers may be damaged by these particles and should, therefore, be analyzed with a gentler probe: He atom scattering allows to determine the symmetry of the unit cell and the detection of phase transitions from diffraction measurements as well as the determination of surface and adsorbate vibrations by time-of-flight resolved detection. Herein, the application of He atom scattering to oxide surfaces is demonstrated on the basis of the examples of MgO and ZnO. MgO(001) is a very inert and stable surface, whereas hydrogen atoms are chemisorbed on the mixed-terminated ZnO(1010) and on both polar faces: ZnO(0001) and ZnO(0001). He atom scattering is very sensitive to the presence of hydrogen on surfaces. In addition ZnO reacts with molecules such as water, CO and CO(2). It is demonstrated that in combination with photoelectron spectroscopy and thermal desorption spectroscopy He atom scattering can also contribute to studies of surface chemistry.     

富锂正极材料Li1.2Mn0.54Co0.13Ni0.13NaxO2表面结构的电子显微分析

采用离子交换加固相烧结法制备出富锂锰基正极材料Li_1.2Mn_0.54Co_0.13Ni_0.13Na_xO₂,利用球差校正扫描透射电子显微镜（STEM）、X射线能谱（EDS）、电子能量损失谱（EELS）等分析手段对材料表面结构与成分展开表征。结果表明：镍（Ni）在样品表面存在选择性富集（垂直于锂扩散通道的表面,如（200）面）,倾向扩散进入锂离子层,并导致表面出现层状结构到岩盐相（rocksalt, Fm3m）结构转变;而钴（Co）在所观察的（001）、（200）表面均存在不同程度的富集,且集中在过渡金属层。进一步研究发现,表面钴（Co）富集不利于层状结构的稳定,时效后样品的（001）面观察到明显的表面重构,存在数量较多的过渡金属（TM）-锂（Li）反位缺陷与岩盐相结构区域。     

Bifunctional Adhesion Promoter for Grafting Polypyrrole Films on Metal/Metal Oxide Surfaces

A new class of pyrrole derivatives, ω-[(3-phenyl) pyrrol-1-yl] alkyl phosphonic acids with long chains of 10 and 12 carbon atoms were synthesised to graft polypyrrole layers on metal/metal oxide surfaces. These compounds are bifunctional containing two reactive moieties, pyrrole as the polymerisable group and phosphonic acid as the anchoring group. Contact angle measurements and X-ray photoelectron spectroscopy (XPS) confirmed adsorption with phosphonic acid group attached to the surface. Surface plasmon resonance (SPR) spectroscopy indicated that adsorption starts in seconds and is completed in few hours. Adsorption is followed by surface induced polymerisation with further monomer. We obtained dense and homogeneous polypyrrole films, which were characterised for their morphology and thickness by atomic force microscopy (AFM). The derivatives form a strongly bonded composite of metal with polymer.     

Porous magnetic manganese oxide nanostructures: synthesis and their application in water treatment

Magnetic manganese oxide nanostructures are fabricated at room temperature by mixing a KMnO(4) solution and oleic acid capped Fe(3)O(4) particles. Oleic acid molecules capped Fe(3)O(4) particles are oxidized by potassium permanganate (KMnO(4)) in an aqueous solution to produce porous magnetic manganese oxide nanostructures. The synthesis technique can be extended to other MnO(x) structures with composition of different nanocrystals, such as quantum dots, noble metal crystals which may have important applications as catalysts, adsorbents, electrodes and advanced materials in many scientific disciplines. Transmission electron microscopy, energy-dispersive X-ray spectroscopy, scanning electron microscopy, X-ray photoelectron spectroscopy, X-ray powder diffraction, Fourier transform infrared spectroscopy, and nitrogen adsorption-desorption measurements are employed to characterize the structures. As an adsorbent in water treatment, the nanostructures possess a large adsorption capability and high organic pollutant removal rates due to the large surface area and pore volume. The nanostructures are recyclable as their adsorption capability can be recovered by combustion. Furthermore, the strong magnetism exhibited by the structures provides an easy and efficient separation means in wastewater treatment under an external magnetic field.     

Decoration of Few-Layer Graphene-Like MoS2 and MoSe2 by Noble Metal Nanoparticles

Graphene has been decorated by nanoparticles of noble metals and other inorganic materials. In the present study, we have decorated graphene-like MoS₂ and MoSe₂, containing 3–5 layers, with Au, Ag and Pt nanoparticles. We have characterized these nanocomposites using X-ray diffraction, electron microscopy and absorption spectroscopy. The studies reveal that the surfaces of the layered inorganic materials get uniformly coated with the noble metal nanoparticles. There are indications that the interaction of the metal particles with these layered materials is rather weak.     

Au nanoparticle monolayers covered with sol-gel oxide thin films: optical and morphological study

In this work, we provide a detailed study of the influence of thermal annealing on submonolayer Au nanoparticle deposited on functionalized surfaces as standalone films and those that are coated with sol-gel NiO and TiO(2) thin films. The systems are characterized through the use of UV-vis absorption, X-ray diffraction (XRD), atomic force microscopy (AFM), scanning electron microscopy (SEM), and spectroscopic ellipsometry. The surface plasmon resonance peak of the Au nanoparticles was found to red-shift and increase in intensity with increasing surface coverage, an observation that is directly correlated to the complex refractive index properties of Au nanoparticle layers. The standalone Au nanoparticles sinter at 200 °C, and a relationship between the optical properties and the annealing temperature is presented. When overcoated with sol-gel metal oxide films (NiO, TiO(2)), the optical properties of the Au nanoparticles are strongly affected by the metal oxide, resulting in an intense red shift and broadening of the plasmon band; moreover, the temperature-driven sintering is strongly limited by the metal oxide layer. Optical sensing tests for ethanol vapor are presented as one possible application, showing reversible sensing dynamics and confirming the effect of Au nanoparticles in increasing the sensitivity and in providing a wavelength dependent response, thus confirming the potential use of such materials as optical probes.     

Liquid crystalline mesophases of pluronics (L64, P65, and P123) and transition metal nitrate salts ([M(H2O)6](NO3)2)

The triblock poly(ethylene oxide)-poly(propylene oxide)-poly(ethylene oxide) copolymers, Pluronics (L64, P65, and P123), form liquid crystalline (LC) mesophases with transition metal nitrate salts (TMS), [M(H(2)O)(n)](NO(3))(2), in the presence and absence of free water in the media. In this assembly process, M-OH(2) plays an important role as observed in a TMS:C(n)EO(m) (C(n)EO(m) is oligo(ethylene oxide) nonionic surfactants) system. The structure of the LC mesophases and interactions of the metal ion-nitrate ion and metal ion-Pluronic were investigated using microscopy (POM), diffraction (XRD), and spectroscopy (FTIR and micro-Raman) techniques. The TMS:L64 system requires a shear force for mesophase ordering to be observed using X-ray diffraction. However, TMS:P65 and TMS:P123 form well structured LC mesophases. Depending on the salt/Pluronic mole ratio, hexagonal LC mesophases are observed in the TMS:P65 systems and cubic and tetragonal LC mesophases in the TMS:P123 systems. The LC mesophase in the water/salt/Pluronic system is sensitive to the concentration of free (H(2)O) and coordinated water (M-OH(2)) molecules and demonstrates structural changes. As the free water is evaporated from the H(2)O:TMS:Pluronic LC mesophase (ternary mixture), the nitrate ion remains free in the media. However, complete evaporation of the free water molecules enforces the coordination of the nitrate ion to the metal ion in all TMS:Pluronic systems.     

Hybrid composites of monodisperse pi-conjugated rodlike organic compounds and semiconductor quantum particles

Composite materials of quantum particles (Q-particles) arranged in layers within crystalline powders of pi-conjugated, rodlike dicarboxylic acids are reported. The synthesis of the composites, either as three-dimensional crystals or as thin films at the air-water interface, comprises a two-step process: 1) The preparation of the Cd salts 6 (Cd), 8 (Cd) or Pb salts 6 (Pb), 8 (Pb) of the oligo(p-phenyleneethynylene)dicarboxylic acids 6 (H), 8 (H), in which the metal ions are arranged in ribbons and are separated by the long axis of the organic molecules, as demonstrated by X-ray powder diffraction analysis of the solids and grazing incidence X-ray diffraction analysis of the films on water. 2) Topotactic solid/gas reaction of these salts with H(2)S to convert the metal ions into Q-particles of CdS or PbS embedded in the organic matrix that consists of the acids 6 (H) and 8 (H). These hybrid materials have been characterized by X-ray photoelectron spectroscopy and transmission electron microscopy.     

Catalytic Etching of Platinoid Gauzes during the Oxidation of Ammonia by Air. Reconstruction of Surface of Platinoid Gauzes at 1133 K in Air,in Ammonia,and in an NH<Subscript>3</Subscript> + O<Subscript>2</Subscript> Reaction Medium

The structure, morphology, and chemical composition of the surface and near-surface layers of platinoid wires of polycrystalline gauzes, containing Pt (81 wt %), Pd (15 wt %), Rh (3.5 wt %), and Ru (0.5 wt %) after treatment at 1133 K in various media—in air, in ammonia, and after NH3 oxidation in air—are studied by X-ray diffraction (XRD), scanning electron microscopy (SEM), energy-dispersive X-ray (EDX) spectroscopy, and X-ray photoelectron spectroscopy (XPS). A thin film is found on the surface of the initial gauze containing an oxide layer of Rh₂O₃ with a thickness of ~2 nm, on the surface of which an inhomogeneous graphite-like layer 10–50 nm thick is located. It is shown that the heat treatment of gauzes in air leads to the partial removal of the surface graphite-like film that forms the reticulated structure on the wire surface. The treatment of gauzes in an ammonia atmosphere leads to the complete removal of the graphite-like and oxide layers and to the growth of metal grains of ~10 μm. After the catalytic reaction of NH3 oxidation, a deep structural rearrangement of the surface layer of the wire takes place, as a result of which crystalline metal agglomerates of ~10 μm are formed. It is supposed that the reaction of NH3 molecules with oxygen atoms penetrated on the defects leads to the local increase of temperature, due to which the metal atoms emerge on the surface and form large crystalline agglomerates and pores in the region of the grain boundaries.     

Relationship between structure and CO oxidation activity of ceria-supported gold catalysts

Gold catalysts supported on cerium oxide were prepared by solvated metal atom dispersion (SMAD), by deposition-precipitation (DP), and by coprecipitation (CP) methods and were characterized by X-ray diffraction (XRD), temperature programmed reduction (TPR), and X-ray photoelectron spectroscopy (XPS). The catalytic activity was tested in the CO oxidation reaction. The structural and surface analyses evidenced the presence of a modified ceria phase in the case of the DP sample and the presence of pure ceria and gold metal crystallites in the case of the SMAD and CP samples. The DP sample, after a mild treatment in air at 393 K, exhibited only ionic gold, and it was very active below 273 K. By comparing the activities of the different catalysts, it is suggested that the presence of small gold particles, as obtained by the SMAD technique, is not the main requisite for the achievement of the highest CO conversion. The strong interaction between ionic gold and ceria, by enhancing the ceria surface oxygen reducibility, may determine the particularly high activity.     

In situ infrared spectroscopic studies of ultrathin inorganic film growth on zinc in non‐polymerizing cold plasmas

The effect of cold plasmas of oxygen, hydrogen, water and carbon dioxide on zinc samples was investigated. Oxygen plasma is known for its cleaning effect, hydrocarbons and water are removed from metal surfaces and the oxide layer is thickened. It was found that other oxygen‐containing gases had a similar effect. In addition, surface layers of other compounds were produced. The samples were investigated using XPS, Kelvin probe measurements and in situ infrared reflection absorption spectroscopy. Copyright © 2003 John Wiley & Sons, Ltd.     

Graphene nanosheets decorated with Pd,Pt,Au,and Ag nanoparticles:Synthesis,characterization,and catalysis applications

We report that noble metal nanopartcles (Pd,Pt,Au,and Ag) decorated-graphene nanosheets can be synthesized with the template of graphene oxide by a one-pot solution-based method.The resulting hybrid materials are characterized by transmission electronic microscopy,energy dispersive X-ray spectroscopy,scanning electronic microscopy,atomic force microscopy,X-ray diffraction,and Raman spectroscopy,which demonstrate that the metal nanoparticles have been uniformly deposited on the surfaces of graphene nanosheet...     

Vanadium Pentoxide Sol and Gel Mesophases

Colloidal suspensions of V₂O₅ ribbon-like particles display optical textures typical of lyotropic nematic phases. Tactoids (small nematic droplets) and then isotropic phases are formed as these systems are diluted. Nematic suspensions can be oriented by applying a magnetic or an electric field. Such a liquid crystal behavior is mainly due to the highly anisotropic shape of vanadium oxide colloidal particles. Acid dissociation at the oxide/water interface gives rise to surface electrical charges and electrostatic repulsion should also be responsible for the stabilization of the nematic phases. Anisotropic xerogel layers are formed when these gels are deposited and dried onto flat substrates. X-ray diffraction patterns of such coatings exhibit a series of 00l harmonics due to the turbostratic stacking of the oxide particles. Dehydration is reversible and fluid mesophases are again obtained via a swelling process when water is added to the xerogel.