Formation and hydrogenation of p(2 × 2)-N on Pt(1 1 1)

The formation of a well-ordered p(2 × 2) overlayer of atomic nitrogen on the Pt(1 1 1) surface and its reaction with hydrogen were characterized with reflection absorption infrared spectroscopy (RAIRS), temperature programmed desorption (TPD), low energy electron diffraction (LEED), Auger electron spectroscopy (AES), and X-ray photoelectron spectroscopy (XPS). The p(2 × 2)-N overlayer is formed by exposure of ammonia to a surface at 85 K that is covered with 0.44 monolayer (ML) of molecular oxygen and then heating to 400 K. The reaction between ammonia and oxygen produces water, which desorbs below 400 K. The only desorption product observed above 400 K is molecular nitrogen, which has a peak desorption temperature of 453 K. The absence of oxygen after the 400 K anneal is confirmed with AES. Although atomic nitrogen can also be produced on the surface through the reaction of ammonia with an atomic, rather than molecular, oxygen overlayer at a saturation coverage of 0.25 ML, the yield of surface nitrogen is significantly less, as indicated by the N₂ TPD peak area. Atomic nitrogen readily reacts with hydrogen to produce the NH species, which is characterized with RAIRS by an intense and narrow (FWHM ∼ 4 cm⁻¹) peak at 3322 cm⁻¹. The areas of the H₂ TPD peak associated with NH dissociation and the XPS N 1s peak associated with the NH species indicate that not all of the surface N atoms can be converted to NH by the methods used here.     

Effect of oxygen exposure on the magnetic properties of ultrathin Co/Ge(1 1 1) films

Influences of oxygen exposure on the magnetic properties of Co/Ge(1 1 1) ultrathin films have been investigated by surface magneto-optic Kerr effect technique. As the oxygen exposure increases on Co/Ge(1 1 1) films, their magnetic properties could be modified. As an example for 15 ML Co/Ge(1 1 1) films, the coercivity increases from 730 to 920 Oe and the remanence Kerr intensity is reduced for 500 Langmuir (L) of oxygen exposure. Corresponding compositions analyzed by Auger electron spectroscopy measurement shows that the amount of oxygen on the surface layers increases with increasing the oxygen exposure time. Oxygen distributes on the topmost layers of the film. The adsorbed oxygen influences the electronic density of states of Co and results in the changes of the magnetic properties. Besides, the appearance of O/Co/Ge interface could modify the stress anisotropy, and as a result the coercivity of ultrathin Co/Ge(1 1 1) film is enhanced.     

Study of adsorption of oxygen on β-Al2O3 + Au and β-Al2O3 + Pt: Work function measurements—proposition of a model

To improve the understanding of the electrochemical effects observed on an original potentiometric gas sensor, interactions of oxygen with the device were investigated. This gas sensor is made of a solid electrolyte (treated Na-β-alumina) associated with two metallic electrodes (gold and platinum) located in the same gas mixture. Adsorption of charged oxygen species, considered responsible for the electrical response developed by the sensor, was investigated by work function measurements. Results showed that charged oxygen species only form on partially gold or platinum covered solid electrolyte. Comparison of these results with those obtained in a previous calorimetric study of interactions between oxygen and the same materials suggests the existence of at least two different oxygen species adsorbed on the surface of the sensitive element. The first one, located on the solid electrolyte surface, is neutral and characterized by an endothermal reaction of formation. The second one is charged and probably produced at the gas/solid electrolyte/metallic electrode interface. A mechanism based on the concept of “three phase boundary” and similar to the “reverse spillover” phenomenon is proposed to account for the adsorption of these oxygen species.     

Carboxylic fused furans for amino acid fluorescent labelling

Four carboxylic fused furans are presented as new fluorescent labels for the amino and hydroxyl functions of organic molecules. Various representative l-amino acids were chosen as models, labelled at their N-terminus and also at their side-chain. Fluorescent derivatives were obtained in high yields, and their absorption and emission properties were studied.     

Behavior of zirconium in the ZrOW(100) system at high temperature, studied by ISS, AES and work-function measurements

The behavior of zirconium atoms at the W(100) surface associated with oxygen adsorption at different sample temperatures has been studied by Auger electron spectroscopy (AES), ion scattering spectroscopy (ISS), and the relative change of the work function (Δф) measured by the onset of the secondary electron energy distribution. The results have revealed: (i) adsorption of zirconium onto the W(100) surface followed by the elevation of the sample temperature up to 1710 K in an oxygen partial pressure of 2.7 × 10⁻⁴ induces complete diffusion of zirconium atoms into the W(100) substrate; (ii) further exposure of oxygen induces co-existence of oxygen and tungsten on the surface at 1710 K, resulting in a work function of 4.37 eV; (iii) keeping the sample temperature at 1710 K, simple evacuation of the system has resulted in surface segregation of zirconium atoms to the surface to form a zirconium atomic layer on the top-most surface, reducing the work function to 2.7 eV. The results have revealed that this specific behavior of zirconium atoms at high temperature assures, with very good reproducibility, the highly stable performance and long service life of Zr---O/W(100)-emitters in practical use, even in a low vacuum of 10⁻⁶ Pa.     

Effects of oxygen in gamma irradiated aromatic polyesters in film

The effect of gamma irradiation in air is investigated on four thermoplastic polyesters (PET, PBT, PEN, PCT-co-ET) in films containing aromatic rings, in order to evaluate the influence of aromatic density and the role of oxygen on radiation resistance. Physical-chemical-nuclear analyses were used to this purpose. EPR measurements were carried out to detect radical stability against oxygen permeation. Viscometric investigations reported a very similar trend for all the investigated polyesters: a chain break effect that decreases at the highest doses. FT-IR analyses focused on the formation of oxidized species. Positron annihilation spectra pointed out a decrease of the intensity of ortho-positronium formation, while its lifetime remains unchanged with radiation dose.     

IR and XPS investigation of visible-light photocatalysis—Nitrogen-carbon-doped TiO2 film

To use solar irradiation or interior lighting efficiently, we sought a photocatalyst with high reactivity under visible light. Nitrogen and carbon doping TiO_2−x−yN_xC_y films were obtained by heating the TiO₂ gel in an ionized N₂ gas and then were calcined at 500 °C. The TiO_2−x−yN_xC_y films have revealed an improvement over the TiO₂ films under visible light (wavelength, 500 nm) in optical absorption and photocatalytic activity such as photodegradation of methyl orange. X-ray photoemission spectroscopy, infrared spectrum and UV-visible (UV-vis) spectroscopy were used to find the difference of two kinds of films. Nitrogen and carbon doped into substitutional sites of TiO₂ has been proven to be indispensable for band-gap narrowing and photocatalytic activity.     

Corrigendum to “EuBaFe2O5+w: Valence mixing and charge ordering are two separate cooperative phenomena” [J. Solid State Chem. 180 (2007) 148-157]

An error in the expression for the Fe²⁺, Fe³⁺ valence-mixing probability in RBaFe₂O_5+w is acknowledged and correct formula is derived. The new formula slightly improves the least-squares fit to the experimental concentrations of the Mössbauer component Fe^2.5+ as a function of the oxygen-nonstoichiometry parameter w for R=Eu.     

掺杂SrTiO3体系上甲烷氧化偶联反应的研究—活性氧物种的作用

本文采用循环氧化还原法,脉冲反应及TPD等实验手段对钙钛矿型氧化物掺杂SrTiO_3体系上甲烷氧化偶联反应中的活性氧物种的作用进行了研究.结果表明,催化剂由于掺杂产生的未被充分还原的氧物种(O~(α-)(0<α<2)是活化甲烷并促使其发生偶联反应的主要的活性中心,而表面晶格氧(O_L~(2-))则主要使甲烷深度氧化;消耗掉的未被充分还原的氧或晶格氧可以在高温下氧气氛中氧化复原.对于掺杂的SrTiO_3样品,体相中的氧在惰性气氛或还原气氛中可以向表面扩散.吸附氧可能不直接与甲烷作用而主要通过催化剂表面活性氧物种(O~(α-)或O_L~(2-))而起作用.