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  • Chemistry  (10)
  • oxygen  (4)
  • Ammonia synthesis  (3)
  • MgO  (2)
  • 1
    Electronic Resource
    Electronic Resource
    Springer
    Catalysis letters 11 (1991), S. 253-265 
    ISSN: 1572-879X
    Keywords: Silver ; oxygen ; selective oxidation ; thermal desorption ; subsurface compounds
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Polycrystalline Ag treated with O2 at pressures up to 1 bar and at temperatures up to 920 K was examined by TDS. It was found that the peak commonly observed at 595±25 K and assigned to adsorbed atomic oxygen (Oa) is shifted to higher desorption temperatures with rising dosing temperatures. Since saturation of the uptake was not possible either, this peak was identified as dissolved atomic oxygen (Od). The existence of a maximum for the O2 uptake after exposure at 820 K was found. Hence, under conditions of formaldehyde synthesis (≈ 920 K) the ability of the catalyst to dissolve oxygen is near its maximum.
    Type of Medium: Electronic Resource
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  • 2
    ISSN: 1572-879X
    Keywords: Ammonia synthesis ; Ru-zeolite ; metal clusters ; conversion measurements
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Na-Y zeolite was cation exchanged with Ru(NH3)6Cl3 yielding at 25% exchange level a light-purple solid which was active in ammonia synthesis at atmospheric pressure. Pulse conversion experiments show that the catalyst stores nitrogen as it was observed with the conventional iron catalyst. At 810 K the conversion reached about 20% of the maximum conversion of the iron catalyst. The catalyst deactivated reversibly within 30 h due to agglomeration. The active species in the catalyst is most likely a cluster-like Ru metal particle prevented from sintering under the reducing conditions of catalysis by the zeolite framework.
    Type of Medium: Electronic Resource
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  • 3
    Electronic Resource
    Electronic Resource
    Springer
    Catalysis letters 22 (1993), S. 215-225 
    ISSN: 1572-879X
    Keywords: Ion-scattering spectroscopy (ISS) ; methanol oxidation ; oxygen ; Raman spectroscopy ; reflection electron microscopy (REM) ; silver ; X-ray photoelectron spectroscopy (XPS)
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Under the applied high reaction temperatures (∼900 K) the Ag surface is restructured and a tightly held oxygen species is formed on the surface (Oγ) apart from O atoms dissolved in the bulk (Oβ). Methanol oxidation to formaldehyde proceeds through this Oγ species as demonstrated by application of a variety of spectroscopic techniques.
    Type of Medium: Electronic Resource
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  • 4
    ISSN: 1572-879X
    Keywords: oxygen ; partial oxidation ; reconstruction ; reflection electron microscopy ; Raman spectroscopy ; silver ; water
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Interaction of water with an oxygenated Ag(111) surface leads to an enhancement of the surface restructuring and an activated formation of hydroxyl groups (OH) located stably on the surface and incorporated in the subsurface region, as evidenced by means of reflection electron microscopy (REM) and in situ Raman spectroscopy. Dehydroxylation of OHads at elevated temperatures releases the strongly bound oxygen species labelled Oγ at the surface, and offers an alternative to the energetically less favorable pathway for the direct formation of the Oγ species from molecular oxygen.
    Type of Medium: Electronic Resource
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  • 5
    Electronic Resource
    Electronic Resource
    Springer
    Topics in catalysis 14 (2000), S. 95-100 
    ISSN: 1572-9028
    Keywords: ruthenium ; ruthenium dioxide ; oxide ; CO oxidation ; oxygen ; chemisorption
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract CO oxidation over ruthenium dioxide (RuO2) dominates the CO/CO2 conversion rate over the catalytically active oxygen-rich Ru(0001) surfaces. In sharp contrast, chemisorbed O overlayers on Ru(0001) (with and without dissolved oxygen) are virtually inactive with respect to CO oxidation.
    Type of Medium: Electronic Resource
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  • 6
    ISSN: 1572-879X
    Keywords: N2 TPD ; N2 adsorption ; Ru ; MgO ; NH3 synthesis ; microkinetic analysis
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The temperature-programmed desorption (TPD) of N2 from a Ru/MgO catalyst used for ammonia synthesis was studied in a microreactor flow system operating at atmospheric pressure. Saturation with chemisorbed atomic nitrogen (N-*) was achieved by exposure to N2 at 573 K for 14 h and subsequent cooling in N2 to room temperature. With a heating rate of 5 K/min in He, a narrow and fairly symmetric N2 TPD peak at about 640 K results. From experiments with varying heating rates a preexponential factor Ades = 1.5×1010 molecules/(site s) and an activation energy Edes = 158 kJ/mol was derived assuming secondorder desorption. This rate constant of desorption is in good agreement with results obtained with a Ru(0001) single crystal surface in ultra-high vacuum (UHV). The rate of dissociative chemisorption was determined by varying the N2 exposure conditions. Determination of the coverage of N-* was based on the integration of the subsequently recorded N2 TPD traces yielding Aads = 2×10−6 (Pa s)−1 and Eads = 27 kJ/mol. The corresponding sticking coefficient of about 10−14 at 300 K is in agreement with the inertness of Ru(0001) in UHV towards dissociative chemisorption of N2. However, if the whole catalytic surface were in this state, then the resulting rate of N2 dissociation would be several orders of magnitude lower than the observed rate of NH3 formation. Hence only a small fraction of the total Rumetal surface area of Ru/MgO seems to be highly active dominating the rate of ammonia formation.
    Type of Medium: Electronic Resource
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  • 7
    ISSN: 1572-879X
    Keywords: Ammonia synthesis ; iron catalyst ; surface characterization ; promoter effects ; nitrides ; ion scattering spectroscopy ; XPS ; HRTEM
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Industrial doubly-promoted iron catalysts and model systems of singly-promoted K- and Al-iron catalysts were characterised by their catalytic performance at 1 bar pressure. The relevance of bulk nitrogen for catalytic performance is shown. The catalysts were also activated in an in-situ reaction chamber of a He-ion scattering spectrometer (ISS) and their top atomic layer elemental composition was determined after they had reached similar performance as in the microreactor tests. The bulk microstructure of these samples was investigated by high resolution transmission electron microscopy (TEM) and microdiffraction. All evidence indicates that small highly crystalline α-Fe platelets act as active phase. Their surfaces are covered to a large extent by promotor compounds which are partly present as poorly crystalline aggregates with iron oxide leaving only a small fraction of elemental iron directly exposed to the gas phase. The intimate contact between iron crystals and promoters particles prevents recrystallisation and is the key to the understanding of the structural stability of the catalyst system.
    Type of Medium: Electronic Resource
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  • 8
    ISSN: 1572-879X
    Keywords: Ammonia synthesis ; supported ruthenium catalyst ; dispersed ruthenium ; instationary kinetics ; lifetime effects ; ruthenium oxidation ; surface analysis ; XPS
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Reaction of Ru(NH3)6Cl3 with Na-A and K-A zeolites yielded oligomeric amino-oxo-complexes supported on the zeolite. Controlled thermal activation under hydrogen converted the precursor in a two-step reaction into an active catalyst with good long-term stability and resistance against small doses of oxygen poison. Several nanometers sized Ru metal particles are chemically bonded to the zeolite surface which provides in the K form an alkali promoter at the metal-zeolite interface. Extensive oxidation breaks the metal-support anchoring and re-reduction produces Ru metal particles sintering rapidly into large metal crystals with only small residual catalytic activity.
    Type of Medium: Electronic Resource
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  • 9
    Electronic Resource
    Electronic Resource
    Springer
    Catalysis letters 53 (1998), S. 77-81 
    ISSN: 1572-879X
    Keywords: SCR of NO ; Ru ; MgO ; frontal chromatography ; TPD ; TPSR
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Ruthenium supported on magnesia was found to be a highly active and selective catalyst for the reduction of NO to N2 with H2. The adsorption of NO on Ru/MgO was studied at room temperature by applying frontal chromatography with a mixture of 2610 ppm NO in He. Subsequently, temperature‐programmed desorption (TPD) and temperature‐programmed surface reaction (TPSR) experiments in H2 were performed. The adsorption of NO was observed to occur partly dissociatively as indicated by the formation of molecular nitrogen. The TPD spectrum exhibited a minor NO peak at 340 K indicating additional molecular adsorption of NO during the exposure to NO at room temperature, and two N2 peaks at 480 K and 625 K, respectively. The latter data are in good agreement with previous results with Ru(0001) single‐crystal samples, where the interaction with NH3 was found to lead to two N2 thermal desorption states with a maximum coverage of atomic nitrogen of about 0.38. Heating up the catalyst after saturation with NO at room temperature in a H2 atmosphere revealed the self‐accelerated formation of NH3 after partial desorption of N2, whereby sites for reaction with H2 become available. As a consequence, the observed high selectivity towards N2 under steady‐state reduction conditions is ascribed to the presence of a saturated N+O coadsorbate layer resulting in an enhanced rate of N2 desorption from this layer and a very low steady‐state coverage of atomic hydrogen. The formation of H2O by reduction of adsorbed atomic oxygen is the slow step of the overall reaction which determines the minimum temperature required for full conversion of NO.
    Type of Medium: Electronic Resource
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  • 10
    Electronic Resource
    Electronic Resource
    Hoboken, NJ : Wiley-Blackwell
    AIChE Journal 39 (1993), S. 89-98 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: The occurrence of instabilities in chemically reacting systems, resulting in unsteady and spatially inhomogeneous reaction rates, is a widespread phenomenon. In this article, we use nonlinear signal processing techniques to extract a simple, but accurate, dynamic model from experimental data of a system with spatiotemporal variations. The approach consists of a combination of two steps. The proper orthogonal decomposition [POD or Karhunen-Loève (KL) expansion] allows us to determine active degrees of freedom (important spatial structures) of the system. Projection onto these “modes” reduces the data to a small number of time series. Processing these time series through an artificial neural network (ANN) results in a low-dimensional, nonlinear dynamic model with almost quantitative predictive capabilities.This approach is demonstrated using spatiotemporal data from CO oxidation on a Pt (110) crystal surface. In this special case, the dynamics of the two-dimensional reaction profile can be successfully described by four modes; the ANN-based model not only correctly predicts the spatiotemporal short-term behavior, but also accurately captures the long-term dynamics (the attractor). While this approach does not substitute for fundamental modeling, it provides a systematic framework for processing experimental data from a wide variety of spatiotemporally varying reaction engineering processes.
    Additional Material: 11 Ill.
    Type of Medium: Electronic Resource
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