共查询到20条相似文献，搜索用时 31 毫秒
1.
Over H Kim YD Seitsonen AP Wendt S Lundgren E Schmid M Varga P Morgante A Ertl G 《Science (New York, N.Y.)》2000,287(5457):1474-1476
The structure of RuO(2)(110) and the mechanism for catalytic carbon monoxide oxidation on this surface were studied by low-energy electron diffraction, scanning tunneling microscopy, and density-functional calculations. The RuO(2)(110) surface exposes bridging oxygen atoms and ruthenium atoms not capped by oxygen. The latter act as coordinatively unsaturated sites-a hypothesis introduced long ago to account for the catalytic activity of oxide surfaces-onto which carbon monoxide can chemisorb and from where it can react with neighboring lattice-oxygen to carbon dioxide. Under steady-state conditions, the consumed lattice-oxygen is continuously restored by oxygen uptake from the gas phase. The results provide atomic-scale verification of a general mechanism originally proposed by Mars and van Krevelen in 1954 and are likely to be of general relevance for the mechanism of catalytic reactions at oxide surfaces. 相似文献
2.
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. 相似文献
3.
The high catalytic activity of gold clusters on oxides has been attributed to structural effects (including particle thickness and shape and metal oxidation state), as well as to support effects. We have created well-ordered gold mono-layers and bilayers that completely wet (cover) the oxide support, thus eliminating particle shape and direct support effects. High-resolution electron energy loss spectroscopy and carbon monoxide adsorption confirm that the gold atoms are bonded to titanium atoms. Kinetic measurements for the catalytic oxidation of carbon monoxide show that the gold bilayer structure is significantly more active (by more than an order of magnitude) than the monolayer. 相似文献
4.
Herzing AA Kiely CJ Carley AF Landon P Hutchings GJ 《Science (New York, N.Y.)》2008,321(5894):1331-1335
Gold nanocrystals absorbed on metal oxides have exceptional properties in oxidation catalysis, including the oxidation of carbon monoxide at ambient temperatures, but the identification of the active catalytic gold species among the many present on real catalysts is challenging. We have used aberration-corrected scanning transmission electron microscopy to analyze several iron oxide-supported catalyst samples, ranging from those with little or no activity to others with high activities. High catalytic activity for carbon monoxide oxidation is correlated with the presence of bilayer clusters that are approximately 0.5 nanometer in diameter and contain only approximately 10 gold atoms. The activity of these bilayer clusters is consistent with that demonstrated previously with the use of model catalyst systems. 相似文献
5.
Bimetallic electrodes are used in a number of electrochemical processes, but the role of particular arrangements of surface metal atoms (ensembles) has not been studied directly. We have evaluated the electrochemical/catalytic properties of defined atomic ensembles in atomically flat PdAu(111) electrodes with variable surface stoichiometry that were prepared by controlled electrodeposition on Au(111). These properties are derived from infrared spectroscopic and voltammetric data obtained for electrode surfaces for which the concentration and distribution of the respective metal atoms are determined in situ by atomic resolution scanning tunneling microscopy with chemical contrast. Palladium monomers are identified as the smallest ensemble ("critical ensemble") for carbon monoxide adsorption and oxidation, whereas hydrogen adsorption requires at least palladium dimers. 相似文献
6.
The selective oxidation of alcohols in aqueous phase over supported metal catalysts is facilitated by high-pH conditions. We have studied the mechanism of ethanol and glycerol oxidation to acids over various supported gold and platinum catalysts. Labeling experiments with (18)O(2) and H(2)(18)O demonstrate that oxygen atoms originating from hydroxide ions instead of molecular oxygen are incorporated into the alcohol during the oxidation reaction. Density functional theory calculations suggest that the reaction path involves both solution-mediated and metal-catalyzed elementary steps. Molecular oxygen is proposed to participate in the catalytic cycle not by dissociation to atomic oxygen but by regenerating hydroxide ions formed via the catalytic decomposition of a peroxide intermediate. 相似文献
7.
氯化物催化合成甲,乙,丙酸异戊酯的活性和机理探讨 总被引：3，自引：0，他引：3
本文分别用氯化铁，氯化铝和氯化铜催化合成甲、乙、丙酸异戊酯，实验证明氯化铁，氯化铝有较高催化活性，对五个碳以下的有机酸和醇的酯化活性较高，并对其机理进行了的探讨。 相似文献
8.
Pedersen CJ 《Science (New York, N.Y.)》1988,241(4865):536-540
The discovery of the crown ethers stemmed from efforts to control the catalytic activity of vanadium and copper by complexation with multidentate ligands. The first crown ether, 2,3,11,12-dibenzo-1,4,7,10,13,16-hexaoxacyclo-octadeca-2,11-diene, was obtained in 0.4% yield during an attempt to prepare a phenolic ligand from catechol and bis(2-chloroethyl)ether. This compound, which complexed with the sodium cation, was the first compound known to display such activity and became known as dibenzo-18-crown-6, an 18-atom heterocycle containing 6 oxygen atoms. Some 60 related compounds were made involving heterocyclic rings containing 12 to 60 atoms including 4 and 10 oxygen atoms. There are optimum polyether ring sizes for the different alkali metal cations: 15 to 18 for sodium, 18 for potassium, and 18 to 21 for cesium. Complexes having polyether to cation ratios of 1:1, 3:2, and 2:1 were prepared. Solubilization of inorganic salts in aprotic solvents, especially by saturated crown ethers, was demonstrated. 相似文献
9.
A mechanism for producing an 11-year oscillation in ozone over the polar caps is the modulation of galactic cosmic rays by the solar wind. This mechanism has been shown to give the observed phase in ozone oscillations and the correct qualitative dependence on latitude. However, the production of nitrogen atoms from cosmic-ray collisions seems inadequate to account for the ozone amplitude. Negative ions are also produced as a result of cosmic-ray ionization, and negative-ion chemistry may be of importance in the stratosphere. Specifically, NO(x)(-) may go through a catalytic cycle in much the same fashion as NO(x), but with the important distinction that it does not depend on oxygen atoms to complete the cycle. Estimates of the relevant rates of reaction suggest that negative ions may be especially important over the winter polar cap. 相似文献
10.
A copper-nitrosyl intermediate forms during the catalytic cycle of nitrite reductase, the enzyme that mediates the committed step in bacterial denitrification. The crystal structure of a type 2 copper-nitrosyl complex of nitrite reductase reveals an unprecedented side-on binding mode in which the nitrogen and oxygen atoms are nearly equidistant from the copper cofactor. Comparison of this structure with a refined nitrite-bound crystal structure explains how coordination can change between copper-oxygen and copper-nitrogen during catalysis. The side-on copper-nitrosyl in nitrite reductase expands the possibilities for nitric oxide interactions in copper proteins such as superoxide dismutase and prions. 相似文献
11.
All known internal covalent cross-links in proteins involve functionalized groups having oxygen, nitrogen, or sulfur atoms present to facilitate their formation. Here, we report a carbon-carbon cross-link between two unfunctionalized side chains. This valine-phenyalanine cross-link, produced in an oxygen-dependent reaction, is generated by its own carboxylate-bridged diiron center and serves to stabilize the metallocenter. This finding opens the door to new types of posttranslational modifications, and it demonstrates new catalytic potential of diiron centers. 相似文献
12.
13.
Behrens M Studt F Kasatkin I Kühl S Hävecker M Abild-Pedersen F Zander S Girgsdies F Kurr P Kniep BL Tovar M Fischer RW Nørskov JK Schlögl R 《Science (New York, N.Y.)》2012,336(6083):893-897
One of the main stumbling blocks in developing rational design strategies for heterogeneous catalysis is that the complexity of the catalysts impairs efforts to characterize their active sites. We show how to identify the crucial atomic structure motif for the industrial Cu/ZnO/Al(2)O(3) methanol synthesis catalyst by using a combination of experimental evidence from bulk, surface-sensitive, and imaging methods collected on real high-performance catalytic systems in combination with density functional theory calculations. The active site consists of Cu steps decorated with Zn atoms, all stabilized by a series of well-defined bulk defects and surface species that need to be present jointly for the system to work. 相似文献
14.
Tao F Grass ME Zhang Y Butcher DR Renzas JR Liu Z Chung JY Mun BS Salmeron M Somorjai GA 《Science (New York, N.Y.)》2008,322(5903):932-934
Heterogeneous catalysts that contain bimetallic nanoparticles may undergo segregation of the metals, driven by oxidizing and reducing environments. The structure and composition of core-shell Rh(0.5)Pd(0.5) and Pt(0.5)Pd(0.5) nanoparticle catalysts were studied in situ, during oxidizing, reducing, and catalytic reactions involving NO, O2, CO, and H2 by x-ray photoelectron spectroscopy at near-ambient pressure. The Rh(0.5)Pd(0.5) nanoparticles underwent dramatic and reversible changes in composition and chemical state in response to oxidizing or reducing conditions. In contrast, no substantial segregation of Pd or Pt atoms was found in Pt(0.5)Pd(0.5) nanoparticles. The different behaviors in restructuring and chemical response of Rh(0.5)Pd(0.5) and Pt(0.5)Pd(0.5) nanoparticle catalysts under the same reaction conditions illustrates the flexibility and tunability of the structure of bimetallic nanoparticle catalysts during catalytic reactions. 相似文献
15.
The insertion of an iridium complex into an N-H bond in ammonia leads to a stable monomeric amido hydride complex in solution at room temperature. This reaction advances the transition-metal coordination chemistry of ammonia beyond its role for more than a century as an ancillary ligand. The precursor for this insertion reaction is an iridium(I) olefin complex with an aliphatic ligand containing one carbon and two phosphorus donor atoms. Kinetic and isotopic labeling studies indicate that olefin dissociates to give a 14-electron iridium(I) fragment, which then reacts with ammonia. This cleavage of the N-H bond under neutral conditions provides a foundation on which to develop future mild catalytic transformations of ammonia, such as olefin hydroamination and arene oxidative amination. 相似文献
16.
Xu RX Hassell AM Vanderwall D Lambert MH Holmes WD Luther MA Rocque WJ Milburn MV Zhao Y Ke H Nolte RT 《Science (New York, N.Y.)》2000,288(5472):1822-1825
Cyclic nucleotides are second messengers that are essential in vision, muscle contraction, neurotransmission, exocytosis, cell growth, and differentiation. These molecules are degraded by a family of enzymes known as phosphodiesterases, which serve a critical function by regulating the intracellular concentration of cyclic nucleotides. We have determined the three-dimensional structure of the catalytic domain of phosphodiesterase 4B2B to 1.77 angstrom resolution. The active site has been identified and contains a cluster of two metal atoms. The structure suggests the mechanism of action and basis for specificity and will provide a framework for structure-assisted drug design for members of the phosphodiesterase family. 相似文献
17.
Studies in heterogeneous catalysis have long speculated on or have provided indirect evidence for the role of hydrogen embedded in the catalyst bulk as a primary reactant. This report describes experiments carried out under single-collision conditions that document the distinctive reactivity of hydrogen embedded in the bulk of the metal catalyst. Specifically, the bulk H atom is shown to be the reactive species in the hydrogenation of CH(3) adsorbed on Ni(111) to form CH(4), while the H atoms bound to the surface were unreactive. These results unambiguously demonstrate the importance of bulk species to heterogeneous catalytic chemistry. 相似文献
18.
The molecular sieve MCM-22 contains structural features previously unobserved in this class of materials. Its framework topology, derived from high-resolution electron micrographs and refined with synchrotron x-ray diffraction powder data, contains two independent pore systems, both of which are accessed through rings composed of ten tetrahedral (T) atoms (such as Si, Al, and B). One of these pore systems is defined by two-dimensional, sinusoidal channels. The other consists of large supercages whose inner free diameter, 7.1 angstroms, is defined by 12 T-O species (12-rings) and whose inner height is 18.2 angstroms. These coexisting pore systems may provide opportunities for a wide variety of catalytic applications in the petrochemical and refining industries. Another structural feature is an unusual -T-O-T- chain that passes through the center of a modified dodecasil-1H [4(3)5(6)6(3)] cage. 相似文献
19.
A method has been developed for the preparation of uniform palladium particles of diameter from 55 to 450 angstroms. Uniform particles of gold layered on palladium were also synthesized. Hydrothermal treatment of aluminum hydroxide sol was used to prepare rods of alumina with uniform cross section from 100 to 500 angstroms and of varying lengths. The palladium was adsorbed as individual particles on alumina rods, both present in aqueous suspension. Then the suspension was dried to give a catalyst containing metal particles of uniform size dispersed in open pores produced by the intermeshing of the alumina rods. This procedure guaranteed the absence of diffusion control in the rate of reactions observed experimentally. All stages of the preparation were monitored with the electron microscope. The kinetics of the ethylene-hydrogen reaction were examined by means of a pulse technique. The number of active sites determined by carbon monoxide titration of the surface was equal to the number of surface atoms as determined by the calculation of the quantities of compounds involved in the synthesis and electron microscope examination. Furthermore, the activity per site depended on the method of preparation, being four times smaller when sodium formate was used as a reducing agent instead of sodium citrate. This may be due to the fact that the shape of particles makes certain crystallographic planes more favorable. Decrease in the size of particles to 56 angstroms produced no effect on catalytic activity beyond that due to the increase in the number of surface atoms. The activity of commercial 5 percent palladium on alumina diluted 100-fold with alumina gave 80.4 percent conversion with propylene and 82.7 percent conversion with ethylene. Thus there was little difference in the behavior of the two olefins. 相似文献
20.
The most common catalyst in the Haber-Bosch process for the hydrogenation of dinitrogen (N(2)) to ammonia (NH(3)) is an iron surface promoted with potassium cations (K(+)), but soluble iron complexes have neither reduced the N-N bond of N(2) to nitride (N(3-)) nor produced large amounts of NH(3) from N(2). We report a molecular iron complex that reacts with N(2) and a potassium reductant to give a complex with two nitrides, which are bound to iron and potassium cations. The product has a Fe(3)N(2) core, implying that three iron atoms cooperate to break the N-N triple bond through a six-electron reduction. The nitride complex reacts with acid and with H(2) to give substantial yields of N(2)-derived ammonia. These reactions, although not yet catalytic, give structural and spectroscopic insight into N(2) cleavage and N-H bond-forming reactions of iron. 相似文献