噻吩在镍基非晶态合金上的吸附和脱附

应用静态吸附、动态吸附、程序升温脱附和程序升温还原等实验方法，考察了噻吩在Ni基非晶态合金上的吸附和脱附行为。常温下，噻吩分子首先吸附在清洁的Ni表面，并立刻被活化，发生氢解反应，C-S键断裂，释放出烃类部分，S留在Ni原子上。噻吩可以在Ni基非晶态合金表面发生强度不同的化学吸附。弱化学吸附的噻吩可以脱附；强化学吸附的噻吩不会脱附，而在高温下发生氢解反应。     

Gas-phase selective oxidation of toluene on TiO2–sepiolite supported vanadium oxides: Influence of vanadium loading on conversion and product selectivities

Gas-phase selective oxidation of toluene has been carried out on vanadium oxide systems (5–20 wt.% of V₂O₅, equivalent to 0.4–1.7 theoretical monolayers) supported on TiO₂–sepiolite (with titania loading around the theoretical monolayer, 12 wt.%) and on sepiolite. A study has been made on both the influence of vanadia loading and of the support on the catalytic behaviour of the supported vanadium systems. The reducibility by H₂ TPR was also studied as well as the acid and basic/redox sites from the results of conversion of the 2-propanol test reaction of the solids. Benzaldehyde, benzoic acid and several coupling products were the main ones detected, attaining over 50% selectivity towards the benzaldehyde and benzoic acid products at a total conversion around 10%. The activity and selectivity to the selective products exhibited by vanadium systems supported on mixed support were superior to those exhibited by the systems supported on sepiolite and increased notably in both series with the increase in vanadium loading. The best catalytic behaviour exhibited by the vanadium systems supported on mixed support, which also exhibited the highest density of sites capable of being reduced (as well as their reducibility) and of those responsible for propanone formation, could be attributed not only to the different balance of the vanadia species existing in the two supports (monomeric + oligomeric/polymeric), but also to such other factors as the nature of the support and, concretely, its chemical composition.     

Preparation of nickel-tungstate catalysts by a novel impregnation method

Nickel-tungstate/γ-alumina (NiW) catalysts were prepared by an incipient wetness impregnation method using citric acid as a complexing agent. Citric acid has been used by our research group in preparing cobalt-molybdate and nickel -molybdate catalysts. The extended X-ray absorption fine structure (EXAFS) data of the impregnating solutions indicated that citric acid contributes to the formation of polytungstate anions that are smaller than the dodecatungstate ions formed when conventional ammoniacal solutions are used. Sulfided NiW catalysts prepared by using citric acid showed higher hydrogenation activity and hydrogenation selectivity than NiW catalysts prepared using the conventional ammoniacal solutions.     

Catalytic Conversion of NO and C3H6 in Exhaust Gases Over Silver Catalysts Under Stoichiometric or Excess Oxygen

The role of Ag in simultaneously catalyzing NO reduction and C₃H₆ oxidation was shown to be strongly dependent on the redox properties of its local environment. Under an atmosphere of 1,000 ppm NO, 3,000 ppm C₃H₆, and 1% O₂ and a GHSV of 30,000 h⁻¹, a perovskite La_0.88Ag_0.12FeO₃ prepared by reactive grinding is active giving a complete NO conversion and 92% C₃H₆ conversion at 500 °C. These values are much higher than the NO conversion of 55% and C₃H₆ conversion of 45% obtained over a 3 wt.% Ag/Al₂O₃ catalyst under the same conditions. Under an excess of oxygen (10% O₂) a good SCR performance with a plateau of N₂ yield above 97% over a wide temperature window of 350–500 °C along with C₃H₆ conversion of 90% at 500 °C was observed over Ag/Al₂O₃, while minor N₂ yields (∼10% at 250–350 °C) and high C₃H₆ conversions (reaching ∼100% at 450 °C) were obtained over La_0.88Ag_0.12FeO₃. Abundant molecular oxygen is desorbed from Ag substituted perovskite after 10% O₂ adsorption as verified by O₂- temperature programmed desorption (TPD). This reflects the strongly oxidative properties of La_0.88Ag_0.12FeO₃, which lead to a satisfactory NO reduction at 1% O₂ due to the ease of nitrate formation but to a significant C₃H₆ combustion above that value. The formation of nitrate species over the less oxidizing Ag/Al₂O₃ was accelerated under an excess of oxygen resulting in an excellent lean NO reduction behavior. The redox properties of silver catalysts could be adjusted via mixing perovskite with alumina for an optimal elimination of both NO and C₃H₆ over the whole range of oxygen concentration between 0 to 10%.     

Sintering of Pt/Al2O3 reforming catalysts: EXAFS study of the behavior of metal particles under oxidizing atmosphere

The effect of an oxidative atmosphere (300 °C) is studied on fresh and sintered unchlorinated naphtha reforming catalysts containing 0.6–1% Pt. The TPR profiles show that only one species is formed using our experimental conditions, regardless of the mean crystallite size of the metal particles. The structural information supplied by EXAFS compared with cuboctahedral particle modeling, implies that such species is a surface platinum oxide, the structure of which is close to that of PtO₂, but largely distorted. This is true whether the catalyst is sintered or not.     

Reduction of NO2 stored in a commercial lean NO x trap at low temperatures

Isothermal storage of NO₂ and subsequent reduction with different reducing agents (H₂, CO or H₂ + CO) in a lean NO _x trap catalyst was tested by Temperature Programmed Desorption (TPD) and Temperature Programmed Reduction (TPR) experiments at temperatures representative of automotive “cold-start” conditions (<200 °C) using a commercial NO _x trap catalyst. Results from the TPR experiments revealed that no reduction of stored NO₂ to N₂ was observed at 100–180 °C, and at 200 °C 10% reduction only of NO₂ to N₂ was measured. A special affinity of H₂ to form NH₃ was observed during the reduction of stored NO₂. The formation of NH₃ increases with increasing amount of stored NO₂ and decreases with increasing storage temperature. Direct relation exists between the amount of adsorbed and/or stored NO₂ and the formation of H₂O and NH₃.     

Investigation of CH4 Reforming with CO2 on Meso-Porous Al2O3-Supported Ni Catalyst

Meso-porous Al₂O₃-supported Ni catalysts exhibited the highest activity, stability and excellent coke-resistance ability for CH₄ reforming with CO₂ among several oxide-supported Ni catalysts (meso-porous Al₂O₃ (Yas1-2, Yas3-8), -Al₂O₃, -Al₂O₃, SiO₂, MgO, La₂O₃, CeO₂ and ZrO₂). The properties of deposited carbons depended on the properties of the supports, and on the meso-porous Al₂O₃-supported Ni catalyst, only the intermediate carbon of the reforming reaction formed. XRD and H₂-TPR analysis found that mainly spinel NiAl₂O₄ formed in meso-porous Al₂O₃ and -Al₂O₃-supported catalysts, while only NiO was detected in -Al₂O₃, SiO₂, CeO₂, La₂O₃ and ZrO₂ supports. The strong interaction between Ni and meso-porous Al₂O₃ improved the dispersion of Ni, retarded its sintering and improved the activated adsorption of CO₂. The coking reaction via CH₄ temperature-programed decomposition indicated that meso-porous Al₂O₃-supported Ni catalysts were less active for carbon formation by CH₄ decomposition than Ni/-Al₂O₃ and Ni/-Al₂O₃.     

Characterization of bimetallic NaY-supported Pt-Pd catalyst by EXAFS,TEM and TPR

NaY-supported bimetallic Pt-Pd catalysts have been studied by TEM, TPR and EXAFS. Small, randomly mixed particles are formed in the zeolite cages. When the Pt content is increased, a Pt core structure appears and the dispersion increases. Particle diameters are about 1–2 nm for bimetallic samples.     

Gold supported on ceria and ceria–alumina promoted by molybdena for complete benzene oxidation

New gold–molybdena catalysts supported on ceria and ceria–alumina in reaction of complete benzene oxidation were studied. The catalysts were characterized by means of XRD, TPR, XPS and Raman spectroscopy. High and stable catalytic activity was established in the temperature region 200–240 °C. The presence of gold causes a modification in ceria structure leading to an increase of Ce³⁺ and oxygen vacancies formation. The loading of Al³⁺ increases additionally the oxygen vacancies, while a tendency of decrease of Ce³⁺ amount was observed. The presence of alumina results also in a larger share of active oxygen species proved by analysis of O 1s XPS spectra. The differences in the activities within the starting temperature range (150–180 °C) and in the region of 100% conversion (200–240 °C) could be explained by supposing that in the LT region the electron transfer between nanosized gold and ceria particles via oxygen vacancies has a crucial role. In the HT region the oxygen mobility, provoked by the defective structure of ceria due to the presence of Al³⁺, becomes of prevailing importance. It was also concluded that alumina prevents the gold and ceria agglomeration, which is the main factor to avoid deactivation under extreme reaction conditions.     

Comments on the characterisation of oxidation catalysts using TPR/TPO

Temperature programmed reduction (TPR) and oxidation (TPO) are used extensively in catalyst characterisation. In this paper, we examine the use of TPR/TPO cycles for the characterisation of a range of molybdates and single oxides. In particular we observe that the first cycle differs from that of subsequent analyses, even when the maximum temperature is limited to that used in the catalytic reaction. The effect is independent of heating rates and cooling atmospheres and has been demonstrated using different bed configurations. This observation has significance when these oxides are used in periodic flow reactors that involve many cyclical reduction/oxidation.