Alkali-stabilized Pt-OHx species catalyze low-temperature water-gas shift reactions

We report that alkali ions (sodium or potassium) added in small amounts activate platinum adsorbed on alumina or silica for the low-temperature water-gas shift (WGS) reaction (H(2)O + CO → H(2) + CO(2)) used for producing H(2). The alkali ion-associated surface OH groups are activated by CO at low temperatures (~100°C) in the presence of atomically dispersed platinum. Both experimental evidence and density functional theory calculations suggest that a partially oxidized Pt-alkali-O(x)(OH)(y) species is the active site for the low-temperature Pt-catalyzed WGS reaction. These findings are useful for the design of highly active and stable WGS catalysts that contain only trace amounts of a precious metal without the need for a reducible oxide support such as ceria.     

(111)晶面暴露的NiO纳米催化剂的制备及其CO催化氧化性能

采用溶剂热法,以Ni(NO_3)_3·6H_2O、均苯三甲酸以及N,N-二甲基甲酰胺(DMF)为原料快速合成金属有机骨架材料Ni_3(BTC)_2·12H_2O晶体。以Ni_3(BTC)_2·12H_2O为前体,通过焙烧得到具有(111)面的NiO颗粒用于CO催化氧化反应,并与由硝酸镍热解得到的NiO(R)催化剂进行对比。通过X射线衍射(XRD)、N_2物理吸附-脱附、透射电子显微镜(TEM)以及X射线光电子能谱(XPS)等方法对具有(111)面的NiO颗粒的组成、结构和形貌进行表征。CO催化氧化结果表明,具有(111)面的NiO颗粒的催化活性优于普通NiO催化剂的催化活性。     

Spectroscopic observation of dual catalytic sites during oxidation of CO on a Au/TiO₂ catalyst

The prevailing view of CO oxidation on gold-titanium oxide (Au/TiO(2)) catalysts is that the reaction occurs on metal sites at the Au/TiO(2) interface. We observed dual catalytic sites at the perimeter of 3-nanometer Au particles supported on TiO(2) during CO oxidation. Infrared-kinetic measurements indicate that O-O bond scission is activated by the formation of a CO-O(2) complex at dual Ti-Au sites at the Au/TiO(2) interface. Density functional theory calculations, which provide the activation barriers for the formation and bond scission of the CO-O(2) complex, confirm this model as well as the measured apparent activation energy of 0.16 electron volt. The observation of sequential delivery and reaction of CO first from TiO(2) sites and then from Au sites indicates that catalytic activity occurs at the perimeter of Au nanoparticles.     

树脂负载Fe(Ⅲ)/Cu(Ⅱ)非均相光Fenton体系降解罗丹明B模拟废水研究

采用浸渍法制备负载有Fe(Ⅲ)/Cu(Ⅱ)、Fe(Ⅲ)和Cu(Ⅱ)的阳离子交换树脂(R)催化剂,在H_2O_2和节能灯照射条件下降解罗丹明B(Rh B)模拟印染废水。在H_2O_2浓度为20 mmol/L、曝气、30℃和光照条件下,0.05 g/L Fe(Ⅲ)/Cu(Ⅱ)/R催化剂在29 h内将20 mg/L的Rh B溶液降解完全,30 h后COD去除率为73.7%,且Fe(Ⅲ)/Cu(Ⅱ)/R催化剂具有最大的反应速率。Fe(Ⅲ)/Cu(Ⅱ)/R催化剂的稳定试验和重复试验表明,该催化剂在78 h光催化反应后,溶液中含有的Fe(Ⅲ)和Cu(Ⅱ)浓度分别为0.5和0.2 mg/L,且在连续使用6次后仍具有较高的催化效率。Fe(Ⅲ)/Cu(Ⅱ)/R催化剂对Rh B的较高催化性能主要归因于铁、铜离子间的协同作用及光照的共同作用。     

Reaction-driven restructuring of Rh-Pd and Pt-Pd core-shell nanoparticles

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.     

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.     

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.     

Carbon monoxide and nitric oxide consumption in polluted air: the carbon monoxide-hydroperoxyl reaction

A recent laboratory measurement of the ratio of the rate constant for the reaction CO + HO (2) --> C0(2) + OH relative to that for H + HO(2) --> 2OH indicates that the former reaction is probably faster than CO + OH --> CO(2) + H. On this basis a simple analysis is given showing that the calculated lifetime of nitric oxide in polluted atmospheres would be appreciably longer than that estimated on the assumption that the carbon monoxide-hydroperoxyl reaction may be neglected. A fast carbon monoxide-hydroperoxyl reaction implies that the cyclic consumption of carbon monoxide (an atmospheric sink) could occur even with no nitric oxide present.     

The hydroperoxyl radical in atmospheric chemical dynamics: reaction with carbon monoxide

From measurements of the photochemical rate of production of CO(2)(16,18) and CO(2)(16,16), produced from the low intensity photolysis of mixtures of CO, H(2)O, Ar, and O(2)(18,18), the rate constant for the reaction HO(2) + CO --> CO(2) + OH has been determined at 300 degrees K to be less than or equal to 10(-20) cubic centimeter per molecule per second. These measurements indicate that the reaction of thermalized HO(2) is of negligible importance as a sink mechanism for converting CO to CO(2) in either the troposphere or the stratosphere.     

制备邻苯基苯酚的Cu-MgO催化剂失活研究

[目的]探讨引起Cu-MgO催化剂失活的微观因素。[方法]采用共沉淀法制备Cu-MgO催化剂,并采用XRD、BET、NH3-TPD、CO2-TPD、H2-TPD、失重等手段对失活前后的Cu-MgO催化剂进行了表征。[结果]Cu-MgO催化剂对环己烯基环己酮脱氢制备邻苯基苯酚(OPP)有较高的活性,双聚的初始转化率达到99%以上,OPP的选择性达到95%以上,但其催化性能随运转时间的延长呈逐渐下降趋势。表征结果显示,在反应条件下催化剂上Cu原子和MgO随运转时间的延长明显聚集长大,导致Cu与MgO之间作用力减弱,氢吸附能力和碱量降低;催化剂表面积炭,改变了催化剂比表面积和孔结构,从而使催化剂活性和选择性下降。[结论]为抑制催化剂失活的研究奠定了基础。     

A New High-Temperature Superconductor: Bi2Sr3-x Cax Cu2O8+y

A new superconductor that displays onset behavior near 120 K has been identified as Bi(2)Sr(3-x)Ca(x)Cu(2)O(8+y), with x ranging from about 0.4 to 0.9. Single crystal x-ray diffraction data were used to determine a pseudo-tetragonal structure based on an A-centered orthorhombic subcell with a = 5.399 A, b= 5.414A, and c = 30.904 A. The structure contains copper-oxygen sheets as in La(2)CuO(4) and YBa(2)Cu(3)O(7), but the copper-oxygen chains present in YBa(2)Cu(3)O(7) do not occur in Bi(2)Sr(3-x)Ca(x)Cu(2)O(8+y). The structure is made up of alternating double copper-oxygen sheets and double bismuth-oxygen sheets. There are Ca(2+) and Sr(2+) cations between the adjacent Cu-O sheets; Sr(2+) cations are also found between the Cu-O and Bi-O sheets. Electron microscopy studies show an incommensurate superstructure along the a axis that can be approximated by an increase of a factor of 5 over the subcell dimension. This superstructure is also observed by x-ray diffraction on single crystals, but twinning can make it appear that the superstructure is along both a and b axes. Flux exclusion begins in our samples at about 116 K and is very strong by 95 K. Electrical measurements on a single crystal of Bi(2)Sr(3-x)Ca(x)Cu(2)O(8+y) show a resistivity drop at about 116 K and apparent zero resistivity at 91 K.     

Stabilization of platinum oxygen-reduction electrocatalysts using gold clusters

We demonstrated that platinum (Pt) oxygen-reduction fuel-cell electrocatalysts can be stabilized against dissolution under potential cycling regimes (a continuing problem in vehicle applications) by modifying Pt nanoparticles with gold (Au) clusters. This behavior was observed under the oxidizing conditions of the O2 reduction reaction and potential cycling between 0.6 and 1.1 volts in over 30,000 cycles. There were insignificant changes in the activity and surface area of Au-modified Pt over the course of cycling, in contrast to sizable losses observed with the pure Pt catalyst under the same conditions. In situ x-ray absorption near-edge spectroscopy and voltammetry data suggest that the Au clusters confer stability by raising the Pt oxidation potential.     

Active nonmetallic Au and Pt species on ceria-based water-gas shift catalysts

Traditional analysis of reactions catalyzed by supported metals involves the structure of the metallic particles. However, we report here that for the class of nanostructured gold- or platinum-cerium oxide catalysts, which are active for the water-gas shift reaction, metal nanoparticles do not participate in the reaction. Nonmetallic gold or platinum species strongly associated with surface cerium-oxygen groups are responsible for the activity.     

Possible Evidence for Superconducting Layers in Single Crystal YBa2Cu3O7-x by Field Ion Microscopy

The high-transition-temperature superconducting ceramic material YBa(2)Cu(3)O(7-x) (0< x < 0.5) has been examined by field ion microscopy. Specimens from nominally superconducting and nonsuperconducting samples(determined by magnetic susceptibility measurements) were studied by field ion microscopy and significant differences were found. Preferential imaging of atomic or molecular layers, due to preferential field evaporation, field ionization, or both, was found in the superconducting phase below the transition temperature and is interpreted as possible evidence for the occurrence of relatively highly conducting layers in the YBa(2)Cu(3)O(7-x) unit cell perpendicular to the orthorhombic c-axis. Similar results were obtained for YbBa(2)Cu(3)(7-x).     

Imaging phonon excitation with atomic resolution

Inelastic electron tunneling spectroscopy at low temperatures was used to investigate vibrations of Au(111) and Cu(111). The low-energy peaks at 9 millielectron volts (meV) on Au(111) and 21 meV on Cu(111) are attributed to phonons at surfaces. On Au(111), the phonon energy is not influenced by the different stacking of the surface atoms, but it is considerably influenced by different atomic distances within the surface layer. The spatial variation of the phonon excitation is measured in inelastic electron tunneling maps on Au(111), which display atomic resolution. This atomic resolution is explained in terms of site-specific phonon excitation probabilities.     

Mass-independent oxygen isotope fractionation in atmospheric CO as a result of the reaction CO + OH

Atmospheric carbon monoxide (CO) exhibits mass-independent fractionation in the oxygen isotopes. An 17O excess up to 7.5 per mil was observed in summer at high northern latitudes. The major source of this puzzling fractionation in this important trace gas is its dominant atmospheric removal reaction, CO + OH --> CO2 + H, in which the surviving CO gains excess 17O. The occurrence of mass-independent fractionation in the reaction of CO with OH raises fundamental questions about kinetic processes. At the same time the effect is a useful marker for the degree to which CO in the atmosphere has been reacting with OH.     

Synthesis of ammonium cyanate and urea by reduction of nitric oxide on platinum, rhodium, and ruthenium catalysts

Nearly quantitative conversion of nitric oxide (NO) into N(2)H(4)CO has been obtained in the reduction of NO with carbon monoxide and hydrogen over platinum and rhodium catalysts. Depending on the temperature of collection, N(2)H(4)CO is isolated as ammonium cyanate or its isomer, urea. The process is an effective way of recovering fixed nitrogen from dilute industrial streams containing NO. Ammonium cyanate may play a role in the reduction of NO in automotive exhaust control.     

Charging effects on bonding and catalyzed oxidation of CO on Au8 clusters on MgO

Gold octamers (Au8) bound to oxygen-vacancy F-center defects on Mg(001) are the smallest clusters to catalyze the low-temperature oxidation of CO to CO2, whereas clusters deposited on close-to-perfect magnesia surfaces remain chemically inert. Charging of the supported clusters plays a key role in promoting their chemical activity. Infrared measurements of the stretch vibration of CO adsorbed on mass-selected gold octamers soft-landed on MgO(001) with coadsorbed O2 show a red shift on an F-center-rich surface with respect to the perfect surface. The experiments agree with quantum ab initio calculations that predict that a red shift of the C-O vibration should arise via electron back-donation to the CO antibonding orbital.     

Reactivity of the gold/water interface during selective oxidation catalysis

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.