共查询到20条相似文献，搜索用时 375 毫秒
1.
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
2.
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. 相似文献
3.
Rare-earth manganites such as La(1-x) Pb(x)MnO(3), with 0.3 x 0.6, and their perovskite-like homologs are active catalysts for the reduction of nitric oxide to molecular nitrogen. At low temperatures, innocuous nitrous oxide rather than anmmonia is the main side product. The activity of single crystalline catalysts and of ceramic catalysts of this type is substantially improved by etching with dilute acids. 相似文献
4.
The high performance of Au-CeO2 and Au-TiO2 catalysts in the water-gas shift (WGS) reaction (H2O + CO-->H2 + CO2) relies heavily on the direct participation of the oxide in the catalytic process. Although clean Au(111) is not catalytically active for the WGS, gold surfaces that are 20 to 30% covered by ceria or titania nanoparticles have activities comparable to those of good WGS catalysts such as Cu(111) or Cu(100). In TiO(2-x)/Au(111) and CeO(2-x)/Au(111), water dissociates on O vacancies of the oxide nanoparticles, CO adsorbs on Au sites located nearby, and subsequent reaction steps take place at the metal-oxide interface. In these inverse catalysts, the moderate chemical activity of bulk gold is coupled to that of a more reactive oxide. 相似文献
5.
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. 相似文献
6.
Mechanism of the selective catalytic reduction of nitric oxide by ammonia elucidated by in situ on-line fourier transform infrared spectroscopy 总被引：1，自引：0，他引：1
Topsøe NY 《Science (New York, N.Y.)》1994,265(5176):1217-1219
The selective catalytic reduction reaction of nitric oxide bv ammonia over vanadia-titania catalysts is one of the methods of removing NOx pollution. In the present study, it has been possible to identify the reaction mechanism and the nature of the active sites in these catalysts by combining transient or steady-state in situ (Fourier transform infrared spectroscopy) experiments directly with on-line activity studies. The results suggest a catalytic cycle that consists of both acid and redox reactions and involves both surface V-OH (Br?nsted acid sites) and V=O species. A fundamental microkinetic model is proposed, which accounts for the observed industrial kinetics performance. 相似文献
7.
Stamenkovic VR Fowler B Mun BS Wang G Ross PN Lucas CA Marković NM 《Science (New York, N.Y.)》2007,315(5811):493-497
The slow rate of the oxygen reduction reaction (ORR) in the polymer electrolyte membrane fuel cell (PEMFC) is the main limitation for automotive applications. We demonstrated that the Pt3Ni(111) surface is 10-fold more active for the ORR than the corresponding Pt(111) surface and 90-fold more active than the current state-of-the-art Pt/C catalysts for PEMFC. The Pt3Ni(111) surface has an unusual electronic structure (d-band center position) and arrangement of surface atoms in the near-surface region. Under operating conditions relevant to fuel cells, its near-surface layer exhibits a highly structured compositional oscillation in the outermost and third layers, which are Pt-rich, and in the second atomic layer, which is Ni-rich. The weak interaction between the Pt surface atoms and nonreactive oxygenated species increases the number of active sites for O2 adsorption. 相似文献
8.
以Ni、Fe、Co等3种不同金属掺杂的TiO2介孔材料作催化剂对中药渣进行催化裂解,研究不同催化剂对生物油产率及油品的影响,采用热值分析和气质联用(GC-MS)分析裂解油的特性,利用N2吸附-脱附对催化剂进行表征。研究表明,Ni/TiO2的催化效果优于Fe/TiO2和Co/TiO2,Ni/TiO2作催化剂时,裂解油中脂肪烃和烷基苯的种数最多,且其中与汽油或柴油相近的组分占大多数,而芳香族化合物数量明显较少。在Ni/TiO2的催化作用下,大分子中的氧多以H2O分子的形式脱去,因而生物油中含水率较高,导致其热值降低。 相似文献
9.
Nolte P Stierle A Jin-Phillipp NY Kasper N Schulli TU Dosch H 《Science (New York, N.Y.)》2008,321(5896):1654-1658
The microscopic insight into how and why catalytically active nanoparticles change their shape during oxidation and reduction reactions is a pivotal challenge in the fundamental understanding of heterogeneous catalysis. We report an oxygen-induced shape transformation of rhodium nanoparticles on magnesium oxide (001) substrates that is lifted upon carbon monoxide exposure at 600 kelvin. A Wulff analysis of high-resolution in situ x-ray diffraction, combined with transmission electron microscopy, shows that this phenomenon is driven by the formation of a oxygen-rhodium-oxygen surface oxide at the rhodium nanofacets. This experimental access into the behavior of such nanoparticles during a catalytic cycle is useful for the development of improved heterogeneous catalysts. 相似文献
10.
Hino T Matsumoto Y Nagano S Sugimoto H Fukumori Y Murata T Iwata S Shiro Y 《Science (New York, N.Y.)》2010,330(6011):1666-1670
Nitric oxide reductase (NOR) is an iron-containing enzyme that catalyzes the reduction of nitric oxide (NO) to generate a major greenhouse gas, nitrous oxide (N(2)O). Here, we report the crystal structure of NOR from Pseudomonas aeruginosa at 2.7 angstrom resolution. The structure reveals details of the catalytic binuclear center. The non-heme iron (Fe(B)) is coordinated by three His and one Glu ligands, but a His-Tyr covalent linkage common in cytochrome oxidases (COX) is absent. This structural characteristic is crucial for NOR reaction. Although the overall structure of NOR is closely related to COX, neither the D- nor K-proton pathway, which connect the COX active center to the intracellular space, was observed. Protons required for the NOR reaction are probably provided from the extracellular side. 相似文献
11.
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。 相似文献
12.
Winther-Jensen B Winther-Jensen O Forsyth M Macfarlane DR 《Science (New York, N.Y.)》2008,321(5889):671-674
The air electrode, which reduces oxygen (O2), is a critical component in energy generation and storage applications such as fuel cells and metal/air batteries. The highest current densities are achieved with platinum (Pt), but in addition to its cost and scarcity, Pt particles in composite electrodes tend to be inactivated by contact with carbon monoxide (CO) or by agglomeration. We describe an air electrode based on a porous material coated with poly(3,4-ethylenedioxythiophene) (PEDOT), which acts as an O2 reduction catalyst. Continuous operation for 1500 hours was demonstrated without material degradation or deterioration in performance. O2 conversion rates were comparable with those of Pt-catalyzed electrodes of the same geometry, and the electrode was not sensitive to CO. Operation was demonstrated as an air electrode and as a dissolved O2 electrode in aqueous solution. 相似文献
13.
Quantification of the influence of surface structure on C--h bond activation by iridium and platinum
The trapping-mediated dissociative chemisorption of ethane on the closest packed Ir(111) surface has been investigated, and the activation energy and preexponential factor of the surface reaction rate coefficient have been measured. These results are compared to those of ethane activation on Pt(111) and on the missing row reconstructed Ir(110)-(1x2) and Pt(110)-(1x2) surfaces, allowing a quantitative determination of the effect surface structure has on the catalytic activation of C-H bonds. In the order Pt(111), Pt(110)-(1x2), Ir(111), and Ir(110)-(1x2), the activation energies for the dissociative chemisorption of ethane are 16.6, 10.5, 10.3, and 5.5 kilocalories per mole, demonstrating that the electronic and geometric effects are of approximately equal importance for ethane activation on these catalysts. 相似文献
14.
The prohibitive cost of platinum for catalyzing the cathodic oxygen reduction reaction (ORR) has hampered the widespread use of polymer electrolyte fuel cells. We describe a family of non-precious metal catalysts that approach the performance of platinum-based systems at a cost sustainable for high-power fuel cell applications, possibly including automotive power. The approach uses polyaniline as a precursor to a carbon-nitrogen template for high-temperature synthesis of catalysts incorporating iron and cobalt. The most active materials in the group catalyze the ORR at potentials within ~60 millivolts of that delivered by state-of-the-art carbon-supported platinum, combining their high activity with remarkable performance stability for non-precious metal catalysts (700 hours at a fuel cell voltage of 0.4 volts) as well as excellent four-electron selectivity (hydrogen peroxide yield <1.0%). 相似文献
15.
A novel and convenient synthesis of isocyanic acid (HNCO) and its trimer isocyanuric acid has been obtained by the conversion of nitric oxide (NO). Nitric oxide, carbon monoxide, and hydrogen mixed in helium at the level of 0.3 to 5 percent reacted over iridium and palladium catalysts at 280 degrees to 450 degrees C to form HNCO in 60 to 75 percent yield. Major side products were ammonium cyanate at low temperature and ammonia or nitrogen at high temperature. Total conversion of nitrogen from NO to NCO reached 73 percent over palladium and 86 percent over iridium. 相似文献
16.
丹参对溃疡性结肠炎患者外周血中性粒细胞的凋亡、O-2和NO产生的调节作用 总被引：4，自引：0，他引：4
目的:观察丹参(SM)对溃疡性结肠炎患者外周血中性粒细胞(PM N)凋亡及超氧阴离子(O2-)和一氧化氮(NO)产生的影响。方法:选择中度活动期溃疡性结肠炎(UC)患者15例(UC组)和健康体检者18例(对照组),采用人外周血PM N体外培养细胞模型进行实验研究,采用流式细胞术检测PM N凋亡,以细胞色素C还原法、化学比色法分别检测PM N产生O2-和NO的量。结果:UC组外周血PM N凋亡率明显低于对照组(P<0.01),产生O2-和NO的量高于对照组(P<0.01)。在体外丹参明显促进UC患者PM N凋亡(P<0.01),在500 m g/L内呈剂量依赖性;同时丹参可抑制UC患者PM N释放O2-、合成NO。结论:SM对体外PM N的凋亡及其产生O2-和NO有调节作用。 相似文献
17.
The formation of hydrogen cyanide during the catalytic reduction of nitric oxide (NO) with carbon monoxide and hydrogen was studied with a bench-scale flow reactor. The previously reported inhibition by sulfur dioxide of the formation of hydrogen cyanide was found to be counteracted by transient admission of oxygen to the catalyst. These results are discussed in the context of the control of automotive emissions of NO and the prevention of hydrogen cyanide production during such control. 相似文献
18.
Zhai Y Pierre D Si R Deng W Ferrin P Nilekar AU Peng G Herron JA Bell DC Saltsburg H Mavrikakis M Flytzani-Stephanopoulos M 《Science (New York, N.Y.)》2010,329(5999):1633-1636
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. 相似文献
19.
Hydrogen rich gas was produced using rice husk as biomass material on the continuous biomass pyrolysis apparatus which consisted of continuous pyrolysis reactor and secondary catalytic cracking reactor. Ni based catalysts of different Ni/Al mass ratio and calcined temperature were prepared by impregnating method. The catalysts were characterized by X-ray diffraction (XRD), scan electron microscope (SEM) and FT-IR Spectrometer (FT-IR). Ni based catalyst showed good selectivity for H2 production from biomass. Catalysts prepared under different conditions had little influence on the yields of three states products when used at the same cracking temperature. Ni/Al mass ratio played an important role in products selectivity. However, the content of NiO increased further when Ni/Al mass ratio values reached 0.7 : 10, and the yield of H2 slightly increased. Hydrogen yield was greatly impacted by calcined temperature. Catalyst calcined at 550℃ performed best. When the catalyst was calcined at high temperature, NiO in the catalyst transformed into NiAl2O4, and the acid site also changed, which caused the deactivation of the catalyst. The hydrogen yield increased with the cracking temperature. The highest stable yield of hydrogen was about 30% without increasing with the cracking temperature. 相似文献
20.
Unland ML 《Science (New York, N.Y.)》1973,179(4073):567-569
Isocyanate species have been detected on the surface of noble metal catalysts during the reactions of carbon monoxide with nitric oxide. The intensity of the surface isocyanate infrared band correlates with the known ammonia-forming tendencies among the noble metals. The discovery of this isocyanate species suggests a new mechanistic pathway to the ammonia formed during catalytic reduction of nitrogen oxides in automobile exhaust. 相似文献