Asymmetric hydrogenation of unfunctionalized, purely alkyl-substituted olefins

Asymmetric hydrogenation of olefins is one of the most useful reactions for the synthesis of optically active compounds, especially in industry. However, the application range of the catalysts developed so far is limited to alkenes with a coordinating functional group or an aryl substituent next to the double bond. We have found a class of chiral iridium catalysts that give high enantioselectivity in the hydrogenation of unfunctionalized, trialkyl-substituted olefins. Because these catalysts do not require the presence of any particular functional group or aryl substituent in the substrate, they considerably broaden the scope of asymmetric hydrogenation.     

Coking- and sintering-resistant palladium catalysts achieved through atomic layer deposition

We showed that alumina (Al(2)O(3)) overcoating of supported metal nanoparticles (NPs) effectively reduced deactivation by coking and sintering in high-temperature applications of heterogeneous catalysts. We overcoated palladium NPs with 45 layers of alumina through an atomic layer deposition (ALD) process that alternated exposures of the catalysts to trimethylaluminum and water at 200°C. When these catalysts were used for 1 hour in oxidative dehydrogenation of ethane to ethylene at 650°C, they were found by thermogravimetric analysis to contain less than 6% of the coke formed on the uncoated catalysts. Scanning transmission electron microscopy showed no visible morphology changes after reaction at 675°C for 28 hours. The yield of ethylene was improved on all ALD Al(2)O(3) overcoated Pd catalysts.     

Hydrocarbon separations in a metal-organic framework with open iron(II) coordination sites

The energy costs associated with large-scale industrial separation of light hydrocarbons by cryogenic distillation could potentially be lowered through development of selective solid adsorbents that operate at higher temperatures. Here, the metal-organic framework Fe(2)(dobdc) (dobdc(4-) : 2,5-dioxido-1,4-benzenedicarboxylate) is demonstrated to exhibit excellent performance characteristics for separation of ethylene/ethane and propylene/propane mixtures at 318 kelvin. Breakthrough data obtained for these mixtures provide experimental validation of simulations, which in turn predict high selectivities and capacities of this material for the fractionation of methane/ethane/ethylene/acetylene mixtures, removal of acetylene impurities from ethylene, and membrane-based olefin/paraffin separations. Neutron powder diffraction data confirm a side-on coordination of acetylene, ethylene, and propylene at the iron(II) centers, while also providing solid-state structural characterization of the much weaker interactions of ethane and propane with the metal.     

主要萜类化合物催化加氢研究进展

综述了国内外主要萜类化合物催化加氢研究进展状况.主要介绍蒎烯、双戊烯、香茅醛、柠檬醛、香叶醇和橙花醇等萜类化合物的加氢催化剂种类及其工艺条件.     

NMR studies of simple molecules on metal surfaces

In recent years, improvements in the sensitivity of nuclear magnetic resonance have made it possible to detect progressively smaller numbers of nuclei. Experiments and studies previously thought to be impractical can now be undertaken, for example, the study of phenomena at surfaces. Nuclear magnetic resonance has been applied to study simple molecules (carbon monoxide, acetylene, and ethylene) adsorbed on metal surfaces (ruthenium, rhodium, palladium, osmium, iridium, and platinum). The metals, in the form of clusters 10 to 50 angstroms in diameter, supported on alumina, are typical of real catalysts. The experiments provide information about the bonding of the molecules to the metal, the structures the molecules assume after adsorption, the motion of molecules on the surface, the breakup of molecules induced by heating, and the products of such breakup.     

Nitrogen fixation by gloeocapsa

The continuous growth in a medium free of combined nitrogen and the experimental production of ethylene via acetylene reduction indicate that nitrogen fixation by blue-green algae is not solely confined to filamentous genera with heterocysts. Axenic cultures of Gloeocapsa sp., adapted to nitrate-free medium, form ethylene at rates comparable to those of species known to fix nitrogen.     

Renewable hydrogen from ethanol by autothermal reforming

Ethanol and ethanol-water mixtures were converted directly into H2 with approximately 100% selectivity and >95% conversion by catalytic partial oxidation, with a residence time on rhodium-ceria catalysts of <10 milliseconds. Rapid vaporization and mixing with air with an automotive fuel injector were performed at temperatures sufficiently low and times sufficiently fast that homogeneous reactions producing carbon, acetaldehyde, ethylene, and total combustion products can be minimized. This process has great potential for low-cost H2 generation in fuel cells for small portable applications where liquid fuel storage is essential and where systems must be small, simple, and robust.     

The roles of subsurface carbon and hydrogen in palladium-catalyzed alkyne hydrogenation

Alkynes can be selectively hydrogenated into alkenes on solid palladium catalysts. This process requires a strong modification of the near-surface region of palladium, in which carbon (from fragmented feed molecules) occupies interstitial lattice sites. In situ x-ray photoelectron spectroscopic measurements under reaction conditions indicated that much less carbon was dissolved in palladium during unselective, total hydrogenation. Additional studies of hydrogen content using in situ prompt gamma activation analysis, which allowed us to follow the hydrogen content of palladium during catalysis, indicated that unselective hydrogenation proceeds on hydrogen-saturated beta-hydride, whereas selective hydrogenation was only possible after decoupling bulk properties from the surface events. Thus, the population of subsurface sites of palladium, by either hydrogen or carbon, governs the hydrogenation events on the surface.     

Linear metal nanostructures and size effects of supported metal catalysts

Nickel metal catalysts composed of nanometer by micrometer strips have been produced with solid-state microfabrication techniques. The strips are actually the edges of nickelcatalyst thin films, which are sandwiched between separating support layers, which are also nanometers thick. These linear nanostructures constitute well-defined and well-controlled catalytic entities that reproduce the size of traditional supported metal clusters in one dimension, thus separating size from total number of atoms in the catalyst. Examination of their catalytic activity showed that they duplicate the behavior of conventional supported clusters. A specific rate maximum was observed for the hydrogenolysis of ethane at a nanoscale dimension similar to the cluster size at which the rate is maximum in the case of the supported cluster studies, whereas the hydrogenation of ethylene shows no such size dependency. The results suggest that the surface-to-volume ratio or the number of atoms in the catalytic entity cannot be the source of these size effects and that either support effects or nonequilibrium surface structures are the determining factors.     

Nitrogen fixation in some anoxic lacustrine environments

Low rates of acetylene reduction to ethylene in water samples from two dystrophic lakes indicate the presence of nitrogenase and in situ nitrogen fixation. Highest rates were found in anoxic water from the aphotic zone. Environmental conditions in these lakes suggest the agents of fixation were bacteria.     

The Cassini UVIS stellar probe of the Titan atmosphere

The Cassini Ultraviolet Imaging Spectrometer (UVIS) observed the extinction of photons from two stars by the atmosphere of Titan during the Titan flyby. Six species were identified and measured: methane, acetylene, ethylene, ethane, diacetylene, and hydrogen cyanide. The observations cover altitudes from 450 to 1600 kilometers above the surface. A mesopause is inferred from extraction of the temperature structure of methane, located at 615 km with a temperature minimum of 114 kelvin. The asymptotic kinetic temperature at the top of the atmosphere determined from this experiment is 151 kelvin. The higher order hydrocarbons and hydrogen cyanide peak sharply in abundance and are undetectable below altitudes ranging from 750 to 600 km, leaving methane as the only identifiable carbonaceous molecule in this experiment below 600 km.     

Chemoselective hydrogenation of nitro compounds with supported gold catalysts

The selective reduction of a nitro group when other reducible functions are present is a difficult process that often requires stoichiometric amounts of reducing agents or, if H2 is used, the addition of soluble metals. Gold nanoparticles supported on TiO2 or Fe2O3 catalyzed the chemoselective hydrogenation of functionalized nitroarenes with H2 under mild reaction conditions that avoided the accumulation of hydroxylamines and their potential exothermic decomposition. These chemoselective hydrogenation gold catalysts also provide a previously unknown route for the synthesis of the industrially relevant cyclohexanone oxime from 1-nitro-1-cyclohexene.     

Production of liquid alkanes by aqueous-phase processing of biomass-derived carbohydrates

Liquid alkanes with the number of carbon atoms ranging from C7 to C15 were selectively produced from biomass-derived carbohydrates by acid-catalyzed dehydration, which was followed by aldol condensation over solid base catalysts to form large organic compounds. These molecules were then converted into alkanes by dehydration/hydrogenation over bifunctional catalysts that contained acid and metal sites in a four-phase reactor, in which the aqueous organic reactant becomes more hydrophobic and a hexadecane alkane stream removes hydrophobic species from the catalyst before they go on further to form coke. These liquid alkanes are of the appropriate molecular weight to be used as transportation fuel components, and they contain 90% of the energy of the carbohydrate and H2 feeds.     

硫化氢对Pd/c催化剂在环戊二烯加氢反应中性能的影响

本文用固定床反应器考察了Pd/C催化剂硫化前后,在环戊二烯加氢反应中的性能。结果表明环穴二烯的转化率从86.4％上升到98.2％,环戊烯的选择性从86.9％上升到98.8％,确定了最佳硫化条件。应用微型脉冲反应器研究了硫化过程和特性。     

Uptake and continued metabolic activity of azotobacter within fungal protoplasts

Uptake of vegetative cells of Azotobacter vinelandii into protoplasts of the mycorrhizal fungus Rhizopogon sp. can be induced by treatment with polyethylene glycol (molecular weight, 6000). An L-form of the bacteria has been selected for within the differentiated fungal mycelium which is capable of acetylene reduction and nitrogen fixation, as confirmed by nitrogen-15 assays; this allows the fungus to grow on media lacking any combined nitrogen. The fungus grows and reduces acetylene on concentrations of antibiotics that prevent the growth and activity of free-living Azotobacter. Electron microscopy has revealed modified mitochondrial forms or included bacterial L-forms surrounded by an extra fungal membrane within the hyphae of the modified strains. Poly-beta-hydroxybutyric acid, a storage product of Azotobacter cysts, has also been identified in the hyphae. This would appear to be the first report of the transgenosis for acetylene reduction activity and nitrogen fixation into a eukaryote cell.     

Isolated metal atom geometries as a strategy for selective heterogeneous hydrogenations

Facile dissociation of reactants and weak binding of intermediates are key requirements for efficient and selective catalysis. However, these two variables are intimately linked in a way that does not generally allow the optimization of both properties simultaneously. By using desorption measurements in combination with high-resolution scanning tunneling microscopy, we show that individual, isolated Pd atoms in a Cu surface substantially lower the energy barrier to both hydrogen uptake on and subsequent desorption from the Cu metal surface. This facile hydrogen dissociation at Pd atom sites and weak binding to Cu allow for very selective hydrogenation of styrene and acetylene as compared with pure Cu or Pd metal alone.     

硫化氢对Pd/C催化剂在环戊二烯加氢反应中性能的影响

本文用固定床反应器考察了Pd/C催化剂硫化前后 ,在环戊二烯加氢反应中的性能。结果表明环戊二烯的转化率从 86 4%上升到 98 2 % ,环戊烯的选择性从 86 9%上升到 98 8%。确定了最佳硫化条件。应用微型脉冲反应器研究了硫化过程和特性     

载体活性炭的研制(Ⅰ)——松根炭制维尼纶载体炭

本研究以松根炭为原料,利用新研制的粘合剂——复合1~#和复合2~#,制成乙炔气相沸腾床合成醋酸乙烯(维尼纶中间品)催化剂载体活性炭。产品醋酸吸附值为566mg/g、强度(球磨法)71.7％,可替代椰壳、果壳(核)等高强度活性炭。     

Polyolefin spheres from metallocenes supported on noninteracting polystyrene

To obviate the destructive interaction of highly reactive metallocene catalysts with classical silica-based supports while retaining the advantage of supported catalysts, a noninteracting polystyrene support was developed. Supported catalysts for the polymerization of alpha-olefins are prepared by treating lightly cross-linked, chloromethylated polystyrene beads consecutively with a secondary amine, an ammonium salt of a weakly coordinating anion, and a neutral dialkylmetallocene. Catalytic sites are distributed homogeneously throughout the support particle, and the polymerization occurs within the bead, in contrast to traditional surface-supported metallocene catalysts. The copolymerization of ethylene and 1-hexene at 40 degreesC affords discrete spherical polyolefin beads with a size (0.3 to 1.4 millimeters) that varies according to the polymerization time.     

Heterogeneous catalysis: some recent developments

In recent years major progress has been made in the area of heterogeneous catalysis by metals. Much has been learned about the nature of metal catalysts and of catalytic phenomena on metals. Characteristic patterns of catalytic behavior among the metallic elements have been established for certain classes of reactions, and these patterns provide a first step toward a more comprehensive understanding of catalytic specificity. Studies on metal alloys and related bimetallic catalysts have revived interest in a geometric factor in surface catalysis to complement the traditional electronic factor. Closely related to this geometric factor is the discovery that selectivity, rather than activity alone, is a major factor in reactions on bimetallic catalysts. Concurrent with progress in understanding how catalysts work, advances are also being made in the development of new catalyst systems, examples of which are the bimetallic (or polymetallic) cluster catalysts. Research in this area provides an example of how advances in catalyst technology can be realized within a framework of fundamental research on catalytic phenomena (38).