Chemical Bonding of Hydrocarbons to Metal Surfaces

Using x-ray absorption spectroscopy (XAS), x-ray emission spectroscopy (XES) and x-ray photoelectron spectroscopy (XPS) in combination with density functional theory (DFT) the changes in electronic and geometric structure of hydrocarbons upon adsorption are determined. The chemical bonding is analyzed and the results provide new insights in the mechanisms responsible for dehydrogenation in heterogeneous catalysis. In the case of alkanes, n-octane and methane are studied. XAS and XES show significant changes in the electronic structure upon adsorption. XES shows new adsorption induced occupied states and XAS shows quenching of CH*/Rydberg states in n-octane. In methane the symmetry forbidden gas phase lowest unoccupied molecular orbital becomes allowed due to broken symmetry. New adsorption induced unoccupied features with mainly metal character appear just above the Fermi level in XA spectra of both adsorbed methane and n-octane. These changes are not observed in DFT total energy geometry optimizations. Comparison between experimental and computed spectra for different adsorbate geometries reveals that the molecular structures are significantly changed in both molecules. The C-C bonds in n-octane are shortened upon adsorption and the C-H bonds are elongated in both n-octane and methane. In addition ethylene and acetylene are studied as model systems for unsaturated hydrocarbons. The validity of both the Dewar-Chatt-Duncanson chemisorption model and the alternative spin-uncoupling picture is confirmed, as well as C-C bond elongation and upward bending of the C-H bonds. The bonding of ethylene to Cu(110) and Ni(110) are compared and the results show that the main difference is the amount of back-donation into the molecular π* orbital, which allows the molecule to desorb molecularly from the Cu(110) surface, whereas it is dehydrogenated upon heating on the Ni(110) surface. Acetylene is found to adsorb in two different adsorption sites on the Cu(110) surface at liquid nitrogen temperature. Upon heating the molecules move into one of these sites due to attractive adsorbate-adsorbate interaction and only one adsorbed species is present at room temperature, at which point the molecules start reacting to form benzene. The bonding of the two species is very similar in both sites and the carbon atoms are rehybridized essentially to sp2.

Abscheidung und Charakterisierung von Plasmapolymerschichten auf Fluorkohlenstoff- und Siloxan-Basis

In dieser Arbeit wurden Fluorkohlenstoff-basierte und siliziumorganische Plasmapolymerfilme hergestellt und hinsichtlich ihrer strukturellen und funktionalen Eigenschaften untersucht. Beide untersuchten Materialsysteme sind in der Beschichtungstechnologie von großem wissenschaftlichen und anwendungstechnischen Interesse. Die Schichtabscheidung erfolgte mittels plasmachemischer Gasphasenabscheidung (PECVD) an Parallelplattenreaktoren. Bei den Untersuchungen zur Fluorkohlenstoff-Plasmapolymerisation stand die Herstellung ultra-dünner, d. h. weniger als 5 nm dicker Schichten im Vordergrund. Dies wurde durch gepulste Plasmaanregung und Verwendung eines Gasgemisches aus Trifluormethan (CHF3) und Argon realisiert. Die Bindungsstruktur der Schichten wurden in Abhängigkeit der eingespeisten Leistung, die den Fragmentationsgrad der Monomere im Plasma bestimmt, analysiert. Hierzu wurden die Röntgen-Photoelektronenspektroskopie (XPS), Rasterkraftmikroskopie (AFM), Flugzeit-Sekundärionenmassenspektrometrie (ToF-SIMS) und Röntgenreflektometrie (XRR) eingesetzt. Es zeigte sich, dass die abgeschiedenen Schichten ein homogenes Wachstumsverhalten und keine ausgeprägten Interfacebereiche zum Substrat und zur Oberfläche hin aufweisen. Die XPS-Analysen deuten darauf hin, dass Verkettungsreaktionen von CF2-Radikalen im Plasma eine wichtige Rolle für den Schichtbildungsprozess spielen. Weiterhin konnte gezeigt werden, dass der gewählte Beschichtungsprozess eine gezielte Reduzierung der Benetzbarkeit verschiedener Substrate ermöglicht. Dabei genügen Schichtdicken von weniger als 3 nm zur Erreichung eines teflonartigen Oberflächencharakters mit Oberflächenenergien um 20 mN/m. Damit erschließen sich neue Applikationsmöglichkeiten ultra-dünner Fluorkohlenstoffschichten, was anhand eines Beispiels aus dem Bereich der Nanooptik demonstriert wird. Für die siliziumorganischen Schichten unter Verwendung des Monomers Hexamethyldisiloxan (HMDSO) galt es zunächst, diejenigen Prozessparameter zu identifizieren, die ihren organischen bzw. glasartigen Charakter bestimmen. Hierzu wurde der Einfluss von Leistungseintrag und Zugabe von Sauerstoff als Reaktivgas auf die Elementzusammensetzung der Schichten untersucht. Bei niedrigen Plasmaleistungen und Sauerstoffflüssen werden vor allem kohlenstoffreiche Schichten abgeschieden, was auf eine geringere Fragmentierung der Kohlenwasserstoffgruppen zurückgeführt wurde. Es zeigte sich, dass die Variation des Sauerstoffanteils im Prozessgas eine sehr genaue Steuerbarkeit der Schichteigenschaften ermöglicht. Mittels Sekundär-Neutralteilchen-Massenspektrometrie (SNMS) konnte die prozesstechnische Realisierbarkeit und analytische Quantifizierbarkeit von Wechselschichtsystemen aus polymerartigen und glasartigen Lagen demonstriert werden. Aus dem Intensitätsverhältnis von Si:H-Molekülen zu Si-Atomen im SNMS-Spektrum ließ sich der Wasserstoffgehalt bestimmen. Weiterhin konnte gezeigt werden, dass durch Abscheidung von HMDSO-basierten Gradientenschichten eine deutliche Reduzierung von Reibung und Verschleiß bei Elastomerbauteilen erzielt werden kann.

Design of cell adhesive and angiogenic titanium surfaces for cellular stimulation

Die Förderung der Zelladhäsion durch sogenannte biomimetische Oberflächen wird in der Medizin als vielversprechender Ansatz gesehen, um Komplikationen wie z. B. Fremdkörperreaktionen nach der Implantation entgegenzuwirken. Neben der Immobilisierung einzelner Biomoleküle wie z. B. dem RGD-Peptid, Proteinen und Wachstumsfaktoren auf verschiedenen Materialien, konzentriert man sich derzeit in der Forschung auf die Co-Immobilisierung zweier Moleküle gleichzeitig. Hierbei werden die funktionellen Gruppen z. B. von Kollagen unter Verwendung von nur einer Kopplungschemie verwendet, wodurch die Kopplungseffizienz der einzelnen Komponenten nur begrenzt kontrollierbar ist. Das Ziel der vorliegenden Arbeit war die Entwicklung eines Immobilisierungsverfahrens, welches die unabhängige Kopplung zweier Faktoren kontrolliert ermöglicht. Dabei sollten exemplarisch das adhäsionsfördernde RGD-Peptid (Arginin-Glycin-Asparaginsäure) zusammen mit dem Wachstumsfaktor VEGF (Vascular Endothelial Growth Factor) auf Titan gebunden werden. In weiteren Experimenten sollten dann die pro-adhäsiven Faktoren Fibronektin, Kollagen, Laminin und Osteopontin immobilisiert und untersucht werden. rnDie Aminofunktionalisierung von Titan durch plasma polymerisierte Allylaminschichten wurde als Grundlage für die Entwicklung des nasschemischen Co-immobilisierungsverfahren verwendet. Für eine unabhängige und getrennte Anbindung der verschiedenen Biomoleküle stand in diesem Zusammenhang die Entwicklung eines geeigneten Crosslinker Systems im Vordergrund. Die Oberflächencharakterisierung der entwickelten Oberflächen erfolgte mittels Infrarot Spektroskopie, Surface Plasmon Resonance Spektroskopie (SPR), Kontaktwinkelmessungen, Step Profiling und X-Ray Photoelectron Spektroskopie (XPS). Zur Analyse der Anbindungsprozesse in Echtzeit wurden SPR-Kinetik Messungen durchgeführt. Die biologische Funktionalität der modifizierten Oberflächen wurde in vitro an Endothelzellen (HUVECs) und Osteoblasten (HOBs) und in vivo in einem Tiermodell-System an der Tibia von Kaninchen untersucht.rnDie Ergebnisse zeigen, dass alle genannten Biomoleküle sowohl einzeln auf Titan kovalent gekoppelt als auch am Bespiel von RGD und VEGF in einem getrennten Zwei-Schritt-Verfahren co-immobilisiert werden können. Des Weiteren wurde die biologische Funktionalität der gebundenen Faktoren nachgewiesen. Im Falle der RGD modifizierten Oberflächen wurde nach 7 Tagen eine geförderte Zelladhäsion von HUVECs mit einer signifikant erhöhten Zellbesiedlungsdichte von 28,5 % (p<0,05) gezeigt, wohingegen auf reinem Titan Werte von nur 13 % beobachtet wurden. Sowohl VEGF als auch RGD/VEGF modifizierte Proben wiesen im Vergleich zu Titan schon nach 24 Stunden eine geförderte Zelladhäsion und eine signifikant erhöhte Zellbesiedlungsdichte auf. Bei einer Besiedlung von 7,4 % auf Titan, zeigten VEGF modifizierte Proben mit 32,3 % (p<0,001) eine deutlichere Wirkung auf HUVECs als RGD/VEGF modifizierte Proben mit 13,2 % (p<0,01). Die pro-adhäsiven Faktoren zeigten eine deutliche Stimulation der Zelladhäsion von HUVECs und HOBs im Vergleich zu reinem Titan. Die deutlich höchsten Besiedlungsdichten von HUVECs konnten auf Fibronektin mit 44,6 % (p<0,001) und Kollagen mit 39,9 % (p<0,001) nach 24 Stunden beobachtet werden. Laminin zeigte keine und Osteopontin nur eine sehr geringe Wirkung auf HUVECs. Bei Osteoblasten konnten signifikant erhöhte Besiedlungsdichten im Falle aller pro-adhäsiven Faktoren beobachtet werden, jedoch wurden die höchsten Werte nach 7 Tagen auf Kollagen mit 90,6 % (p<0,001) und Laminin mit 86,5 % (p<0,001) im Vergleich zu Titan mit 32,3 % beobachtet. Die Auswertung der Tierexperimente ergab, dass die VEGF modifizierten Osteosyntheseplatten, im Vergleich zu den reinen Titankontrollen, eine gesteigerte Knochenneubildung auslösten. Eine solche Wirkung konnte für RGD/VEGF modifizierte Implantate nicht beobachtet werden. rnInsgesamt konnte gezeigt werden, dass mittels plasmapolymerisierten Allylamin Schichten die genannten Biomoleküle sowohl einzeln gebunden als auch getrennt und kontrolliert co-immobilisiert werden können. Des Weiteren konnte eine biologische Funktionalität für alle Faktoren nach erfolgter Kopplung in vitro gezeigt werden. Wider Erwarten konnte jedoch kein zusätzlicher biologischer Effekt durch die Co-immobilisierung von RGD und VEGF im Vergleich zu den einzeln immobilisierten Faktoren gezeigt werden. Um zu einer klinischen Anwendung zu gelangen, ist es nun notwendig, das entwickelte Verfahren in Bezug auf die immobilisierten Mengen der verschiedenen Faktoren hin zu optimieren. rn

Self-assembly of focal point oligo-catechol ethylene glycol dendrons on titanium oxide surfaces: adsorption kinetics, surface characterization, and nonfouling properties

This work covers the synthesis of second-generation, ethylene glycol dendrons covalently linked to a surface anchor that contains two, three, or four catechol groups, the molecular assembly in aqueous buffer on titanium oxide surfaces, and the evaluation of the resistance of the monomolecular adlayers against nonspecific protein adsorption in contact with full blood serum. The results were compared to those of a linear poly(ethylene glycol) (PEG) analogue with the same molecular weight. The adsorption kinetics as well as resulting surface coverages were monitored by ex situ spectroscopic ellipsometry (VASE), in situ optical waveguide lightmode spectroscopy (OWLS), and quartz crystal microbalance with dissipation (QCM-D) investigations. The expected compositions of the macromolecular films were verified by X-ray photoelectron spectroscopy (XPS). The results of the adsorption study, performed in a high ionic strength ("cloud-point") buffer at room temperature, demonstrate that the adsorption kinetics increase with increasing number of catechol binding moieties and exceed the values found for the linear PEG analogue. This is attributed to the comparatively smaller and more confined molecular volume of the dendritic macromolecules in solution, the improved presentation of the catechol anchor, and/or their much lower cloud-point in the chosen buffer (close to room temperature). Interestingly, in terms of mechanistic aspects of "nonfouling" surface properties, the dendron films were found to be much stiffer and considerably less hydrated in comparison to the linear PEG brush surface, closer in their physicochemical properties to oligo(ethylene glycol) alkanethiol self-assembled monolayers than to conventional brush surfaces. Despite these differences, both types of polymer architectures at saturation coverage proved to be highly resistant toward protein adsorption. Although associated with higher synthesis costs, dendritic macromolecules are considered to be an attractive alternative to linear polymers for surface (bio)functionalization in view of their spontaneous formation of ultrathin, confluent, and nonfouling monolayers at room temperature and their outstanding ability to present functional ligands (coupled to the termini of the dendritic structure) at high surface densities.

Comparative stability studies of poly(2-methyl-2-oxazoline) and poly(ethylene glycol) brush coatings

Non-fouling surfaces that resist non-specific adsorption of proteins, bacteria, and higher organisms are of particular interest in diverse applications ranging from marine coatings to diagnostic devices and biomedical implants. Poly(ethylene glycol) (PEG) is the most frequently used polymer to impart surfaces with such non-fouling properties. Nevertheless, limitations in PEG stability have stimulated research on alternative polymers that are potentially more stable than PEG. Among them, we previously investigated poly(2-methyl-2-oxazoline) (PMOXA), a peptidomimetic polymer, and found that PMOXA shows excellent anti-fouling properties. Here, we compare the stability of films self-assembled from graft copolymers exposing a dense brush layer of PEG and PMOXA side chains, respectively, in physiological and oxidative media. Before media exposure both film types prevented the adsorption of full serum proteins to below the detection limit of optical waveguide in situ measurements. Before and after media exposure for up to 2 weeks, the total film thickness, chemical composition, and total adsorbed mass of the films were quantified using variable angle spectroscopic ellipsometry (VASE), X-ray photoelectron spectroscopy (XPS), and optical waveguide lightmode spectroscopy (OWLS), respectively. We found (i) that PMOXA graft copolymer films were significantly more stable than PEG graft copolymer films and kept their protein-repellent properties under all investigated conditions and (ii) that film degradation was due to side chain degradation rather than due to copolymer desorption.

Photodegradation and photostabilization of weathered wood flour filled polyethylene composites

Wood plastic composites (WPCs) have gained popularity as building materials because of their usefulness in replacing solid wood in a variety of applications. These composites are promoted as being low-maintenance, high-durability products. However, it has been shown that WPCs exposed to weathering may experience a color change and/or loss in mechanical properties. An important requirement for building materials used in outdoor applications is the retention of their aesthetic qualities and mechanical properties during service life. Therefore, it is critical to understand the photodegradation mechanisms of WPCs exposed to UV radiation and to develop approaches to stabilize these composites (both unstabilized and stabilized) as well as the effect of weathering on the color fade and the retention of mechanical properties were characterized. Since different methods of manufacturing WPCs lead to different surface characteristics, which can influence weathering, the effect of manufacturing method on the photodegradation of WPCs was investigated first. Wood flour (WF) filled high-density polyethylene (HDPE) composite samples were either injection molded, extruded, or extruded and then planed. Fourier transform infrared (FTIR) spectroscopy was used to monitor the surface chemistry of the manufactured composites. The spectra showed that the surface of planed samples had more wood component than extruded and injection molded samples, respectively. After weathering, the samples were analyzed for color fade, and loss of flexural properties. The final lightness of the composites was not dependent upon the manufacturing method. However the mechanical property loss was dependent upon manufacturing method. The samples with more wood component at the surface (planed samples) experienced a larger percentage of total loss in flexural properties after weathering due to a greater effect of moisture on the samples. The change in surface chemistry of HDPE and WF/HDPE composites after weathering was studied using spectroscopic techniques. X-ray photoelectron spectroscopy (XPS) was used to characterize the occurrence of surface oxidation whereas FTIR spectroscopy was used to monitor the development of degradation products, such as carbonyl groups and vinyl groups, and to determine changes in HDPE crystallinity. Surface oxidation occurred immediately after exposure for both the neat HDPE and WF/HDPE composites. After weathering, the surface of the WF/HDPE composites was oxidized to a greater extent than the neat HDPE after weathering. This suggests that photodegradation is exacerbated by the addition of the carbonyl functional groups of the wood fibers within the HDPE atrix during composite manufacturing. While neat HDPE may undergo cross-linking in the initial stages of accelerated weathering, the WF may physically hinder the ability of the HDPE to cross-link resulting in the potential for HDPE chain scission to dominate in the initial weathering stages of the WF/HDPE composites. To determine which photostabilizers are most effective for WF/HDPE composites, factorial experimental designes were used to determine the effects of adding two hindered amine light stabilizers, an ultraviolet absorber, and a pigment on the color made and mechanical properties of both unweathered and UV weathered samples. Both the pigment and ultraviolet absorber were more effective photostabilizers for WF/HDPE composites than hinder amine light stabilizers. The ineffectiveness of hindered amine light stabilizers in protecting WPCs against UV radiation was attribuated to the acid/base reactions occurring between the WF and hindered amine light stabilizer. The efficiency of an ultraviolet absorber and/or pigment was also examined by incorporating different concentration of an ultraviolet absorber and/or pigment into WF/HDPE composites. Color change and flexural properties were determined after accelerated UV weathering. The lightness of the composite after weathering was influenced by the concentration of both the ultraviolet absorber by masking the bleaching wood component as well as blocking UV light. Flexural MOE loss was influenced by an increase in ultraviolet absorber concentration, but increasing pigment concentration from 1 to 2% had little influence on MOE loss. However, increasing both ultraviolet absorber and pigment concentration resulted in improved strength properties over the unstabilized composites after 3000 h of weather. Finally, the change in surface chemistry due to weathering of WF/HDPE composites that were either unstabilized or stabilized with an ultraviolet absorber and/or pigment was analyzed using FTIR spectroscopy. The samples were tested for loss in modulus of elasticity, carbonyl and vinyl group formation at the surface, and change in HDPE crystallinity. It was concluded that structural changes in the samples; carbonyl group formation, terminal vinyl group formation, and crystallinity changes cannot reliably be used to predict changes in modulus of elasticity using a simple linear relationship. The effect of cross-linking, chain scission, and crystallinity changes due to ultraviolet exposure as well as the interfacial degradation due to moisture exposure are inter-related factors when weathering HDPE and WF/HDPE composites.

Covalent immobilisation of VEGF on plasma-coated electrospun scaffolds for tissue engineering applications.

Recent findings in the field of biomaterials and tissue engineering provide evidence that surface immobilised growth factors display enhanced stability and induce prolonged function. Cell response can be regulated by material properties and at the site of interest. To this end, we developed scaffolds with covalently bound vascular endothelial growth factor (VEGF) and evaluated their mitogenic effect on endothelial cells in vitro. Nano- (254±133 nm) or micro-fibrous (4.0±0.4 μm) poly(ɛ-caprolactone) (PCL) non-wovens were produced by electrospinning and coated in a radio frequency (RF) plasma process to induce an oxygen functional hydrocarbon layer. Implemented carboxylic acid groups were converted into amine-reactive esters and covalently coupled to VEGF by forming stable amide bonds (standard EDC/NHS chemistry). Substrates were analysed by X-ray photoelectron spectroscopy (XPS), enzyme-linked immuno-assays (ELISA) and immunohistochemistry (anti-VEGF antibody and VEGF-R2 binding). Depending on the reaction conditions, immobilised VEGF was present at 127±47 ng to 941±199 ng per substrate (6mm diameter; concentrations of 4.5 ng mm(-2) or 33.3 ng mm(-2), respectively). Immunohistochemistry provided evidence for biological integrity of immobilised VEGF. Endothelial cell number of primary endothelial cells or immortalised endothelial cells were significantly enhanced on VEGF-functionalised scaffolds compared to native PCL scaffolds. This indicates a sustained activity of immobilised VEGF over a culture period of nine days. We present a versatile method for the fabrication of growth factor-loaded scaffolds at specific concentrations.

Nitrogen-Doping in ZnO via Combustion Synthesis?

We report the synthesis and characterization of colored ZnO-based powders via solution combustion reaction of urea and zinc nitrate hexahydrate in varying molar ratios between 1:1 and 10:1. Among other techniques, we employ X-ray diffraction, nuclear magnetic resonance, and Raman spectroscopy to characterize the products. Within a narrow range of reactant ratios, we reproducibly find an unidentified, crystalline precursor phase related to isocyanuric acid next to ZnO. Finally, we complement our investigations by performing Prompt Gamma Activation Analysis (PGAA) on selected products in order to directly determine elemental bulk compositions and compare these with X-ray photoelectron spectroscopy (XPS) measurements. Our data show traces of nitrogen mainly on the surface of the particles, and thus we question the solution combustion method as a reliable synthesis toward N-doped ZnO. Furthermore, we exclude nitrogen as being responsible for the appearance of the four controversially discussed Raman bands superimposed onto the spectrum of pure ZnO (at 275, 510, 582, and 643 cm–1) and show that the combination of PGAA and XPS is an excellent and complementary method to obtain information about the distribution of the elements in question.

Si(100) versus Ge(100): Watching the interface formation for the growth of III-V-based solar cells on abundant substrates

We investigated the atomic surface properties of differently prepared silicon and germanium (100) surfaces during metal-organic vapour phase epitaxy/chemical vapour deposition (MOVPE/MOCVD), in particular the impact of the MOVPE ambient, and applied reflectance anisotropy/difference spectroscopy (RAS/RDS) in our MOVPE reactor to in-situ watch and control the preparation on the atomic length scale for subsequent III-V-nucleation. The technological interest in the predominant opto-electronic properties of III-V-compounds drives the research for their heteroepitaxial integration on more abundant and cheaper standard substrates such as Si(100) or Ge(100). In these cases, a general task must be accomplished successfully, i.e. the growth of polar materials on non-polar substrates and, beyond that, very specific variations such as the individual interface formation and the atomic step structure, have to be controlled. Above all, the method of choice to grow industrial relevant high-performance device structures is MOVPE, not normally compatible with surface and interface sensitive characterization tools, which are commonly based on ultrahigh vacuum (UHV) ambients. A dedicated sample transfer system from MOVPE environment to UHV enabled us to benchmark the optical in-situ spectra with results from various surfaces science instruments without considering disruptive contaminants. X-ray photoelectron spectroscopy (XPS) provided direct observation of different terminations such as arsenic and phosphorous and verified oxide removal under various specific process parameters. Absorption lines in Fourier-transform infrared (FTIR) spectra were used to identify specific stretch modes of coupled hydrides and the polarization dependence of the anti-symmetric stretch modes distinguished different dimer orientations. Scanning tunnelling microscopy (STM) studied the atomic arrangement of dimers and steps and tip-induced H-desorption proved the saturation of dangling bonds after preparati- n. In-situ RAS was employed to display details transiently such as the presence of H on the surface at lower temperatures (T <; 800°C) and the absence of Si-H bonds at elevated annealing temperature and also surface terminations. Ge buffer growth by the use of GeH4 enables the preparation of smooth surfaces and leads to a more pronounced amplitude of the features in the spectra which indicates improvements of the surface quality.

In situ study of Ge(100) surfaces with tertiarybutylphosphine supply in vapor phase epitaxy ambient

GaInP nucleation on Ge(100) often starts by annealing of the Ge(100) substrates under supply of phosphorus precursors. However, the influence on the Ge surface is not well understood. Here, we studied vicinal Ge(100) surfaces annealed under tertiarybutylphosphine (TBP) supply in MOVPE by in situ reflection anisotropy spectroscopy (RAS), X-ray photoelectron spectroscopy (XPS), and low energy electron diffraction (LEED). While XPS reveals a P termination and the presence of carbon on the Ge surface, LEED patterns indicate a disordered surface probably due to by-products of the TBP pyrolysis. However, the TBP annealed Ge(100) surface exhibits a characteristic RA spectrum, which is related to the P termination. RAS allows us to in situ control phosphorus desorption dependent on temperature.

Promoter effect of sodium in graphene-supported Ni and Ni–CeO2 catalyst for the low-temperature WGS reaction

The low temperature water–gas shift (WGS) reaction has been studied over Ni–CeO2/Graphene and Ni/Graphene. The catalysts were prepared with 5 wt.% Ni and 20 wt.% CeO2 loadings, by deposition-precipitation employing sodium hydroxide and urea as precipitating agents. The materials were characterized by TEM, powder X-ray diffraction, Raman spectroscopy, H2-temperature-programmed reduction and X-ray photoelectron spectroscopy (XPS). The characterization and the reaction results indicated that the interaction between the active species and the support is higher than with activated carbon, and this hinders the reducibility of ceria and thus the catalytic performance. On the other hand, the presence of residual sodium in samples prepared by precipitation with NaOH facilitated the reduction of ceria. The catalytic activity was highly improved in the presence of sodium, what can be explained on the basis of an associative reaction mechanism which is favored over Ni-O-Na entities.

Pt- and Ru-Doped SnO2–Sb Anodes with High Stability in Alkaline Medium

Different Pt- and Ru-doped Ti/SnO2–Sb electrodes were synthesized by thermal decomposition. The effect of the gradual substitution of Sb by Ru in the nominal composition on the physicochemical and electrochemical properties were evaluated. The electrochemical stability of the electrodes was estimated from accelerated tests at 0.5 A cm–2 in 1 M NaOH. Both as-synthesized and deactivated electrodes were thoroughly characterized by scanning electron microscopy (SEM), energy-dispersive X-ray microanalysis (EDX), transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS) and X-ray diffraction analysis (XRD). The incorporation of a small amount (about 3 at. %) of both Pt and Ru into the SnO2–Sb electrodes produced a 400-times increase in their service life in alkaline medium, with no remarkable change in the electrocatalysis of the oxygen evolution reaction (OER). It is concluded that the deactivation of the electrodes is promoted by alkaline dissolution of metal species and coating detachment at high potentials. The introduction of Pt has a coating compacting effect, and Ru(IV), at low amounts until 9.75 at. %, replaces the Sn(IV) cations in the rutile-like SnO2 structure to form a solid solution that strongly increases the stability of the electrodes. The observed Ru segregation and decreased stability for larger Ru contents (x > 9.75 at. %), together with the selective dissolution of Ru after deactivation, suggest that the formation of a homogeneous (RuδSn1−δ)O2 single-phase is crucial for the stabilization of these electrodes.

Carbon nanotube-supported Ni–CeO2 catalysts. Effect of the support on the catalytic performance in the low-temperature WGS reaction

The low temperature water-gas shift (WGS) reaction has been studied over two commercial multiwall carbon nanotubes-supported nickel catalysts promoted by ceria. For comparison purposes, activated carbon-supported catalysts have also been studied. The catalytic performance and the characterization by N2 adsorption analysis, powder X-ray diffraction (XRD), temperature-programmed reduction with H2 (TPR-H2), X-ray photoelectron spectroscopy (XPS) and transmission electron microscopy (TEM) analysis showed that the surface chemistry has an important effect on the dispersion of ceria. As a result, ceria was successfully dispersed over the carbon nanotubes (CNTs) with less graphitic character, and the catalyst afforded better activity in WGS than the catalyst prepared over massive ceria. Moreover, a 20 wt.% CeO2 loading over this support was more active than the analogous catalyst with a 40 wt.% loading. The ceria nanoparticles were smaller when the support was previously oxidized, however this resulted in a decrease of the activity.

Colour changes by laser irradiation of reddish building limestones

We have used X-ray photoelectron spectroscopy (XPS) as a novel method to investigate the causes of colour changes in a reddish limestone under irradiation by a Q-switched Nd:YAG 1064 nm laser. We irradiated clean dry and wet surfaces of Pidramuelle Roja, a building stone frequently used in the Asturian heritage, at fluences ranging from 0.12 to 1.47 J cm−2. We measured the colour coordinates and undertook XPS analysis of the state of oxidation of iron both before and after irradiation. Visible colour changes and potential aesthetic damage occurred on dry surfaces from a fluence of 0.31 J cm−2, with the stone showing a greening effect and very intense darkening. The colour change on dry surfaces was considerably higher than on wet surfaces, which at the highest fluence (1.47 J cm−2) was also above the human visual detection threshold. The use of XPS demonstrated that the change in colour (chroma and hue) is associated with a reduction in the iron oxidation state on dry surfaces during laser irradiation. This points out to a potential routinary use of XPS to analyse causes of colour changes during laser cleaning in other types of coloured building stones.

Preparation and catalytic properties of ZrO2-Al2O3 composite oxide supported nickel catalysts for methane reforming with carbon dioxide

ZrO2-Al2O3 composite oxides and supported Ni catalysts were prepared, and characterized by N-2 adsorption/desorption, X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS) techniques. The catalytic performance and carbon deposition was also investigated. This mesoporous composite oxide is shown to be a promising catalyst support. An increase in the catalytic activity and stability of methane and carbon dioxide reforming reaction was resulted from the zirconia addition, especially at 5wt% ZrO2 content. The Ni catalyst supported ZrO2-Al2O3 has a strong resistance to sintering and the carbon deposition in a relatively long-term reaction.