Hydrothermal growth of mesoporous SBA-15 silica in the presence of PVP-stabilized Pt nanoparticles: synthesis, characterization, and catalytic properties

A novel high surface area heterogeneous catalyst based on solution phase colloidal nanoparticle chemistry has been developed. Monodisperse platinum nanoparticles of 1.7-7.1 nm have been synthesized by alcohol reduction methods and incorporated into mesoporous SBA-15 silica during hydrothermal synthesis. Characterization of the Pt/SBA-15 catalysts suggests that Pt particles are located within the surfactant micelles during silica formation leading to their dispersion throughout the silica structure. After removal of the templating polymer from the nanoparticle surface, Pt particle sizes were determined from monolayer gas adsorption measurements. Infrared studies of CO adsorption revealed that CO exclusively adsorbs to atop sites and red-shifts as the particle size decreases suggesting surface roughness increases with decreasing particle size. Ethylene hydrogenation rates were invariant with particle size and consistent with a clean Pt surface. Ethane hydrogenolysis displayed significant structure sensitivity over the size range of 1-7 nm, while the apparent activation energy increased linearly up to a Pt particle size of approximately 4 nm and then remained constant. The observed rate dependence with particle size is attributed to a higher reactivity of coordinatively unsaturated surface atoms in small particles compared to low-index surface atoms prevalent in large particles. The most reactive of these unsaturated surface atoms are responsible for ethane decomposition to surface carbon. The ability to design catalytic structures with tunable properties by rational synthetic methods is a major advance in the field of catalyst synthesis and for the development of accurate structure-function relationships in heterogeneous reaction kinetics.     

Cytochemical labeling for fungal and host components in plant tissues inoculated with fungal wilt pathogens.

Antibodies to detect pectin in present investigations attached to distinct fibrils in vessel lumina. In carnation infected with an isolate of Fusarium oxysporum f.sp., labeling of pathogen cells also occurred; in a resistant cultivar (cv.), it was coincident with proximate pectin fibrils and linked to altered fungal walls, which was the opposite in the susceptible cv., indicating that hindrance of pathogen ability to degrade pectin may be related to resistance. Labeling of the fungus in culture was nil, except in media containing pectin, showing that pectin is not native to the pathogen. Labeling of fungal walls for cellulose in elm (inoculated with Ophiostoma novo-ulmi) and carnation also occurred, linked to adsorbed host wall components. The chitin probe often attached to dispersed matter, in vessel lumina, traceable to irregularly labeled fungal cells and host wall degradation products. With an anti-horseradish peroxidase probe, host and fungal walls were equally labeled, and with a glucosidase, differences of labeling between these walls were observed, depending on pH of the test solution. Fungal extracellular matter and filamentous structures, present in fungal walls, predominantly in another elm isolate (Phaeotheca dimorphospora), did not label with any of the probes used. However, in cultures of this fungus, extracellular material labeled, even at a distance from the colony margin, with an anti-fimbriae probe.     

Proton polarization and differential cross section for the (3He,p) reaction on 6Li and 9Be at 14 MeV

Angular distributions of the proton polarization and the differential cross section have been measured for the reaction (³He, p) initiated by 14 MeV incident ³He particles and proceeding to the ground and the first excited states of the final nuclei ⁸Be and ¹¹B. Large polarization values were observed, especially for the ⁹Be(³He, p)¹¹B reaction leading to both the ground and the first excited states in ¹¹B. The experimental results have been analysed in terms of a two-nucleon transfer spindependent distorted-waves theory using finite-range formalism and including corrections due to the non-locality of the optical potentials. A proper coherent summation over L and S, whenever necessary was included in the DWBA calculations of the polarization and the differential cross section as implied by the presence of the spin-orbit terms in the optical-model potentials used to generate the distorted waves.     

Polarized Light and Quantum Mechanics: An Optical Analog of the Stern–Gerlach Experiment

Lecture demonstrations involving polarization of light are presented and discussed from the quantum theoretical point of view. The demonstrations clearly show that only two base states are required to describe the quantum state of a photon and they illustrate an optical analog of the Stern—Gerlach experiment that involved electrons.     

Direct synthesis of luminescent SiC quantum dots in water by laser ablation

Direct synthesis of luminescent SiC quantum dots in pure deionized water by laser ablation is reported. A zeta‐potential of –49 mV, higher than for nanoparticles produced by electrochemical etching, suggests a higher colloidal stability of the laser‐produced nanoparticles. IR spectroscopy shows that surface charges related to carboxylate anions ensure long‐term stability of the colloidal solutions based on the as‐prepared SiC quantum dots. Main radiative channel at room temperature corresponds to the recombination of quantumly confined photogenerated charge carriers. Emission from the nanoparticles is mainly centred at 2.75 eV regardless of laser power used for ablation. According to photoluminescence spectra, a partial transformation of the SiC quantum dots from cubic to hexagonal crystalline arrangement is supposed. (© 2011 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Fractal aggregates in simulated reduced gravity

We have developed a study of fractal aggregates in the laboratory geared towards their final production in a microgravity environment, on board of space shuttles and stations. Floating particles in gases and fluids have allowed simulation of conditions in reduced gravity. Production methods and dimensional analysis are described.     

The reaction 2H(α,αp)n near threshold and excited states of 6Li

The reaction ²H(α,αp)n has been studied in a kinematically complete experiment between E_α=9.22 and 11.3 MeV (3.07 to 3.77 MeV in the CM system). Data at the highest energies are dominated by αp and αn final-state interactions and at the same time indicate the relevance of the broad state (J^π=2⁺, T=0) centered at 4.7 MeV in ⁶Li ignored heretofore in theoretical calculations. Possible effects due to three-body forces are discussed.     

Adsorption and co-adsorption of ethylene and carbon monoxide on silica-supported monodisperse Pt nanoparticles: volumetric adsorption and infrared spectroscopy studies

The adsorption of carbon monoxide and ethylene, and their sequential adsorption, was studied over a series of Pt/SBA-15 catalysts with monodisperse particle sizes ranging from 1.7 to 7.1 nm by diffuse-reflectance infrared spectroscopy and chemisorption. Gas adsorption was dependent on the Pt particle size, temperature, and sequence of gas exposure. Adsorption of CO at room temperature on Pt/SBA-15 gives rise to a spectroscopic feature assigned to the C-O stretch: nu(CO) = 2075 cm-1 (1.9 nm); 2079 cm-1 (2.9 nm); 2082 cm-1 (3.6 nm); and 2090 cm-1 (7.1 nm). The intensity of the signal decreased in a sigmoidal fashion with increasing temperature, thereby providing semiquantitative surface coverage information. Adsorption of ethylene on Pt/SBA-15 gave rise to spectroscopic features at approximately 1340, approximately 1420, and approximately 1500 cm-1 assigned to ethylidyne, di-sigma-bonded ethylene, and pi-bonded ethylene, respectively. The ratio of these surface species is highly dependent on the Pt particle size. At room temperature, Pt particles stabilize ethylidyne as well as di-sigma- and pi-bonded ethylene; however, ethylidyne predominated on the surfaces of larger particles. Ethylidyne was the only identifiable species at 403 K, with its formation being more facile on larger particles. Co-adsorption experiments reveal that the composition of the surface layer is dependent on the order of exposure to gases. Exposure of a C2H4-covered Pt surface to CO resulted in an approximately 50% decrease in chemisorbed CO compared to a fresh Pt surface. The nu(CO) appeared at 2050 cm-1 on Pt/SBA-15 pretreated with C2H4 at room temperature. The di-sigma-bonded and pi-bonded species are the most susceptible to displacement from the surface by CO. The formation of ethylidyne appeared to be less sensitive to the presence of adsorbed carbon monoxide, especially on larger particles. Upon exposure of C2H4 to a CO-covered Pt surface, little irreversible uptake occurred due to nearly 100% site blocking. These results demonstrate that carbon monoxide competes directly with ethylene for surface sites, which will have direct implications on the poisoning of the heterogeneously catalyzed conversion of hydrocarbons.