Adsorption of 5-Fluorouracil on Au(111) and Cu(111) surfaces

The adsorption of 5-Fluorouracil (5FU) on Au(111) and Cu(111) surfaces as a function of molecular coverage and temperature has been studied, using x-ray photoelectron spectroscopy (XPS) and near-edge x-ray absorption fine structure (NEXAFS) spectroscopy. The nature of 5-Fluorouracil bonding with the two substrates is remarkably different. The Cu substrate forms a chemisorbed complex with 5-FU while the Au substrate shows only physisorption. NEXAFS data at the C, N and O K-edge show a strong angular dependence, indicating that 5-FU lies nearly parallel on the inert Au(111) surface, and at a steep angle on the Cu(111) surface. 5-FU is a biomolecule used for cancer treatment and the results are relevant for those using metal surfaces to prepare 5-FU for applications such as drug delivery.The adsorption of 5-Fluorouracil (5FU) on Au(111) and Cu(111) surfaces as a function of molecular coverage and temperature has been studied, using x-ray photoelectron spectroscopy (XPS) and near-edge x-ray absorption fine structure (NEXAFS) spectroscopy. The nature of 5-Fluorouracil bonding with the two substrates is remarkably different. The Cu substrate forms a chemisorbed complex with 5-FU while the Au substrate shows only physisorption. NEXAFS data at the C, N and O K-edge show a strong angular dependence, indicating that 5-FU lies nearly parallel on the inert Au(111) surface, and at a steep angle on the Cu(111) surface. 5-FU is a biomolecule used for cancer treatment and the results are relevant for those using metal surfaces to prepare 5-FU for applications such as drug delivery

On the interaction of Mg with the (111) and (110) surfaces of ceria

The catalytic activity of cerium dioxide can be modified by deposition of alkaline earth oxide layers or nanoparticles or by substitutional doping of metal cations at the Ce site in ceria. In order to understand the effect of Mg oxide deposition and doping, a combination of experiment and first principles simulations is a powerful tool. In this paper, we examine the interaction of Mg with the ceria (111) surface using both angle resolved X-ray (ARXPS) and resonant (RPES) photoelectron spectroscopy measurements and density functional theory (DFT) corrected for on-site Coulomb interactions (DFT + U). With DFT + U, we also examine the interaction of Mg with the ceria (110) surface. The experiments show that upon deposition of Mg, Ce ions are reduced to Ce3+, while Mg is oxidised. When Mg is incorporated into ceria, no reduced Ce3+ ions are found and oxygen vacancies are present. The DFT + U simulations show that each Mg that is introduced leads to formation of two reduced Ce3+ ions. When Mg is incorporated at a Ce site in the (111) surface, one oxygen vacancy is formed for each Mg to compensate the different valencies, so that all Ce ions are oxidised. The behaviour of Mg upon interaction with the (110) surface is the same as with the (111) surface. The combined results provide a basis for deeper insights into the catalytic behaviour of ceria-based mixed oxide catalysts

Adsorption of cytosine and aza derivatives of cytidine on Au single crystal surfaces

The adsorption of cytosine on the Au(111) and Au(110) surfaces has been studied using both aqueous deposition and evaporation in vacuum to prepare the samples. Soft X-ray photoelectron spectroscopy (XPS) and near edge X-ray absorption fine structure spectroscopy (NEXAFS) were used to determine the electronic structure and orientation of the adsorbates. In addition, three derivatives of cytosine, 6-azacytosine, 6-azacytidine and 5- azacytidine, were studied. Monolayer films of the latter three samples were adsorbed on Au(111) from aqueous solution, and the nature of bonding was determined. Spectra have been interpreted in the light of published calculations of free cytosine molecules and new ab initio calculations of the other compounds. Surface core level shifts of Au 4f imply that all of these compounds are chemisorbed. Cytosine adsorbs as a single tautomer, but in two chemical states with different surface-molecule bonding. For deposition in vacuum, a flat-lying molecular state bonded through the N(3) atom of the pyrimidine ring dominates, but a second state is also present. For deposition from solution, the second state dominates, with the molecular plane no longer parallel to the surface. This state also bonds through the N(3) atom, but in addition interacts with the surface via the amino group. Two tautomers of 6-azacytosine were observed, and they and 6-azacytidine adsorb with similar geometries, chemically bonding via the azacytosine ring. The ribose ring does not appear to perturb the adsorption of azacytidine compared with azacytosine. The azacytosine ring is nearly but not perfectly parallel to the surface, like 5-azacytidine, which adsorbs as an imino tautomer. ...Comment: 40 pages, 3 tables and 8 figure

Phosphorus poisoning during wet oxidation of methane over Pd@CeO2/graphite model catalysts

10siThe influence of phosphorus and water on methane catalytic combustion was studied over Pd@CeO2 model catalysts supported on graphite, designed to be suitable for X-ray Photoelectron Spectroscopy/Synchrotron Radiation Photoelectron Spectroscopy (XPS/SRPES) analysis. In the absence of P, the catalyst was active for the methane oxidation reaction, although introduction of 15% H2O to the reaction mixture did cause reversible deactivation. In the presence of P, both thermal and chemical aging treatments resulted in partial loss of activity due to morphological transformation of the catalyst, as revealed by Scanning Electron Microscopy (SEM) and Atomic Force Microscopy (AFM) analysis. At 600 °C the combined presence of PO43− and water vapor caused a rapid, irreversible deactivation of the catalyst. XPS/SRPES analysis, combined with operando X-ray Absorption Near Edge Structure (XANES) and AFM measurements, indicated that water induces severe aggregation of CeO2 nanoparticles, exposure of CePO4 on the outer layer of the aggregates and incorporation of the catalytic-active Pd nanoparticles into the bulk. This demonstrates a temperature-activated process for P-poisoning of oxidation catalysts in which water vapor plays a crucial role.partially_openembargoed_20171009Monai, Matteo; Montini, Tiziano; Melchionna, Michele; Duchoň, Tomáš; Kúš, Peter; Tsud, Nataliya; Prince, Kevin C.; Matolin, Vladimir; Gorte, Raymond J.; Fornasiero, PaoloMonai, Matteo; Montini, Tiziano; Melchionna, Michele; Duchoň, Tomáš; Kúš, Peter; Tsud, Nataliya; Prince, Kevin C.; Matolin, Vladimir; Gorte, Raymond J.; Fornasiero, Paol

Nitridation of InP(1 0 0) surface studied by synchrotron radiation

The nitridation of InP(1 0 0) surfaces has been studied using synchrotron radiation photoemission. The samples were chemically cleaned and then ion bombarded, which cleaned the surface and also induced the formation of metallic indium droplets. The nitridation with a Glow Discharge Cell (GDS) produced indium nitride by reaction with these indium clusters. We used the In 4d and P 2p core levels to monitor the chemical state of the surface and the coverage of the species present. We observed the creation of In-N and P-N bonds while the In-In metallic bonds decrease which confirm the reaction between indium clusters and nitrogen species. A theoretical model based on stacked layers allows us to assert that almost two monolayers of indium nitride are produced. The effect of annealing on the nitridated layers at 450 $^\circ$C has also been analysed. It appears that this system is stable up to this temperature, well above the congruent evaporation temperature (370 $^\circ$C) of clean InP(1 0 0): no increase of metallic indium bonds due to decomposition of the substrate is detected as shown in previous works [L. Bideux, Y. Ould-Metidji, B. Gruzza, V. Matolin, Surf. Interface Anal. 34 (2002) 712] studying the InP(1 0 0) surfaces

Probing the Roughness of Porphyrin Thin Films with X-ray Photoelectron Spectroscopy

Thin-film growth of molecular systems is of interest for many applications, such as for instance organic electronics. In this study, we demonstrate how X-ray photoelectron spectroscopy (XPS) can be used to study the growth behavior of such molecular systems. In XPS, coverages are often calculated assuming a uniform thickness across a surface. This results in an error for rough films, and the magnitude of this error depends on the kinetic energy of the photoelectrons analyzed. We have used this kinetic-energy dependency to estimate the roughnesses of thin porphyrin films grown on rutile TiO2(110). We used two different molecules: cobalt (II) monocarboxyphenyl-10,15,20-triphenylporphyrin (CoMCTPP), with carboxylic-acid anchor groups, and cobalt (II) tetraphenylporphyrin (CoTPP), without anchor groups. We find CoMCTPP to grow as rough films at room temperature across the studied coverage range, whereas for CoTPP the first two layers remain smooth and even; depositing additional CoTPP results in rough films. Although, XPS is not a common technique for measuring roughness, it is fast and provides information of both roughness and thickness in one measurement.Fil: Kataev, Elmar. Universitat Erlangen-Nuremberg; AlemaniaFil: Wechsler, Daniel. Universitat Erlangen-Nuremberg; AlemaniaFil: Williams, Federico José. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Instituto de Química, Física de los Materiales, Medioambiente y Energía. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Instituto de Química, Física de los Materiales, Medioambiente y Energía; Argentina. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Departamento de Química Inorgánica, Analítica y Química Física; ArgentinaFil: Köbl, Julia. Universitat Erlangen-Nuremberg; AlemaniaFil: Tsud, Natalia. Karlova Univerzita (cuni); República ChecaFil: Franchi, Stefano. Istituto di Struttura della Materia; Italia. Consiglio Nazionale delle Ricerche; ItaliaFil: Steinruck, Hans Peter. Universitat Erlangen-Nuremberg; AlemaniaFil: Lytken, Ole. Universitat Erlangen-Nuremberg; Alemani

The effect of sulfur dioxide on the activity of hierarchical Pd-based catalysts in methane combustion

SO2 poisoning of methane oxidation over alumina-supported, Pd@CexZr1-xO2 nanoparticle catalysts was systematically studied by means of advanced PhotoElectron Spectroscopy (PES) methods. The Pd@CexZr1-xO2 units were synthesized and deposited on two modified-alumina supports, i.e. high surface area modified alumina and a model alumina prepared by Atomic Layer Deposition (ALD) of alumina on Indium Tin Oxide (ITO)/quartz slides. The model support was designed to be suitable for PES analysis and was stable to high temperature treatments (850 degrees C). Characterization of the high-surface-area (HSA) catalysts by X-Ray Diffraction (XRD), N-2 physisorption, CO chemisorption and Transmission Electron Microscopy (TEM) indicated formation of CeO2-ZrO2 (CZ) mixed-oxide crystallites that stabilize the Pd active phase against sintering. Correlation of methane-oxidation rates with PES results demonstrated two distinct mechanisms for deactivation by SO2. Below 450 degrees C, the presence of SO2 in the feed led to partial reduction of the active PdO phase and to the formation of sulfates on the Pd. Above 500 degrees C, poisoning by SO2 was less severe due to spillover of the sulfates onto the oxide promoter. Pd@ZrO2 catalysts showed the best resistance to SO2 poisoning, outperforming analogous Pd@CZ mixed-oxide catalysts, because there was less sulfate formation and the sulfates that did form could be removed during regeneration

Investigation of metal-substrate interaction on Pd/Al_2O_3 model catalysts and Pd/SnO_2 based sensors.

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