Ab-initio density functional study of O on the Ag(001) surface

The adsorption of oxygen on the Ag(001) is investigated by means of density functional techniques. Starting from a characterization of the clean silver surfaces oxygen adsorption in several modifications (molecularly, on-surface, sub-surface, Ag$_2$O) for varying coverage was studied. Besides structural parameters and adsorption energies also work-function changes, vibrational frequencies and core level energies were calculated for a better characterization of the adsorption structures and an easier comparison to the rich experimental data.Comment: 26 pages, 8 figures, Surf. Sci. accepte

Vanadium oxide monolayer catalysts. I. Preparation, characterization, and thermal stability

Vanadium oxide catalysts of the monolayer type have been prepared by means of chemisorption of vanadate(V)-anions from aqueous solutions and by chemisorption of gaseous V2O3(OH)4. Using Al2O3, Cr2O3, TiO2, CeO2 and ZrO2, catalysts with an approximately complete monomolecular layer of vanadium(V) oxide on the carrier oxides can be prepared, if temperature is not too high. Divalent metal oxides like CdO and ZnO may already form threedimensional surface vanadates at moderate temperature. \ud The thermal stability of a monolayer catalyst is related to the parameter z/a, i. e. the ratio of the carrier cation charge to the sum of ionic radii of carrier cation and oxide anion. Thus, monolayer catalysts will be thermally stable only under the condition that z/a is not too high (aggregated catalyst) nor too small (ternary compound formation)

Why is a noble metal catalytically active? The role of the O-Ag interaction in the function of silver as an oxidation catalyst

Extensive density-functional theory calculations, and taking into account temperature and pressure, affords a comprehensive picture of the behavior and interaction of oxygen and Ag(111), and provides valuable insight into the function of silver as an oxidation catalyst. The obtained phase-diagram reveals the most stable species present in a given environment and thus identifies (and excludes) possibly active oxygen species. In particular, for the conditions of ethylene epoxidation, a thin oxide-like structure is most stable, suggesting that such atomic O species are actuating the catalysis, in contrast to hitherto proposed molecular-like species.Comment: 4 pages including 3 figures, Related publications can be found at http://www.fhi-berlin.mpg.de/th/paper.htm

Effect of the semi-conductive properties of the passive layer on the current provided by stainless steel microbial cathodes

Geobacter sulfur reducens biofilms were formed under constant polarisation at −0.6 V vs. Ag/AgCl on stainless steel cathodes to catalyse the reduction of fumarate. The time-evolution of the current strongly depended on the quality of the inoculum. Inoculating with young cells significantly shortened the initial lag-phase and using the same inoculum improved the reproducibility of the current–time curves. The whole set of experiments showed that 254SMO stainless steel provided higher current densities (on average 14.1 A/m2) than biofilms formed on 316L stainless steel (on average 4.5 A/m2). Biofilm coverage assessed by epifluorescent microscopy showed that coverage ratios were generally higher for 316L than for 254SMO. It must be concluded that 254SMO is more efficient in transferring electrons to bacterial cells than 316L. Mott–Schottky diagrams recorded on both materials under conditions of electrolysis in the absence of microorganisms showed that the surface oxide layers had similar n-type semi-conductive behaviour for potential values higher than the flat band potential. In contrast, 316L exhibited slight p-type behaviour at potential lower than the flat band potential, while 254SMO did not. The higher electrochemical performances of biocathodes formed on 254SMO are explained by semi-conductive properties of its passive layer, which prevented the p-type behaviour occurring in cathodic electrolysis conditions

Tunnel current in self-assembled monolayers of 3-mercaptopropyltrimethoxysilane

The current density-voltage (J-V) characteristics of self assembled monolayers of 3-mercaptopropyltrimethoxysilane (MPTMS) chemisorbed on the native oxide surface of p+-doped Si demonstrate the excellent tunnel dielectric behavior of organic monolayers down to 3 carbon atoms. The J-V characteristics of MPTMS SAMs on Si are found to be asymmetric, and the direction of rectification has been found to depend upon the applied voltage range. At voltages < 2.45V, the reverse bias current was found to be higher than forward bias current; while at higher voltages this trend was reversed. This result is in agreement with Simmons theory. The tunnel barrier heights for this short chain (2.56 and 2.14 eV respectively at Au and Si interfaces) are in good agreement with the ones for longer chains (>10 carbon atoms) if the chain is chemisorbed at the electrodes. These results extend all previous experiments on such molecular tunnel dielectrics down to 3 carbon atoms. This suggests that these molecular monolayers, having good tunnel behavior (up to 2.5 eV) over a large bias range, can be used as gate dielectric well below the limits of Si-based dielectrics.Comment: Small, in pres

O adsorption and incipient oxidation of the Mg(0001) surface

First principles density functional calculations are used to study the early oxidation stages of the Mg(0001) surface for oxygen coverages 1/16 <= Theta <= 3 monolayers. It is found that at very low coverages O is incorporated below the topmost Mg layer in tetrahedral sites. At higher oxygen-load the binding in on-surface sites is increased but at one monolayer coverage the on-surface binding is still about 60 meV weaker than for subsurface sites. The subsurface octahedral sites are found to be unfavorable compared to subsurface tetrahedral sites and to on-surface sites. At higher coverages oxygen adsorbs both under the surface and up. Our calculations predict island formation and clustering of incorporated and adsorbed oxygen in agreement with previous calculations. The calculated configurations are compared with the angle-scanned x-ray photoelectron diffraction experiment to determine the geometrical structure of the oxidized Mg(0001) surface.Comment: 10 pages, 5 figure

Adsorption and binding dynamics of graphene-supported phospholipid membranes using the QCM-D technique

We report on the adsorption dynamics of phospholipid membranes on graphene-coated substrates using the quartz crystal microbalance with dissipation monitoring (QCM-D) technique. We compare the lipid vescle interaction and membranne formation on gold and silicon dioxide QCM crystal surfaces with their graphene oxide (GO) and reduced (r)GO coated counterparts, and report on the different lipid structures obtained. We establish graphene derivative coatings as support surfaces with tuneable hydrophobicity for the formation of controllable lipid structures. One structure of interest formed are lipid monolayer membrannes which were formed on rGO, which are otherwise challenging to produce. We also demonstrate and monitor biotin-avidin binding on such a membranne, which will then serve as a platform for a wide range of biosensing applications. The QCM-D technique could be extended to both fundamental studies and applications of other covalent and non-covalent interactions in 2-dimensional materials

Self-Organization at the Nanoscale Scale in Far-From-Equilibrium Surface Reactions and Copolymerizations

An overview is given of theoretical progress on self-organization at the nanoscale in reactive systems of heterogeneous catalysis observed by field emission microscopy techniques and at the molecular scale in copolymerization processes. The results are presented in the perspective of recent advances in nonequilibrium thermodynamics and statistical mechanics, allowing us to understand how nanosystems driven away from equilibrium can manifest directionality and dynamical order.Comment: A. S. Mikhailov and G. Ertl, Editors, Proceedings of the International Conference "Engineering of Chemical Complexity", Berlin Center for Studies of Complex Chemical Systems, 4-8 July 201