Production of the industrial chemical propylene oxide is energy-intensive and environmentally unfriendly. Catalysts based on bulk silver surfaces with direct propylene epoxidation by molecular oxygen have not resolved these problems because of substantial formation of carbon dioxide. We found that unpromoted, size-selected Ag3 clusters and approximately 3.5-nanometer Ag nanoparticles on alumina supports can catalyze this reaction with only a negligible amount of carbon dioxide formation and with high activity at low temperatures. Density functional calculations show that, relative to extended silver surfaces, oxidized silver trimers are more active and selective for epoxidation because of the open-shell nature of their electronic structure. The results suggest that new architectures based on ultrasmall silver particles may provide highly efficient catalysts for propylene epoxidation.

Small clusters are known to possess reactivity not observed in their bulk analogues, which can make them attractive for catalysis. Their distinct catalytic properties are often hypothesized to result from the large fraction of under-coordinated surface atoms. Here, we show that size-preselected Pt(8-10) clusters stabilized on high-surface-area supports are 40-100 times more active for the oxidative dehydrogenation of propane than previously studied platinum and vanadia catalysts, while at the same time maintaining high selectivity towards formation of propylene over by-products. Quantum chemical calculations indicate that under-coordination of the Pt atoms in the clusters is responsible for the surprisingly high reactivity compared with extended surfaces. We anticipate that these results will form the basis for development of a new class of catalysts by providing a route to bond-specific chemistry, ranging from energy-efficient and environmentally friendly synthesis strategies to the replacement of petrochemical feedstocks by abundant small alkanes.

We introduce high surface area ZnO nanotube photoanodes templated by anodic aluminum oxide for use in dye-sensitized solar cells (DSSCs). Atomic layer deposition is utilized to coat pores conformally, providing a direct path for charge collection over tens of micrometers thickness. Compared to similar ZnO-based devices, ZnO nanotube cells show exceptional photovoltage and fill factors, in addition to power efficiencies up to 1.6%. The novel fabrication technique provides a facile, metal-oxide general route to well-defined DSSC photoanodes.

The strontium, zirconium, molybdenum, and barium isotopic compositions predicted in the mass-losing envelopes of asymptotic giant branch (AGB) stars of solar metallicity and mass 1.5, 3, and 5 M are discussed and compared with recent measurements in single presolar silicon carbide (SiC) grains from the Murchison meteorite. Heavy-element nucleosynthesis via the s-process occurs in the helium intershell, the region between the helium-burning and hydrogen-burning shells, producing heavy elements beyond iron. After a limited number of thermal runaways of the helium shell (thermal pulses), at the quenching of each instability, the convective envelope penetrates into the top layers of the helium intershell (third dredge-up), mixing newly synthesized 12 C and s-process material to the stellar surface. Eventually, the envelope becomes carbon-rich (C ! O), a necessary condition for SiC grains to condense. In the helium intershell, neutrons are released by (, n) reactions on 13 C and 22 Ne during interpulse phases and the thermal pulses, respectively. A 13 C pocket is assumed to form in a tiny region in the top layers of the helium intershell by injection of a small amount of protons from the envelope during each third dredge-up episode. This 13 C then burns radiately during the interpulse phase. The average neutron density produced is low, but of long duration, so the total neutron exposure is high. We have explored a large range of possible 13 C abundances in the pocket. In low-mass AGB stars (1:5 M M 4 M ), a second small burst of neutrons is released by marginal 22 Ne burning in the thermal pulse. The neutron density reaches quite a high peak value but is of short duration, so the neutron exposure is low. In intermediate-mass AGB stars (4 M < M 8 M ), the 22 Ne neutron source is more efficiently activated. The neutron capture process has been followed with a postprocessing code that considers all relevant nuclei from 4 He to 210 Po. The predicted isotopic compositions of strontium, zirconium, molybdenum, and barium in the envelopes of low-mass AGB stars of solar metallicity are in agreement with the isotopic ratios measured in individual presolar SiC grains, whereas predictions for intermediate-mass stars exclude them as the sources of these grains. A multiplicity of low-mass AGB stars with metallicity around solar, having different masses and experiencing different neutron exposures, are required to account for the measured spread in heavy-element isotopic compositions among single presolar SiC grains. The range of neutron exposures corresponds, on average, to a lower mean neutron exposure than that required to reproduce the s-process main component in the solar system.

Modern dye-sensitized solar cell (DSSC) technology was built upon nanoparticle wide bandgap semiconductor photoanodes. While versatile and robust, the sintered nanoparticle architecture exhibits exceedingly slow electron transport that ultimately restricts the diversity of feasible redox mediators. The small collection of suitable mediators limits both our understanding of an intriguing heterogeneous system and the performance of these promising devices. Recently, a number of pseudo-1D photoanodes that exhibit accelerated charge transport and greater materials flexibility were fabricated. The potential of these alternative photoanode architectures for advancing, both directly and indirectly, the performance of DSSCs is explored.