Use of colloidal ruthenium particles in the electrochemical reduction of benzene by solvated electrons

Ruthenium colloidal particles prepared by the decomposition of a ruthenium acid sulfite complex increased the electrochemical reduction of benzene from 45% to 60% at room temperature and 10 psig of hydrogen. The reduction was carried out in a 21 mole % ethanol - 79 mole % hexamethylphosporamide. The significant increase in the percent of benzene reduced was accompanied by an apparent current efficiency of 98%. Comparison with analogous experiments employing colloidal platinum particles indicates that the above increase in benzene reduction can be attributed to direct catalytic hydrogenation by the ruthenium.     

Predicting oxide stability in high-temperature water vapor

The importance of understanding and predicting the interactions of oxides with water vapor at high temperatures is demonstrated in this article. Methods for observing volatilization phenomena and identifying the chemical formulae for volatile metal hydroxides are discussed. In addition, techniques for obtaining accurate thermodynamic data for gaseous metal hydroxide species are described. Detailed examples of the stability of the principle structural and/or protective oxides chromia (Cr₂O₃), silica (SiO₂), and alumina (Al₂O₃) in high-temperature water vapor are included.     

Self-assembled patterned CoFe2O4-SrRuO3 electrodes: Enhanced functional properties by polar nano-regions reorientation

Epitaxial CoFe₂O₄ (CFO) and SrRuO₃ (SRO) nanopillar heterostructures were deposited on Pb(Mg_1/3Nb_2/3)_0.70Ti_0.30O₃ (PMN-30PT) single crystal substrates by switch pulsed laser deposition (SPLD). Since the CFO nanopillars are insulating, and the SRO matrix conductive, this self-assembled nanopillar heterostructure served as a patterned electrode on PMN-PT, which then enhances the dielectric and piezoelectric constant of the substrate. Cross-sectional electron microscopy images revealed the formation of a nanopillar heterostructure layer with CFO nanopillars within a SRO matrix. AFM and XRD revealed good topography and epitaxy, indicating a high quality SRO-CFO self-assembled nanopillar structure. Using a SRO-CFO thin film patterned electrode, PMN-PT was found to have a notably higher (30%) dielectric constant with increasing electric field and enhanced transverse broadening in reciprocal spacing mapping (RSM) scans.     

Thermodynamics of high-temperature aluminum,zirconium, and yttrium hydroxide and oxyhydroxide vapor species

Thermodynamic parameters are reported for gaseous hydroxides and oxyhydroxides of Al, Zr, and Y. The structures and vibrational frequencies are calculated using density functional theory with the B3LYP functional. This yields entropies at 298.15 K and heat capacities. The enthalpies are calculated from appropriate reactions and the CCSD(T) (Coupled Cluster, Singles, Doubles, and perturbative Triples) approach. The hydroxide groups are treated as hindered rotors for all species. The results are compared to the limited experimental and theoretical calculations for these species. Finally, the data are put into a database for a free-energy minimizer and the vapor pressures for each species are compared.     

Combining effects of TiO6 octahedron rotations and random electric fields on structural and properties in Na0.5Bi0.5TiO3

The structural and dielectric properties of Na_0.5Bi_0.5TiO₃ (NBT) ceramics and crystals have been investigated and are compared to that of Pb(Zr_0.55Ti_0.45)O₃ (PZT55/45) and Pb(Mg_1/3Nb_2/3)_0.72Ti_0.28O₃ (PMNT 72/28) ceramics. X-ray diffraction (XRD) profiles for (100), (110), (111), (200), (220), and (222) (referred to cubic structure) reveal that the monoclinic structure with Cc space group exists both in the NBT single crystal and ceramics. The diffraction profile obtained with high resolution laboratory XRD for the NBT single crystal can be well described, using Cc model instead of R3c model. The dielectric constant of NBT below T_hump shows some similarity to that of PZT45/55 ceramics below 50°C in which oxygen octahedron rotations cause the frequency dispersion of the dielectric constant. The temperature-dependent dielectric constant for NBT can be deconvolved into two independent processes. The lower temperature process shows a typical relaxor characteristic and follows the Vogel-Fulcher relationship. The other process at higher temperature shows less frequency-dependent behavior. Comparing the dielectric constant of NBT with that of PZT55/45 and PMNT72/28 reveals that both oxygen octahedral rotations and random electric fields play an important role in the frequency dispersion of the dielectric constant for NBT relaxor feroelectric.