Complementary spectroscopic techniques to model the association of contaminant uranium with structural surfaces

Contaminant uranium poses unique problems for decontamination of former weapons processing and nuclear power facilities, as well as chemical plants, waste storage sites and former mining facilities. In addition, dealing with the possibility of intentional (i.e., a terrorist act) or accidental release of radioactive material in a populated area requires an accurate understanding of the nature of the association of such material with structural surfaces. These surfaces must also be considered in the context of repeated contamination, and the importance of atmospheric exposure, interaction with other possible contaminants, and corrosion or surface degradation due to such exposure must be taken into account. Complementary spectroscopic techniques, especially surface spectroscopies, are essential in developing models for the interaction of contaminants with surfaces and interfaces. In this review (which also presents new data on uranium association with corroding steel surfaces), we collect models of this association as determined by spectroscopic techniques, assess the important considerations in the development of more accurate models, and address some of the questions which remain.     

A Tin(IV) Porphyrin with Two Axial Organometallic NCN‐Pincer Platinum Units

A tin(IV) porphyrin was combined with two axial NCN‐pincer platinum(II) fragments by utilizing the oxophilicity of the apical positions on the tin atom and the acidic nature of the NCN‐pincer platinum derived benzoic acid. The solid‐state structure determined by X‐ray crystallography revealed some close contacts between the pincer complexes and the meso‐p‐tolyl subsitutents of the porphyrin. It was shown by ¹H NMR spectroscopy that these close contacts were not present in solution and that this compound can potentially act as a novel building block for supramolecular architectures.     

Lorentz-Compton佯谬与一个双赢判决性散射实验设计

通过对“可见光区域是否存在Compton效应”的讨论而进一步深化到经典条件下“光的量子理论能否包含光的经典电磁理论”的实验验证,发现了Lorentz-Compton佯谬,并基于逆Compton散射设计了一个敏感而又可行的双赢判决性散射实验来解决此佯谬。     

Magnetic Properties of Metallic Multilayered Systems

Hyperfine Interactions - The giant magnetoresistance (GMR) effect was an epoch-making discovery in the field of magnetic materials research. In this article, studies on magnetic multilayered...     

Synthesis and structures of nitroxyalkyl methylphosphonates

The reactions of ethylene glycol mononitrate and glycerol 1,3-dinitrate with methylphosphonic dichloride afforded new nitroxyalkyl methylphosphonates.     

Mössbauer and X-ray diffraction characterization of Fe60Al40 coatings prepared by thermal spraying

Microstructured (atomized) and nanostructured (milled) Fe₆₀Al₄₀ powders together with their corresponding coatings synthesized by High Velocity Oxy-fuel (HVOF) or Atmospheric Plasma Spray (APS) thermal spraying techniques have been characterized by Mössbauer Spectroscopy (MS) and X-ray Diffraction (XRD). The evolution of the microstructure and the atomic ordering degree in the powders and coatings are discussed at the light of the various processing conditions. The operational correlation between the parameters of the duplex morphology of coatings and the processing parameters is discussed.     

Preliminary studies on a variable energy positron annihilation lifetime spectroscopy system

There are many advantages in being able to perform positron annihilation lifetime spectroscopy (PALS) using a variable energy positron beam, the most obvious being the easy identification of different defect types at different depths. The difficulty in conducting variable energy (VE) PALS studies lies in the fact that a “start” signal is required to signal the entry of the positron into the target. Two methods have been used to overcome this problem, namely the bunching technique, which employs radio frequency (RF) cavities and choppers, and secondly the use of secondary electrons emitted from the target. The latter technique is in terms of experimental complexity much simpler, but has in the past suffered from poor time resolution (typically ∼500 ps). In this work, we present a series of computer simulations of a design based on the secondary electron emission from thin C-foils in transmission mode which shows that significant improvements in time resolution can be made with resolutions ∼200 ps being in principle possible.     

A detailed analysis of the photoemission spectra of basic thioaromatic monolayers on noble metal substrates

Analysis of photoemission spectra of complex thioaromatic self-assembled monolayers (SAMs) requires the knowledge and understanding of such spectra for the basic systems. Keeping this goal in mind, synchrotron-based high-resolution X-ray photoelectron spectroscopy was used to characterize SAMs formed from the simplest thioaromatic compounds, namely thiophenol, 1,1′-biphenyl-4-thiol and 1,1′;4′,1″-terphenyl-4-thiol on evaporated Au(1 1 1) and Ag(1 1 1) substrates. The acquired S 2p and C 1s spectra were analyzed in terms of fine structure and initial and final state effects in the photoemission process. The assignment of the individual spectral features was considered in detail. Conclusions on quality and chemical and structural homogeneity of the investigated SAMs were derived.     

Investigation of chemical decomposition of CCl4 on TiO2 near room temperature

Dissociative adsorption of CCl₄ on TiO₂ at 35 °C has been studied by Fourier-transform infrared spectroscopy, X-ray photoelectron spectroscopy, and electron spin resonance. CCl₄ decompose to form CO, CO₂, and CO₃ on the surface, at such a low temperature, in which CO₂ formation is not from CO oxidation on TiO₂, but CO₃ can be produced by CO and CO₂ adsorption. The Cl generated from CCl₄ decomposition is left on the surface and bonded to titanium ions. Mineralization of CCl₄ on TiO₂ involves the lattice oxygens. Thermodynamical driving force and possible reaction routes for CO and CO₂ formation in the CCl₄ decomposition on TiO₂ are discussed.     

Growth and characterization of model oxide catalysts

Oxide catalysts are frequently used to convert toxic species to environmentally benign molecules, and to prevent the formation of toxic species in the first place. In this paper, growth and characterization of model oxide systems employed in both approaches is discussed. An example of the former approach is the selective catalytic reduction (SCR) of NO emitted from power plants by NH₃, which employs tungsten and vanadium oxides supported on the anatase polymorph of TiO₂. To model SCR catalysts, epitaxial titanium, vanadium and tungsten oxide films were grown using molecular beam epitaxy and magnetron sputtering. Two different anatase orientations were grown on LaAlO₃ substrates and their interactions with vanadia were characterized. On LaAlO₃ (0 0 1), anatase exposed a (4 × 1) reconstructed (0 0 1) surface. Vanadia lifted the reconstruction and at 1 ML a (1 × 1) surface with mostly V⁵⁺ was observed. Continued V₂O₅ growth led to loss of order, but at high temperatures epitaxial VO₂ could be grown; vanadia behaved similarly on anatase films on LaAlO₃ (1 1 0). Results suggested that the monolayer is pseudomorphic with O adsorption oxidizing the surface V to 5+, since the anatase structure cannot accommodate more bulk oxygen, only a monolayer can be pseudomorphic and have only V⁵⁺. Thus the vanadia monolayer has unique structural and chemical properties that can help explain why vanadia monolayers on TiO₂ are much more active than bulk V₂O₅. For WO₃, a series of added row reconstructions were observed as the epitaxial films were reduced. The effect of these structures on surface chemistry was characterized by studying 1-propanol adsorption. The results indicated that the structure of the WO₃ surface did not alter its catalytic function but had a strong effect on reaction kinetics. As an example of a system where catalysts prevent the formation of toxic species, the reactivity of oxidized Pd surfaces used in CH₄ catalytic combustion were studied. An ordered PdO-like monolayer was found to be less reactive towards CO than adsorbed O on Pd. On the other hand, the PdO layer favored a lower activation energy C₃H₆ oxidation pathway. The results indicated that Pd oxidation reduces the sticking coefficient of reactive species but once molecules adsorb, the oxide surface can reduce the activation energy for subsequent reaction.