Structural behavior of Pby_yBi1.95−y_{1.95-y}Sr1.49_{1.49}La0.4_{0.4}Cu1.15_{1.15}O6+δ_{6+\delta} for 0<y<0.53

In the Bi cuprates, the presence of a near 1$\times$5 superstructure is well known. Usually, this superstructure is suppressed by the substitution of lead, but there have been reports of a phase separation in so called {\alpha} and {\beta} phases. This paper shows in high detail time how and why the phase separation develops and what happens to the quasi-1$\times$5 superstructure upon lead substitution. For this purpose, the lanthanum- and lead-substituted single-layered superconductor Bi$_{2+z}$Sr$_{2-z}$CuO$_{6+\delta}$ has been investigated by scanning tunneling microscopy and low-energy electron diffraction. The La content was kept constant at slightly under-doped concentration while the Pb content was changed systematically. Thermodynamic considerations show that a phase mixture of {\alpha} and {\beta} phases is inevitable.Comment: 17 pages, 4 figure

Nanoclusters and nanolines: the effect of molybdenum oxide substrate stoichiometry on iron self-assembly

The growth of Fe nanostructures on the stoichiometric MoO₂/Mo(110) and oxygen-rich MoO₂+x /Mo(110) surfaces has been studied using low-temperature scanning tunnelling microscopy (STM) and density functional theory calculations. STM results indicate that at low coverage Fe nucleates on the MoO₂/Mo(110) surface, forming small, well-ordered nanoclusters of uniform size, each consisting of five Fe atoms. These five-atom clusters can agglomerate into larger nanostructures reflecting the substrate geometry, but they retain their individual character within the structure. Linear Fe nanocluster arrays are formed on the MoO₂/Mo(110) surface at room temperature when the surface coverage is greater than 0.6 monolayers. These nanocluster arrays follow the direction of the oxide rows of the strained MoO₂/Mo(110) surface. Slightly altering the preparation procedure of MoO₂/Mo(110) leads to the presence of oxygen adatoms on this surface. Fe deposition onto the oxygen-rich MoO₂+x /Mo(110) surface results in elongated nanostructures that reach up to 24 nm in length. These nanolines have a zigzag shape and are likely composed of partially oxidised Fe formed upon reaction with the oxygen-rich surface

A review on substances and processes relevant for optical remote sensing of extremely turbid marine areas, with a focus on the Wadden Sea

The interpretation of optical remote sensing data of estuaries and tidal flat areas is hampered by optical complexity and often extreme turbidity. Extremely high concentrations of suspended matter, chlorophyll and dissolved organic matter, local differences, seasonal and tidal variations and resuspension are important factors influencing the optical properties in such areas. This review gives an overview of the processes in estuaries and tidal flat areas and the implications of these for remote sensing in such areas, using the Wadden Sea as a case study area. Results show that remote sensing research in extremely turbid estuaries and tidal areas is possible. However, this requires sensors with a large ground resolution, algorithms tuned for high concentrations of various substances and the local specific optical properties of these substances, a simultaneous detection of water colour and land-water boundaries, a very short time lag between acquisition of remote sensing and in situ data used for validation and sufficient geophysical and ecological knowledge of the area. © 2010 The Author(s)

Homolytic cleavage of molecular oxygen by manganese porphyrins supported on Ag(111).

Oxygen binding and cleavage are important for both molecular recognition and catalysis. Mn-based porphyrins in particular are used as catalysts for the epoxidation of alkenes, and in this study the homolytic cleavage of O2 by a surface-supported monolayer of Mn porphyrins on Ag(111) is demonstrated by scanning tunneling microscopy, X-ray absorption, and X-ray photoemission. As deposited, {5,10,15,20-tetraphenylporphyrinato}Mn(III)Cl (MnClTPP) adopts a saddle conformation with the average plane of its macrocycle parallel to the substrate and the axial Cl ligand pointing upward, away from the substrate. The adsorption of MnClTPP on Ag(111) is accompanied by a reduction of the Mn oxidation state from Mn(III) to Mn(II) due to charge transfer between the substrate and the molecule. Annealing the Mn(II)ClTPP monolayer up to 510 K causes the chlorine ligands to desorb from the porphyrins while leaving the monolayer intact. The Mn(II)TPP is stabilized by the surface acting as an axial ligand for the metal center. Exposure of the Mn(II)TPP/Ag(111) system to molecular oxygen results in the dissociation of O2 and forms pairs of Mn(III)OTPP molecules on the surface. Annealing at 445 K reduces the Mn(III)OTPP complex back to Mn(II)TPP/Ag(111). The activation energies for Cl and O removal were found to be 0.35 ± 0.02 eV and 0.26 ± 0.03 eV, respectively

Rotated domain network in graphene on cubic SiC 001

The atomic structure of the cubic SiC 001 surface during ultra high vacuum graphene synthesis has been studied using scanning tunneling microscopy STM and low energy electron diffraction. Atomically resolved STM studies prove the synthesis of a uniform, millimeter scale graphene overlayer consisting of nanodomains rotated by 13.5 relative to the amp; 9001;110 amp; 9002; directed boundaries. The preferential directions of the domain boundaries coincide with the directions of carbon atomic chains on the SiC 001 c 2 2 reconstruction, fabricated prior to graphene synthesis. The presented data show the correlation between the atomic structures of the SiC 001 c 2 2 surface and the graphene SiC 001 rotated domain network and pave the way for optimizing large area graphene synthesis on low cost cubic SiC 001 Si 001 wafer

Thermodynamics of CeO2 Thermochemical Fuel Production

In this work the thermodynamics of thermochemical fuel production using a CeO2 redox cycle are studied. The need to reduce the oxygen partial pressure in order to improve efficiency is investigated, with both sweep gas and vacuum pumping considered as methods of achieving this. At ambient pressure the cycles can be maximized with respect to the temperature swing, the minimum oxygen partial pressure, and the extent of the oxidation reaction. For reduction at 1500 °C the maximum efficiency was found to be 4.5%, which is significantly lower than the values found in previous studies. In Addition isothermal operation had very low efficiency (less than 2%) under all of the conditions considered. If the system is operated at lower than ambient pressure, the pumping efficiency will depend on the pressure. From an investigation of commercially available pumps the pressure dependence was given an analytical expression. The results showed the cycles have an optimal operating pressure and that using sweep gas, as well as pumping, only reduced the overall efficiency. The efficiency was maximized with respect to the temperature swing, the reduction pressure, and the extent of oxidation, giving a peak efficiency of 7.5% for a reduction temperature of 1500 °C. Reducing the pressure during reduction could also be beneficial due to improved reaction kinetics at lower pressure and an increased yield due to lower oxygen partial pressures. Recovering heat from both the high temperature ceria and the oxidation reaction, and using it as process heat, was also considered. With 60% of this heat being recovered, the peak efficiency for the 1500 °C pumped cycle increased to 11%. Finally the practicality of the cycles, in terms of the quantity of ceria required to maintain continuous operation, are considered, and some suggestions for improving the cycle are given