The effect of the particle size on the kinetics of CO electrooxidation on high surface area Pt catalysts

Using high-resolution transmission electron microscopy (TEM), infrared reflection-absorption spectroscopy (IRAS), and electrochemical (EC) measurements, platinum nanoparticles ranging in size from 1 to 30 nm are characterized and their catalytic activity for CO electrooxidation is evaluated. TEM analysis reveals that Pt crystallites are not perfect cubooctahedrons, and that large particles have "rougher" surfaces than small particles, which have some fairly smooth (111) facets. The importance of "defect" sites for the catalytic properties of nanoparticles is probed in IRAS experiments by monitoring how the vibrational frequencies of atop CO (nu(CO)) as well as the concomitant development of dissolved CO(2) are affected by the number of defects on the Pt nanoparticles. It is found that defects play a significant role in CO "clustering"on nanoparticles, causing CO to decrease/increase in local coverage, which yields to anomalous redshift/blueshift nu(CO) frequency deviations from the normal Stark-tuning behavior. The observed deviations are accompanied by CO(2) production, which increases by increasing the number of defects on the nanoparticles, that is, 1 < or = 2 < 5 < 30 nm. We suggest that the catalytic activity for CO adlayer oxidation is predominantly influenced by the ability of the surface to dissociate water and to form OH(ad) on defect sites rather than by CO energetics. These results are complemented by chronoamperometric and rotating disk electrode (RDE) data. In contrast to CO stripping experiments, we found that in the backsweep of CO bulk oxidation, the activity increases with decreasing particle size, that is, with increasing oxophilicity of the particles.     

Effects of polarization of 1.4 microm femtosecond laser pulses on the formation and fragmentation of naphthalene molecular ions compared at the same effective ionization intensity

Naphthalene was ionized with 130 fs pulses of different polarizations at 1.4 microm. In contrast to the results of ionization by 0.8 microm pulses, fragmentation was dramatically suppressed and naphthalene molecular ions of up to 3+ were produced. The use of this simple model of ionization and large electron kinetic energy enabled us to study the electron-recollision-induced fragmentation and/or double ionization more precisely. The failure of the theoretical prediction of ion yield for the case of naphthalene prevented us from judging the electron recollision solely by a comparison with theoretical curves. Therefore, the effects of laser polarization on the ratios between differently charged states and between molecular and total ions were compared at the same effective (peak) intensity instead of average intensity. Comparison under the same effective intensity enabled us to identify the effects of ellipticity clearly. Evidence of the electron recollision was found in the doubly charged molecular ion formation but not in the fragmentation. The single-electron recollision event was not sufficient to induce fragmentation because of its low energy transfer efficiency. We concluded that the fragmentation originated in the unstable nature of the highly charged molecular ion itself and in the Coulomb explosion in the case of naphthalene.     

A highly efficient carbon-carbon bond formation reaction via nucleophilic addition to N-alkylaldimines without acids or metallic species

A nucleophilic addition reaction to N-methylaldimines without acid or metal species is described. A novel reagent, dicyanomethyl acetate, is used as a nucleophile to give alpha-(N-methyl-N-acetyl)amino acid methyl esters in excellent yield.     

Solid State Radical Recombination and Charge Transfer across the Boundary between Indomethacin and Silica under Mechanical Stress

A composite of indomethacin (IM) and SiO₂ was prepared in a solid state by cogrinding. Dehydration was observed as a consequence of a chemical reaction between silanol groups of SiO₂ and carboxyl groups of IM. Several specific radical species found on separately ground SiO₂ disappeared preferentially after cogrinding as a result of their recombination. These chemical interactions under mechanical stress bring about a charge transfer, as confirmed by X-ray photoelectron spectroscopy, leading to Si-O-C bridging bond formation at the IM/SiO₂ interface.     

Investigation of Rust Formed on Steel Surfaces and Related Oxyhydroxides

In order to indentity the corrosion products formed on steel surfaces from ⁵⁷Fe Mössbauer spectroscopy, detailed Mössbauer parameters have been determined for various kinds of iron-oxyhydroxides: -FeOOH, -FeOOH, -FeOOH and -FeOOH. ⁵⁷Fe Mössbauer measurements of the iron oxyhydroxides indicate the following results. Fe occupies a single site in -FeOOH, but below the Néel temperature as at e.g., 300 K the Mössbauer spectrum is always broad, showing a distribution of the strength of the magnetic exchange interactions. Its shape depends on the grain-size and synthetic methods of the specimen. Fe occupies 3 sites in -FeOOH. High-purity reagents of -FeOOH always contain small amounts of -FeOOH and their Néel temperatures depend on the synthetic methods of the specimen. Mössbauer spectroscopy of the synthetic -FeOOH shows very broad distribution of the hyperfine magnetic fields.     

Versatile enantiocontrolled synthesis of (+)-fostriecin

Fostriecin, a potent protein phosphatase inhibitor and antitumor agent, has been enantioselectively synthesized in naturally occurring form via a versatile route, which also allows one to secure all possible stereoisomeres of the C1-C13 fragment including the C11 stereocenter and the geometry of the delta 12-double bond.     

Phase boundary between uniaxial and planar ferromagnets in layered perovskite manganite La2−2xSr1+2xMn2O7 (0.313⩽x⩽0.350)

We have examined magnetizations as a function of temperature and magnetic field in layered perovskite manganites La_2−2xSr_1+2xMn₂O₇ single crystals (x=0.313, 0.315, 0.318, 0.320 and 0.350) in order to determine the phase boundary between two ferromagnets (one is an uniaxial ferromagnet whose easy axis is parallel to the c-axis and the other is a planar ferromagnet whose easy axis is within the ab-plane) and following results are obtained: (i) all the present manganites exhibit magnetic transitions from a ferromagnet to a paramagnet at 76, 107, 116, 120 and 125 K for x=0.313, 0.315, 0.318, 0.320 and 0.350, respectively; (ii) for x=0.318, 0.320 and 0.350, the magnetic structure is a planar ferromagnet below Curie temperature; (iii) for x=0.313 and 0.315, the magnetic structure changes from an uniaxial to a planar ferromagnet at 66 and 85 K, respectively. From the results described above we have constructed the magnetic phase diagram of layered perovskite manganite La_2−2xSr_1+2xMn₂O₇ (0.313?x?0.350).     

Frequency dependence of third harmonic generation in polyacetylene

The frequency dependence of the third harmonic generation in trans-polyacetylene is quantitatively interpreted by considering the bands of finite chain and the damping of excitation. Our theory shows that there are two distinct peaks in the spectrum of the third harmonic generation. The first one around 0.6 eV comes from the three-photon resonant transition between the edges of the valence band and conduction band; the second one around 0.9 eV is produced by the two-photon interband transition. The excitation-dependent damping is essential to determine the position of the second peak. The theoretical results agree well with the experimental data.