Visualizing gas molecules interacting with supported nanoparticulate catalysts at reaction conditions

Understanding how molecules can restructure the surfaces of heterogeneous catalysts under reaction conditions requires methods that can visualize atoms in real space and time. We applied a newly developed aberration-corrected environmental transmission electron microscopy to show that adsorbed carbon monoxide (CO) molecules caused the {100} facets of a gold nanoparticle to reconstruct during CO oxidation at room temperature. The CO molecules adsorbed at the on-top sites of gold atoms in the reconstructed surface, and the energetic favorability of this reconstructed structure was confirmed by ab initio calculations and image simulations. This atomic-scale visualizing method can be applied to help elucidate reaction mechanisms in heterogeneous catalysis.     

Powering fuel cells with CO via aqueous polyoxometalates and gold catalysts

Electricity was produced by catalytic oxidation of carbon monoxide (CO) by using gold catalysts at room temperature. The observed rates are faster than conventional processes operating at 500 kelvin or higher for the conversion of CO with water to produce hydrogen and carbon dioxide through the water-gas shift (WGS). By eliminating the WGS reaction, we remove the need to transport and vaporize liquid water in the production of energy for portable applications. This process can use CO-containing gas streams from the catalytic reforming of hydrocarbons to produce an aqueous solution of reduced polyoxometalate compounds that can be used to generate power. The reduced polyoxometalate can be reoxidized in fuel cells that contain simple carbon anodes.     

Identification of non-precious metal alloy catalysts for selective hydrogenation of acetylene

The removal of trace acetylene from ethylene is performed industrially by palladium hydrogenation catalysts (often modified with silver) that avoid the hydrogenation of ethylene to ethane. In an effort to identify catalysts based on less expensive and more available metals, density functional calculations were performed that identified relations in heats of adsorption of hydrocarbon molecules and fragments on metal surfaces. This analysis not only verified the facility of known catalysts but identified nickel-zinc alloys as alternatives. Experimental studies demonstrated that these alloys dispersed on an oxide support were selective for acetylene hydrogenation at low pressures.     

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.     

Antiarthritic gold compounds effectively quench electronically excited singlet oxygen

Although certain gold [Au(I)] compounds have been used effectively in the treatment of rheumatoid arthritis for some years, the molecular basis for such therapeutic action has been unclear. One possible mechanism of the action of Au(I) compounds is that they protect unsaturated membrane lipids and proteins against oxidative degradation caused by activated phagocytes that are not properly regulated. In this study it has been shown that superoxide ion (O-2.), a product of activated phagocytes, can be oxidized to electronically excited singlet oxygen (O1(2)delta g), an agent that is capable of peroxidation of unsaturated fatty acid derivatives. It has also been shown that antiarthritic Au(I) compounds are effective deactivators of O1(2)delta g with quenching constants on the order of 10(7) M-1 sec-1.     

Mechanism of the relation between the content of nitro and nitroso compounds in amnion and allantois of chicken embryos and rate of posthatch chick growth

It is established that metabolism of nitric oxide (NO) in the chicken embryo and posthatch growth rate of chicks have a direct relation which is determined both by the genotype and by external factors influencing posthatch growth rate.     

不同催化剂条件下毛竹材液化反应动力学研究

为了筛选出高效液化竹材催化剂,达到竹材温和条件下液化,该文利用等温差示热量扫描曲线方法,分析了不同催化剂（KCl和K2 CO3）对毛竹材液化剂苯酚液化反应的影响。在20～300℃温度范围内,运用Kissinger方程在不同的升温速率（5、10、15和20℃/min）下进行动力学研究。结果表明:竹材液化反应是吸热反应;随着升温速率的增加,特征液化温度向高温方向移动;不同催化剂（K2 CO3、KCl、无催化剂）条件下竹材液化反应表观活化能依次是45.95、59.99、58.00 kJ/mol,可见K2 CO3适合做竹材液化的催化剂。由外推法得出竹材液化反应最佳工艺为:催化剂为K2 CO3,初始液化温度为691℃,液化峰高温度为97.3℃,液化峰终温度为111.9℃。      

NMR imaging of catalytic hydrogenation in microreactors with the use of para-hydrogen

Catalysis is vital to industrial chemistry, and the optimization of catalytic reactors attracts considerable resources. It has proven challenging to correlate the active regions in heterogeneous catalyst beds with morphology and to monitor multistep reactions within the bed. We demonstrate techniques, using magnetic resonance imaging and para-hydrogen (p-H2) polarization, that allow direct visualization of gas-phase flow and the density of active catalyst in a packed-bed microreactor, as well as control over the dynamics of the polarized state in space and time to facilitate the study of subsequent reactions. These procedures are suitable for characterizing reactors and reactions in microfluidic devices where low sensitivity of conventional magnetic resonance would otherwise be the limiting factor.     

Biomineralization of gold: biofilms on bacterioform gold

Bacterial biofilms are associated with secondary gold grains from two sites in Australia. 16S ribosomal DNA clones of the genus Ralstonia that bear 99% similarity to the bacterium Ralstonia metallidurans-shown to precipitate gold from aqueous gold(III) tetrachloride-were present on all DNA-positive gold grains but were not detected in the surrounding soils. These results provide evidence for the bacterial contribution to the authigenic formation of secondary bacterioform gold grains and nuggets.     

Mechanism and stereoselectivity of asymmetric hydrogenation

Rhodium complexes containing chiral phosphine ligands catalyze the hydrogenation of olefinic substrates such as alpha-aminoacrylic acid derivatives, producing chiral products with very high optical yields. Elucidation of the mechanisms of such reactions leads to the conclusion that the stereoselection is dictated not by the preferred initial binding of the substrate to the chiral catalyst, but rather by the much higher reactivity of the minor diastereomer of the catalyst-substrate adduct corresponding to the less favored binding mode.     

Flash hydrogenation of a bituminous coal

Flash heating of Illinois coal (to 700 degrees C in 1 second) in flowing hydrogen at 100 atmospheres, limiting the vapor residence time at 700 degrees C to 3 seconds, converts 14 percent of the coal's carbon to methane, 7 percent to ethane, and 10 percent to benzene, toluene, and xylenes. The remainder is coke; the carbon balance shows that heavy tar, if any exists, is less than 3 percent.     

Electrically supported column of liquid

Applicctiont of an electric field normal to the interface of certain liquids causes a liquid column of uniform diameter to be formed parallel to the electric field. A column of amyl alcohol supported in aim by a high voltage was investigated experimentally; the diameter of the column varied aS the voltage raised to the 3.5 power.     

Enhanced ethylene and ethane production with free-radical cracking catalysts

A series of free-radical catalysts have been discovered that increase the yield of highly valuable olefins from the cracking of low molecular weight paraffins. For example, catalytic cracking of n-butane, isobutane, and propane over manganese or iron supported on magnesium oxide (MgO) gave product distributions different from those given by thermal (free-radical) cracking or cracking over traditional acid catalysts. With n-butane and propane feeds, the products from catalytic cracking included large amounts of ethylene and ethane; with isobutane feed, propylene was the major product. Physical characterization of the MgO-supported catalyst showed the manganese to be in a 2+ oxidation state in the reduced catalyst and a 4+ oxidation state in the fully oxidized catalyst. Manganese was also shown to be uniformly distributed in the support material with very little enrichment at the surface. Matrix isolation of the gasphase radicals from n-butane feed showed that ethyl and methyl radicals were produced over the active catalysts. In the thermal process, only methyl radicals were produced. The mechanism of the catalytic reaction appears to be selective formation of primary carbanions at the catalyst surface followed by electron transfer and release of primary hydrocarbon radicals to the gas phase.     

Atmospheric reactions of polycyclic aromatic hydrocarbons: facile formation of mutagenic nitro derivatives

Directly active mutagens are formed on exposure of the promutagen benzo[a]pyrene to gaseous pollutants in smog. In simulated atmospheres containing 1 part per million nitrogen dioxide and traces of nitric acid, directly mutagenic nitro derivatives are readily formed from both benzo[a]pyrene and perylene, a non-mutagen in the Ames reversion assay. Possible formation of direct mutagens by such reactions on sample collection filters, in exhaust effluents, and in the atmosphere should be recognized.     

Reversible control of hydrogenation of a single molecule

Low-temperature scanning tunneling microscopy was used to selectively break the N-H bond of a methylaminocarbyne (CNHCH3) molecule on a Pt(111) surface at 4.7 kelvin, leaving the C-H bonds intact, to form an adsorbed methylisocyanide molecule (CNCH3). The methylisocyanide product was identified through comparison of its vibrational spectrum with that of directly adsorbed methylisocyanide as measured with inelastic electron tunneling spectroscopy. The CNHCH3 could be regenerated in situ by exposure to hydrogen at room temperature. The combination of tip-induced dehydrogenation with thermodynamically driven hydrogenation allows a completely reversible chemical cycle to be established at the single-molecule level in this system. By tailoring the pulse conditions, irreversible dissociation entailing cleavage of both the C-H and N-H bonds can also be demonstrated.     

钙钛矿催化剂用于氨选择性还原氮氧化物的研究进展

氨选择性催化还原氮氧化物(NO_x)技术是目前应用较为广泛的催化脱硝技术,钙钛矿材料因其独特的结构、良好的稳定性且环保无害的特点成为选择性催化还原NO_x领域的研究热点。本文综述了近年来国内外关于钙钛矿NH_3-SCR催化剂的研究进展,较为全面地对钙钛矿催化剂的主要类型、脱硝活性、构效关系进行了论述,同时介绍了钙钛矿在光辅助SCR技术这一全新领域的研究进展,并总结了钙钛矿催化剂的NH_3-SCR反应机制,对该领域未来可能的发展方向和研究目标进行了展望。     

镉离子在三正辛胺为载体的支撑液膜中的传输

用三正辛胺为载体，聚丙烯微孔膜为支撑体的支撑液膜体系处理含镉料液，得出影响镉离子传输的参数。