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Undoped and Ni-doped TiO2 thin films, with Ni concentration in the range 3–9 at.%, were obtained by reactive magnetron co-sputtering. A combined analysis by X-ray photoelectron spectroscopy and extended X-ray absorption-edge fine structure shows that Ni2+ substitutes for Ti4+ in the TiO2 lattice and promotes, at higher Ni amounts, a structural transition of the host from anatase to rutile. Several difficulties of the extended X-ray absorption-edge fine structure analysis, in the case of Ni-doped TiO2, are also discussed. X-ray diffraction data revealed that a large amount of the films material is in amorphous state. The films are very smooth, with root mean square roughness values (below 1.5 nm) decreasing with the increase of the Ni content. The hydrophilic properties of TiO2, modified by Ni doping, are also investigated.

The “ one-pot ” hydrolyltic hydrogenation of cellulose towards C2-C6 sugar alcohols has been recognized as one of the most promising biomass valorization routes for the production of high added-value chemicals. In this work, we studied the performance of Ru and Pt catalysts supported on micro/mesoporous activated carbon, in the hydrolytic hydrogenation of microcrystalline and ball-milled cellulose, in neat water, at 180 °C and at relatively low hydrogen pressure of 2 MPa. The impact of metal loading (1–5 wt.%), metal reduction method (H 2 at 350 °C or NaBH 4 ) and acidification (sulfonation) of the AC support on cellulose conversion and selectivity to the various products were systematically addressed. It was shown that Pt is significantly more selective towards hexitols (sorbitol and mannitol) compared to Ru, in glucose-rich reaction media, such as those offered by the easily hydrolyzed ball-milled cellulose. For example, the 5wt%Pt/AC-SO 3 H catalyst afforded hexitols yield of 69.5 wt.% (at 96.1% conversion) compared to 10.9 wt.% (at 95.2% wt.% conversion) obtained by the corresponding Ru catalyst, the latter being also selective towards glycerol and propane-1,2-diol (propylene glycol). A relatively moderate metal loading, such as in 3 wt.%Ru/AC-SO 3 H, was more favorable for hexitols production (44.5 wt.% yield, at 94.8 wt.% conversion) with Ru catalysts. These results were also verified by glucose hydrogenation experiments that were conducted at the same experimental conditions. Both Pt and Ru exhibited relatively high glucose hydrogenation activity towards hexitols, versus retro-aldol reactions that lead directly to smaller C2–C4 compounds, while the difference in the final product yields between the two metals was attributed to the higher hexitols hydrogenolysis (C C cleavage) reactivity of Ru. HRTEM data showed the formation of metallic crystalline Pt and Ru nanoparticles (≤4 nm, depending on loading) as well as of amorphous oxygen-rich M(O) x δ+ phases, which were also confirmed by the XPS data. The presence of these phases which may be a source of acidity, as well as the bacisity of the parent AC used in this study, were mainly responsible for inducing isomerization, retro-aldol and dehydration reactions leading eventually to increased glycerol and propylene glycol selectivity, as was observed for both low-metal catalysts, i.e. 1 wt.% Pt or Ru/AC.

We report the structural, electronic and magnetic investigation using extended X-ray absorption fine structure spectroscopy (EXAFS), photoelectron microscopy, spin-resolved photoemission and magneto-optical Kerr effect on the properties of Mn $$_{x}$$ Ge $$_{1-x}$$ systems obtained by molecular beam epitaxy deposition of manganese on Ge(001) wafers annealed on temperatures between 50 and 450 $$^{\circ }$$ C. Magnetic ordering can be achieved when the substrate temperature is higher than 250 $$^{\circ }$$ C, when the manganese tends to diffuse into the Ge matrix and segregate in Mn $$_{5}$$ Ge $$_{3}$$ -like compounds, as proved by EXAFS. High spatial resolution photoelectron spectroscopy reveals Mn inhomogeneities in the 5–10 $$\upmu $$ m range, even though Mn is found mostly in the same chemical state all over the surface.

EuFeO3 perovskite was considered as a case study of the cooperative effects of the rare earth and transition metal elements in the total catalytic oxidation of aromatic hydrocarbons. For this purpose, a EuFeO3 perovskite was prepared using the citrate route. Extensive characterization was performed via ex situ and in situ methods. EXAFS revealed that oxygen vacancies are formed in the nearest neighborhood of Fe and next-nearest neighborhood of Eu. Combining 151Eu and 57Fe Mossbauer experiments also suggested local oxygen defects in the proximity of the Eu cations during the reaction, as well as cooperative electron delocalization effects between Eu and Fe. XPS has shown the +3 oxidation state of both Eu and Fe cations and the relatively strong ionicity of the Fe–O chemical bonds, as suggested by the weakened 2p3/2 satellite in the Fe2p spectrum. A systematic change of this satellite with the A cation in AFeO3 perovskites was also discussed. The thermal treatment of the catalyst at 623 K, in air or toluene, was accompanied by a partial reduction of Fe and a partial oxidation of Eu, respectively. The interaction between the two elements appeared to be influenced mainly by the temperature and only slightly by the sample environment during further treatments. Catalytic oxidation of toluene on this perovskite led only to the production of carbon dioxide and water with no side-product formation from partial oxidation reactions. All the characterization and catalytic results preferably agree with a Volkenstein mechanism.

Amorphous titania thin films with increasing Fe content have been prepared by RF magnetron sputtering. X-ray absorption spectroscopy revealed modifications of both local structures/environment of the Ti and Fe atoms, with formation of phases containing amorphous material and a magnetite-like phase. The temperature dependence of the electrical conductivity of the films was investigated for temperatures higher than half of the Debye temperature (T > 391 K). It was found that the electrical conductivity in the amorphous Fe/TiO2 films obeys the Meyer–Neldel rule. The origin of this behavior is explained on the basis of the multiphonon-assisted hopping model.

Samarium is deposited on Si(001) at various temperatures (room temperature to 400 °C), and the surface structure, interface reactivity, electron configuration, and magnetic properties are investigated by low-energy electron diffraction (LEED), X-ray photoelectron spectroscopy (XPS), and magneto-optical Kerr effect (MOKE), respectively. It is found that metal Sm is present on samples prepared at room temperature with an interface layer containing mostly Sm2+ and a lower amount of Sm3+. When samples are prepared at high temperature, much less Sm0 is found with an increasing amount of Sm2+. Freshly prepared Sm0 and SmSi2 layers react strongly with oxygen from the residual gas, promoting formation of Sm2O3 at the expense of both metal Sm and SmSi2. Room temperature ferromagnetism is observed for all prepared layers with a decrease of the saturation magnetisation when samples are prepared at high temperature. It is found that ferromagnetism implies mostly Sm3+ and Sm metal. In addition to these findings, this work proposes a new assignment of the Sm 3d chemically shifted components. Also, a noticeable variation of the XPS Sm 3d spin-orbit splitting is found as a function of the Sm ionization state.

Vitamin K4 (menadiol diacetate, MDD) can be easily synthesized through cleaner and more efficient catalytic alternatives following the green chemistry principles. Ionic gold-based hydroxylated fluorides are active bi-functional catalysts for the one-pot hydroacetylation of menadione leading to MDD with 77% selectivity. Unprecedent results were obtained in the presence of oxide-fluoride cat- alysts by using a microwave-assisted hydrogen- transfer (Meerwein-Ponndorf-Verley reaction) cou- pled with an acetylation approach, yielding very high selectivities for the target product (95%).

This study presents a correlated study of structural, reactivity, and magnetic properties of ultrathin Fe layers grown on Si(001) by molecular beam epitaxy in ultrahigh vacuum. The interface reactivity is characterized by Auger electron spectroscopy. The surface structure is characterized by low electron energy diffraction with spot profile analysis. The magnetism of the synthesized layers is investigated by magneto-optical Kerr effect. At room temperature, metal Fe layers with poor long-range order are synthesized; these layers are ferromagnetic with an extremely low coercitive field (below 1 Oe). The reactivity with Si is low in this case, with formation of an interface layer of about 8 A Fe equivalent thickness with about 7 at.% Si diffused. Samples synthesized at higher temperatures (500 °C) exhibit better long-range order, though the Fe reactivity with Si is higher and leads to the formation of an interface compound whose approximate stoichiometry is very close to Fe3Si. Once this compound is formed (for an equivalent Fe thickness of about 14 monolayers), disordered metal Fe islands are developing with subsequent Fe deposition, which contain also about 8 at.% Si diffused. These structures exhibit a much lower ferrimagnetism, with saturation magnetization about one order of magnitude lower than in the case of the room temperature synthesis. In this case of high temperature synthesis, two phases are observed, a ferrimagnetic one and a superparamagnetic one.

Cobalt-doped vanadium oxide thin layers prepared by pulsed laser ablation are investigated from the following points of view: (1) the chemical states by X-ray photoelectron spectroscopy (XPS), (2) the local atomic order by X-ray absorption fine structure at both vanadium and cobalt K-edges, (3) the morphology of the films by atomic force microscopy (AFM) and (4) the magnetic properties by magneto-optical Kerr effect (MOKE). The chemical composition of the host matrix was found to be close to VO2 at the sample surface, with V2O3 in the bulk. Co ions are found near the surface in high ionisation states Co4+ (for the samples synthesised in a high vacuum condition, denoted by VO1), or with Co(4− δ )+ (for the samples synthesised in an oxygen atmosphere, denoted by VO2), whereas in the bulk, Co1.5+ is obtained for VO1 and Co2+ is obtained for VO2. The AFM revealed nanoparticles with sizes 10–25 nm for VO1 samples, whereas a few bigger nanoparticles are observed for VO2 samples. The VO1 samples presented high c...

Nitrogen doped TiO 2 aerogels were obtained by sol–gel process followed by supercritical drying with liquid CO 2 . Urea and NH 3 (25% aqueous solution) were used as nitrogen sources. The as-prepared aerogels were submitted to thermal treatments performed under different experimental conditions (temperature and heating time). Increasing the temperature from 450 °C to 550 °C a decrease about 32% and 15.4% of the particle size and surface OH groups’ concentration, respectively and an increase about 21.4% of the incorporated nitrogen in TiO 2 lattice were observed. The immersion of the TiO 2 aerogels in NH 3 solution induced a decreasing by 48.86% and by 80% of the S BET and the aerogel porosity, respectively. The photocatalytic activity of the obtained N-doped TiO 2 was found to depend mainly on the nitrogen incorporation in the TiO 2 lattice.

Unimodal porous system (denoted as SnTf-MCM-41) and bimodal porosity (denoted as SnTf-UVM-7) were prepared in a two-step synthesis. The triflic acid was incorporated into previously synthesized Sn-containing porous silicas. Chemical analysis was carried out by electron probe microanalysis (EPMA), textural properties were determined by transmission electron microscopy (TEM) and from nitrogen adsorption–desorption isotherms (77 K), while structural characterization by X-ray absorption near-edge structure (XANES), X-ray photoelectron spectroscopy (XPS) and Auger electron spectroscopy (AES) measurements. The structural characterization provided evidences on the direct interaction of triflate with incorporated tin species. The acidity of these catalysts was determined from the ammonia chemisorption measurements. The catalysts have been tested for transesterification of sunflower oil under both microwave and ultrasound activation. These experiments showed a direct reaction between the acidity of the catalysts and catalytic performances. No leaching of the triflate species or catalyst deactivation have been detected over several runs.

TiO2 nanopowders, doped with Fe3+ and Eu3+ were obtained by high-energy ball milling and their physical properties were investigated as a function of the doping content and ball milling time. A noticeable red shift and high photoactivity in the degradation and catalytic oxidation reactions of styrene and phenol were found for all doped specimens.

Iron- and europium-doped (≤1 at.%) TiO 2 nanoparticles powders have been synthesized by a hydrothermal route at 200 °C, starting with TiCl 4 , FeCl 3 ·6H 2 O and EuCl 3 ·6H 2 O. The structure, morphology and optical peculiarities were investigated by means of X-ray diffraction (XRD), transmission electron microscopy (TEM), extended X-ray absorption fine structure (EXAFS), Mossbauer spectroscopy and UV–vis measurements. The photocatalytic performance was analysed in the photodegradation reaction of phenol. Rietveld refinements of XRD patterns reveal that the as-prepared samples consist in iron- and europium-doped TiO 2 in the tetragonal anatase structural shape, with particle size as low as 15 nm. By means of Mossbauer spectroscopy on both 57 Fe and 151 Eu isotopes as well as by EXAFS analyses, the presence of Fe 3+ and/or Eu 3+ ions in the nanosized powders has been evidenced. It was found that iron and europium ions can substitute for titanium in the anatase structure. From the UV–vis reflection spectra, by using the transformed Kubelka–Munk functions, the band gap energy ( E g ) of the hydrothermal samples has been determined in comparison with that of Degussa P-25 photocatalyst. A decrease of E g from 2.9 eV found for Degussa photocatalyst to 2.8 eV for the titania doped with 1 at.% Fe has been evidenced, indicating a valuable absorption shift (∼20 nm) towards visible light region. However, the best photocatalytic activity in the photodegradation reaction of phenol was evidenced for the hydrothermal sample, TiO 2 : 1 at.% Fe, 0.5 at.% Eu, in both UV and visible light regions. The photocatalytic activities of iron-doped and iron–europium-codoped samples are high and practically the same only in visible light. The photocatalytic properties in correlation with the structural and optical peculiarities of the hydrothermal samples are discussed.

Carbon layers grown on lead zirco-titanate (PZT) weakly interact with the substrate and exhibit a nearly two dimensional character, up to a carbon surface density approaching that of graphene. The first feature is evidenced by X-ray photoelectron spectroscopy, and the second by angle resolved near-edge-absorption spectroscopy (NEXAFS). The binding energies and lineshape parameters of C 1s are similar to that of graphene. The dichroism of C K-edge NEXAFS shows the prevalence of in-plane sp2 bonds for layers whose effective coverage is below the graphene surface density. The polarization state of the substrate, oriented outwards, is preserved upon carbon deposition. The surface Pb content is strongly affected by the carbon ad-layers.

Stroke incidence in hemodialysis patients is up to 10 times greater than in the general population and is associated with a worse prognosis. Factors influencing stroke risk by subtype and subsequent prognosis are poorly described in the literature.Retrospective single-center cohort study.2,384 established maintenance hemodialysis patients at a single center from January 1, 2002, to June 1, 2009.Patient demographics, comorbid conditions.Incidence of acute stroke (International Classification of Diseases, 9th Revision codes 430, 431, 432.9, 433.1, and 434.1 with evidence of compatible neuroimaging), patient survival.Cumulative patient survival, incidence of acute fatal and nonfatal stroke.127 strokes occurred during 9,541 total patient-years of follow-up. First (incident) stroke occurred at a rate of 14.9/1,000 patient years (95% CI, 12.2-17.9) with a predominance of ischemic compared with hemorrhagic subtypes (11.2 vs 3.7/1,000 patient-years). 54% of hemorrhagic strokes occurred in patients of South Asian ethnicity compared with ischemic strokes, which occurred predominantly in white patients (45% of events). Diabetes mellitus (HR, 1.92; 95% CI, 1.29-2.85; P = 0.001) and prior cerebrovascular disease (HR, 4.54; 95% CI, 3.07-6.72; P < 0.001) were independently associated with incident cerebrovascular accident on multivariate analysis. Acute stroke was associated with worse patient survival (HR, 3.26; 95% CI, 2.47-4.30; P < 0.001) and overall 1-year mortality of 24%, which was significantly worse in patients with hemorrhagic events (39% vs 19% mortality for ischemic subtypes). Serum albumin level >3.5 g/L (HR, 0.38; 95% CI, 0.19-0.76; P = 0.007) and C-reactive protein level >3.0 mg/l (HR, 1.36; 95% CI, 1.12-1.64; P = 0.002) influenced survival after stroke on multivariate analysis.Retrospective analysis of data cannot prove causality.The high incidence of stroke in hemodialysis patients is associated with high mortality, especially hemorrhagic subtypes. Strict management of hypertension, better appreciation of hemodialysis anticoagulation, and large-scale interventional studies are urgently required to direct prevention and treatment of this significant disease.

We report here on the characteristics of RF-sputtered 300 nm thick films of TiO2–2xNx prepared on glass substrates at 350 °C, by adjusting the N2:Ar partial pressure ratio in the deposition chamber between 0.00 and 0.33. XRD, XPS, AFM and contact angle data were used to derive film structure, elemental composition and oxidation state of Ti, surface morphology and hydrophilicity, respectively. The band gap was derived from spectral data in the 350–450 nm range. Film structure and composition were changed by adjusting the partial pressure of the reactive gases during sputtering and by post-deposition annealing at 400 °C in air, for 90 min. The values of the contact angle of films' surface with de-ionized water and of surface free energy per unit area show that films are super-hydrophilic for high-nitrogen content. Correlations are made between film structure, elemental composition, electronic and wettability properties.

Nitrogen doping was proposed recently as a low-cost means to shift the absorption edge of titania towards 450–500 nm. Results are reported here on the preparation of nitrogen-doped 250 nm thick TiO2 films on glass substrates by RF magnetron sputtering. The nitrogen content in the films was modified by changing the N2 partial pressure in the discharge from 0.00 to 0.27 Pa. An additional amount of oxygen was added in the deposition chamber (pO2 = 0.11 Pa) to compensate for oxygen depletion in the films. Surface composition and structure were derived from XPS and XRD data, respectively. XRD data revealed a mixture of amorphous phase and rutile polymorph in the as-deposited films, while an anatase-rich phase occurs in the samples deposited under N2 pressure of 0.05 and 0.16 Pa. Above 0.16 Pa, a rutile-rich phase is present. Surface wettability was investigated from contact angle data of de-ionized water with solid surface. The films deposited under mid-range N2 pressure in the discharge are super-hydrophilic. The photo-induced super-hydrophilicity decays after 36 h. Film wettability is discussed in terms of the synergic effects of surface roughness (measured by AFM) and rutile–anatase TiO2 phase transition, induced by doping. The TiO2 surface super-hydrophilicity (and catalytic efficiency) are related to beneficial properties of anatase phase (Eg = 3.2 eV), associated with a low recombination rate of charge carriers in the surface.

Fe-doped titania films were deposited by RF sputtering onto different substrates (glass and ITO/glass) in the same deposition run. The rutile nanocrystalline structure of Fe-doped thin films deposited on glass substrates and anatase nanocrystalline structure of Fe-doped thin films deposited on ITO/glass substrates were evidenced by XRD. SEM investigations showed a smooth surface with a dense nanostructure. XPS study evidenced an almost stoichiometric composition with different iron contents. EPR and XPS studies evidenced that iron entered into TiO 2 lattice by substitution, as isolated and dimer species. In Fe-doped thin films deposited on ITO/glass substrates the iron content is ten times higher than in Fe-doped thin films deposited on glass substrates and that a part of them entered as Fe 2+ .

The influence of the Mn, Se and Sb impurities on the structure and morphology of CdS thin films grown on p + Si wafers was studied. The starting powders were mixed in the same molar ratios (0.3%) and deposited in the same conditions by vacuum thermal evaporation. X-ray diffraction(XRD), X-ray photoelectron spectroscopy (XPS), atomic force microscopy (AFM) and reflectance studies made on thermal treated thin films (573 K, 2 h in air) evidenced that thin films have a hexagonal oriented structure, and that dopants enter into the CdS lattice merely by substitution. The dopant nature influences the thin film thickness and chemical composition. The doped CdS thin films have roughness in nanometer region and a reflectivity lower than 40%. Silicon substrate acts as a template and favors the retention of Mn and scatters the Sb dopants. The CdS:Se thin film is thicker than CdS:Mn and CdS:Sb ones and is a mixture of doped and undoped nanocrystals.

Results are reported on the characterization of 200–250 nm thick TiO x transparent films grown at temperatures of 150 °C and 500 °C by reactive pulsed-laser ablation of a metallic Ti target under 0.13–13.3 Pa oxygen atmosphere. Film structure and composition were investigated by X-ray diffraction and X-ray photoelectron spectroscopy. The samples deposited at 150 °C reveal a mixture of amorphous TiO 2 and Ti 2 O 3 , irrespective of oxygen pressure. The O:Ti atomic ratio fluctuates in their surface around 1.83 for oxygen pressure ranging between 0.13 Pa and 2.66 Pa. The samples deposited at 500 °C feature different characteristics, as a function of oxygen pressure: (a) below 2.66 Pa of O 2 the films contain a mixture of significant amount of anatase and rutile TiO 2 phases, along with titanium suboxides; (b) above this threshold, the rutile phase vanishes, the anatase TiO 2 phase remaining dominant along with small amounts of nanocrystalline suboxides. The size of the anatase nanocrystallites decreases with the increase of oxygen pressures. The samples deposited at 500 °C feature a slight improvement of surface stoichiometry, from roughly TiO 1.8 to TiO 1.9 . The films deposited at high substrate temperature and oxygen pressure are highly hydrophilic.

An icosahedral (i) Al–Mn–Ce nanophase is formed in rapidly quenched alloys. Ce induces a gradual change of the six-dimensional (6D) lattice from a simple icosahedral (SI) to a face-centered icosahedral (FCI) symmetry with relaxation of lattice distortions. X-ray diffraction (XRD) and extended X-ray absorption fine structure (EXAFS) data support Ce location on FCI sites, although off-center positions are suggested.

The substitution of up to 7 at. % of gold into icosahedral Al62Cu25.5Fe12.5 quasicrystals has been investigated by 197Au and 57Fe Mossbauer spectroscopy. Gold was found to replace copper on BC1 sites and to hybridise strongly with its Al neighbours. In addition, particularly at the higher gold concentrations, the precipitation of small amounts of AuAl2 and β-FeAl was observed.

Structure of metal clusters and of the C60 matrix in Au/C60 and Cu/C60 nanosystems was investigated by X-ray diffraction. Results support a charge-transfer-type interaction at the metal-C60 interface, which affects the size distribution of metal clusters, favouring interstitial location of metal ions in the fullerite lattice.

Ru-zeolites prepared via deposition of aqueous solution of ruthenium chloride on X, L, ZSM-5 and APO-54 were investigated. The impregnated solids were characterized by the following techniques: N-2 sorption, H-2 chemisorption, TPR, XRD, XPS, EXAFS and Mossbauer spectroscopy. It was found that deposition of Ru is influenced by the pore structure and the chemical composition of the supports, in particular the concentration and strength of the protonic sites, with the formation of the different species. The packing of Ru as well as the degree of the reduction and the metal particle size are different according to the penetration depth of the metal and the nature of the zeolite. The amount of chlorine possibly remaining as adatoms of Ru is very low or inexistent. In calcined and reduced catalysts no chloride peak could be evidenced by XPS. The experiments confirmed that the use of large amounts of Ru chloride precursor leads to rather large metal particles. (C) 1999 Elsevier Science B.V. All rights reserved.

In case of a metal finely dispersed in a C60 matrix, the metal-to-C60 charge transfer lowers the interface energy. The total cohesive energy per metal atom Etot was estimated for Au clusters in fullerite. The results show that, for a charge Qf ≥ 1 electron (e) transferred from the metal clusters to each C60 cage, a minimum appears in Etot, defining a most stable cluster size. Thereby, the equilibrium dispersion state of the metal in the fullerite matrix depends on Qf.

Au-substituted Al - Cu - Fe icosahedral phases, , were prepared by melt spinning. EDS data showed that Cu as well as Al atoms are effectively substituted for with Au. The hypercubic lattice parameter of as-quenched samples slowly increases with x, while phonon- and phason-type disorders are not affected by Au substitution. Experimental structure factors for `sum' lines were used to derive an average radius of the atomic hypersurfaces. Comparison of experimental versus calculated ratios of structure factors for different models yielded information about the Au distribution over the icosahedral sites. It was inferred that a fraction of the gold shapes its Al surrounding in a -type configuration. Evidence was found for d - sp hybridization of Au - Al bonds, on the basis of the `white-line' area at the Au absorption edge.

A sweet catalyst: A catalyst formed of Ru/functionalized silica-coated magnetite nanoparticles is highly efficient in the one-pot production of sorbitol and glycerol, starting from cellulose and in the absence of an external hydrogen source. The ease of recoverability of the catalyst from the solid residues, and its reuse without loss of activity or selectivity for several runs, is an important green element of the process.

Au L3 x-ray-absorption near-edge spectra were measured with synchrotron radiation on a series of Au-X compounds, with X5Ga, In, Ge, and Sn. The white-line feature of the spectra, as a rough measure of charge transfer upon compound formation, was related to the local composition around the Au atoms. This enabled us to estimate the local Au environment, in cases where its knowledge is missing. Chemical bonding in intermetallic compounds of transition metals ( T) with less electronegative elements ( X) in the same d row or in groups III-IV-V of the periodic table has stimulated intense theoretical and experimental work. A valence-electron charge-transfer mechanism, initially proposed by Pauling for CuAl 2 , 1 was subsequently developed 2 to explain the chemical interaction between the metallic components. It emphasizes a non-d-character charge being transferred onto the T atoms, as an effect of their higher electronegativity, compensated by a back transfer of d charge off T, preserving its charge neutrality. Such a mechanism is equivalent to T-X hybridization, 3 with antibonding T(d)X( sp ) states upshifted above the Fermi level ( EF), corresponding to the T(d) and X( sp ) states ‘‘emptied’’ by the d-non-d charge transfer. Spectroscopic techniques like x-ray-absorption, x-ray emission, and photoemission were used to probe the electronic structure on both sides of EF and give an experimental evidence of the bonding effects. 4 A large series of T12xXx (T5Au,Pt,Ir,Re,Ag,Pd; X5Al,Ga,In,Si,Ge,Sn! com

The gradual substitution of Cu by Ag in the Al62Cu25.5-xAgxFe12.5 icosahedral phase (x less than or equal to 10) is investigated by X-ray diffraction from the viewpoint of the induced structural changes. The phonon and random phason disorders, estimated from diffraction linewidths, increase with x, the latter showing, however, an induction range of Ag concentrations. EXAFS results at the CuK and FeK edges show. for low Ag contents, and enhanced disorder in the first coordination sphere, partly relaxed for higher x values. The 6D hypercubic lattice parameter is found to be independent of the Ag content, despite the large diameter of monovalent Ag. The latter facts suggest a d-sp hybridization of the Ag bonds to the surrounding Al, taking place above a certain x value.

Applied surface science 267, 106 - 111 (2013). doi:10.1016/j.apsusc.2012.08.016, The surface structure, interface reactivity, electron configuration and magnetic properties of Sm layers deposited on Si(0 0 1) at various temperatures are investigated by low-energy electron diffraction (LEED), X-ray photoelectron spectroscopy (XPS), X-ray absorption spectroscopy (XAS) and magneto-optical Kerr effect (MOKE). It is found that metal Sm is present on samples prepared at low temperature, with an interface layer containing SmSi2 and Sm4Si3. When samples are prepared at high temperature, much less metal Sm is found, with an increasing amount of SmSi2. Room temperature ferromagnetism is observed for all prepared layers, with a decrease of the saturation magnetization when samples are prepared at high temperature. It is found that ferromagnetism implies mostly a compound with approximate stoichiometry Sm4Si3. Also, the decrease in the intensity of the XAS 2p3/2 → 3d white lines with the corresponding increasing amount of SmSi2 may be explained by assuming a higher occupancy of Sm 5d orbitals (5d2 configuration), most probably due to hybridation effects., Published by North-Holland, Amsterdam

Cobalt environment and magnetic defects nature in hydrothermal synthesized anatase CoxTi1−xO2 nanopowders (0 ≤ x ≤ 0.1) are investigated by x-ray diffraction and a variety of spectroscopic techniques. One shows that cobalt is partially inserted in the anatase lattice, as Co2+ ions located on substitutional and interstitial sites. The fraction of the diluted Co is limited to 3 at. % for x ≥ 0.05, while the rest of the Co atoms gather into Co3O4 clusters. As found by electron paramagnetic resonance, the Co doping brings about hole- and electron-excess defects.

Two Pd-Dy/γ-Al2O3 catalysts, with 1 wt.% Dy and various Pd loadings (0.1 and 0.5 wt.%) have been investigated by EXAFS at the Dy LIII-edge, and compared with 1 % Dy/γ-Al2O3. The Dy-carrier interaction was found to change with the Pd dispersity.

The aim of the present work is the investigation of the core-shell Fe@Au nanoparticles obtained by the inverse micelles method. Also hybrid structures between Fe@Au nanoparticles and the well-known conducting polymer polypyrrole (PPY) were obtained and investigated. The properties of the composites were investigated by TEM, HRTEM, X-ray diffraction (XRD), X-ray Photoelectron spectroscopy (XPS) and magnetization measurements. The TEM, HRTEM measurements show that two categories of core-shell nanoparticles with mean diameters of 5 nm and 25 nm, respectively, are formed. The XPS investigations of the core-shell Fe@Au nanoparticles indicate that besides Fe 0 inside the cores, small amounts of Fe II,III , located onto the gold surface ,were also formed during the samples preparation. The magnetization of the investigated nanocomposites measured versus increasing and decreasing magnetic field shows no hysteresis loop, this behavior being consistent with a superparamagnetic behavior. The behavior of the SQUID magnetization vs. temperature under field cooled (FC) and zero field cooled (ZFC) at 0.1 T magnetic field for Fe@Au nanoparticles confirmed the existence of superparamagnetism. The superparamagnetic model was used to fit the experimental magnetization vs. applied magnetic field as it was measured by SQUID up to 5 T.

The Mn, Sb and Se doped CdS thin films have been prepared using vacuum thermally evaporated mixed powders. XRD, AFM, optical spectroscopy and electrical measurements investigated the films deposited onto glass and silicon wafer substrates. The thin films have a textured hexagonal structure and after a heat treatment at 723 K become all transparent and have a low reflectivity. The CdS thin films doped with Sb and Se perform a relatively high electrical conductivity.

Silicalite embedded BiOx clusters were prepared both with and without Na using sodium silicate and tetraethylorthosilicate as silicium precursors. Catalysts with 3 and 5 wt% Bi were obtained. The MFI structure was established from XRD, TEM, and N2 adsorption measurements. No deterioration of the silicalite framework by bismuth was observed. Bi exists as BiOx clusters as evidenced from XPS and EXAFS characterization. These clusters are localized inside the silicalite channels. Py-FTIR measurements indicated that 5wt% Bi led to the formation of strong Lewis acid sites. Epoxidation of cyclohexene was found to depend on both Bi and Na content. On 3%Bi-ZSM-5 it occurred with rather good conversion and selectivity to epoxide. No visible leaching was evidenced. The catalysts were reused for several runs.

Summary Hydrogenation of a prostaglandin intermediate has been carried out on some Rumolecular sieves prepared via deposition of RuCl3. Characterization of these catalysts using different tools like WAXS, XPS or EXAFS indicated differences due to both the different metal loading and the different structure and topology of the investigated molecular sieves (L, APO-34 and ZSM-5). The prostaglandin intermediate has two kinds of unsaturation, a double C=C bond and a prochiral C=O bond. Therefore hydrogenation could imply two different selectivities. On simple Ru-molecular sieves, hydrogenation occurs with different reaction rates and selectivities as a function of the catalysts characteristics. Thus, d.e. of about 100% for a selectivity to the alcohol of 99% were obtained for Ru(12wt.%)-L. However, on these catalysts only the epi configuration was obtained. Modification of the catalysts using L (+) tartaric acid leads to the increase of the reaction rate and the decrease of the d.e. Adding of the pivalic acid to the reaction mixture determined a supplementary increase of the reaction rate. More important in this case is the change of the stereoselectivity, the main product becoming the natural configuration.

Pd-Ln/γ-Al 2 O 3 (Ln-Sm, Gd, Dy, Ho, Tm) catalysts containing 0.1%Pd- 1%Ln, 0.3%Pd -1% Ln and respectively, 0.5% Pd -1% Ln (percentage in wt.%) were investigated. Introduction of Ln leads to an increase of the vinylbenzenes conversion comparatively with monometallic Pd/γ-Al 2 O 3 catalysts. The turnover frequency (TOF) calculus of the latter catalysts suggests that there are no difference among these. In the case of bicomponent Pd-Ln/γ-Al 2 O 3 catalysts, if one considers that the reaction occurs only on the palladium particles, then introduction of Ln seems to increase the TOF and vinylbenzenes hydrogenation seems to be, controlled by the mass transfer processes as indicated by the Koros-Nowak criterion. However, by taking Ln into consideration when calculate the TOF, it results that bicomponent catalysts behave like those monocomponent and the slope of the Koros-Novak dependence is included in a range typical for kinetically controlled reactions. This behavior could be associated to direct participation of Ln to reaction using hydrogen spilled over from the palladium particles.

Ru(III)/functionalized silica-coated magnetic nanoparticles (Ru(III)-MNP) were proven to be a highly active, selective and easily recoverable catalyst for the oxidation of levulinic acid to succinic acid under green conditions.

Preparation of modified ruthenium molecular sieves has been investigated in two steps-depositionof ruthenium and modifying of ruthenium molecular sieves in presence of ligands. As support sieve there were used two molecular sieves with large pore apertures and low acidity strength (zeolite L and APO-34). Correlation of in situ UV-VIS ruthenium deposition measurements with catalyst characterisation revealed that ruthenium deposition takes place not only through ionic exchange but also through adsorption of ruthenium hydrolysed species. Modifying of the ruthenium molecular sieves catalysts with ligands has as effect a diminution of electronic charge on metal. The experimental data indicate that the presence of ligand favours an enantioselective hydrogenation of D-fructose to D-mannitol even if the yields are not very high.

Real regenerated supported palladium (0.5wt.%Pd-LiAl5O8) catalysts used in the hydrogenation of alkenes or alkynes and alkadienes were sintered at high temperatures (300, 500 or 600 °C) in a hydrogen atmosphere, and subjected to alternative treatments in either reducing and/or oxidizing atmospheres. X-ray diffraction analysis indicated hydride formation in the reducing stage, with intermediate compositions ranging between α-PdH and β-PdH, while on using the extended X-ray absorption fine structure technique palladium oxide was observed in catalysts subjected to oxidizing conditions. The statistics of the palladium-crystallite size distributions, as obtained by transmission electron microscopy, showed evidence of sintering and/or redispersion (splitting), as a result of the alternative reducing or oxidizing treatments. The catalytic activity in the alkadiene hydrogenation reaction is influenced by the treatment sequence applied to the regenerated catalysts.

The extended structure of the Pt L3 X-ray absorption edge for some platinum compounds was measured and Fourier inverted. It is shown that the way in which the contribution of the isolated atom is subtracted from the absorption spectrum may influence the shape of the first peak in the Fourier transform and possibly lead to erroneous structural interpretations concerning the first-neighbour shell of the absorbing atom. These errors are the more important the smaller the separation between the absorbing atom and its nearest neighbours. An improved method of subtraction of the isolated-atom absorption is proposed and checked.