Characterization and Catalytic Properties of Combustion Synthesized Au/CeO2 Catalyst

Ceria-supported Au catalyst has been synthesized by the solution combustion method for the first time and characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM) and X-ray photoelectron spectroscopy (XPS). Au is dispersed as Au⁰ as well as Au³⁺ states on CeO₂ surface of 20-30 nm crystallites. On heating the as-prepared 1% Au/CeO₂ in air, the concentration of Au³⁺ ions on CeO₂ increases at the expense of Au⁰. Catalytic activities for CO and hydrocarbon oxidation and NO reduction over the as-prepared and the heat-treated 1% Au/CeO₂ have been carried out using a temperature-programmed reaction technique in a packed bed tubular reactor. The results are compared with nano-sized Au metal particles dispersed on -Al₂O₂ substrate prepared by the same method. All the reactions over heat-treated Au/CeO₂ occur at lower temperature in comparison with the as-prepared Au/CeO₂ and Au/Al₂O₂. The rate of NO + CO reaction over as-prepared and heat-treated 1% Au/CeO₂ are 28.3 and 54.0 mol g^-1 s^-1 at 250 and 300 °C respectively. Activation energy (E _a) values are 106 and 90 kJ mol^-1 for CO + O₂ reaction respectively over as-prepared and heat-treated 1% Au/CeO₂ respectively.     

Kinetics of the methanation of carbon dioxide over a supported Ni-La2O3 catalyst

The kinetics of the methanation of carbon dioxide was investigated using an alumina supported Ni-La₂O₂ catalyst in a differential and integral reactor. In the differential reactor the molar ratio of H₂ to CO₂ was varied from 0.6 to 30. In the integral reactor the rates were measured with up to 90% conversion. Both reactor tests were carried out at temperatures between 513 and 593 K. The experimental results were described by a Langmuir-Hinshelwood type equation. The kinetics can be explained by assuming equilibrium of dissociative carbon dioxide and hydrogen adsorption, and assuming hydrogenation of surface carbon as the rate determining step.     

IR study of the interaction of hydroxyl groups of silica gel with Cr species of Phillips' type catalysts

Spectroscopic evidence for the interaction of hydroxyl groups and chromium ions was obtained using a catalyst prepared from chromyl chloride. A new OH peak, observed at 3705 cm^–1 after pumping away CO gas, is attributed to the direct interaction of OH with the low-valent chromium. This peak shifts to 3590 cm^–1 on contact with O₂ at room temperature and it is assigned to a hydroxyl interacting with the oxidized chromium. New assignments are also proposed for IR bands of CO presorbed on the catalyst. The peak due to CO at 2188 cm^–1 decreases as the OH intensity at 3705 cm^–1 increases, suggesting that the former peak arises from adsorption on Cr(II) species to which two oxygen atoms are attached.     

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.     

Activation of a Au/TiO2 Catalyst by Loading a Large Amount of Fe–Oxide: Oxidation of CO Enhanced by H2 and H2O

Catalytic activity of a 1 wt% Au/TiO₂ catalyst is markedly improved by loading a large amount of FeO_x, on which the oxidation of CO in excess H₂ is selectively promoted at temperature lower than 60 °C. Oxidation of CO with O₂ on the FeO_x/Au/TiO₂ catalyst is markedly enhanced by H₂, and H₂O moisture also enhances the oxidation of CO but its effect is not so large as the promotion by H₂. We deduced that activation of Au/TiO₂ catalyst by loading FeO_x is not caused by the size effect of Au particles but a new reaction path via hydroxyl carbonyl intermediate is responsible for the superior activity of the FeO_x/Au/TiO₂ catalyst.     

Mg、Ce修饰纳米Al_2O_3负载Ni催化剂对CH_4、CO_2重整反应制合成气的影响

考察了助剂Mg、Ce修饰的纳米A l2O3负载N i催化剂对CH4、CO2重整反应制合成气的反应性能影响,采用正交实验筛选催化剂。结果表明,N i含量在9%~13%时,催化剂表现出较好的活性;随Mg含量的增加,反应活性基本呈下降趋势,说明Mg降低了催化剂体系的反应性能;Ce的加入总体上提高了反应活性,但是当Ce含量为3%时,反应活性最好;从不经预还原实验和低温点反应实验推断出,CH4和CO2重整反应中关键反应步骤是CH4的裂解;助剂Ce有利于提高催化剂的稳定性,而Mg却会使催化剂的稳定性下降很快。     

Effect of Pretreatment Atmosphere on CuO/TiO2 Activities in NO + CO Reaction

Using TiO₂ as carrier, CuO/TiO₂ catalysts with different CuO loading were prepared by the impregnation method. The catalytic activities in NO+CO reaction were examined with a micro-reactor gas chromatography reaction system and the methods of TPR, XPS and NO-TPD. It was found that the catalytic activities were affected by pretreatment atmosphere, i.e. H₂ atmosphere > reduction–reoxidation > 10%CO/He > reaction gas (fresh sample). NO decomposition was better by low-valence Cu species than by high-valence Cu species, i.e. Cu⁰>Cu⁺>Cu²⁺. The XPS results indicated that Cu species on CuO/TiO₂ were Cu⁰, Cu⁺, normal Cu²⁺(Cu²⁺(I)) and chain-structured Cu²⁺(Cu²⁺(II)) as –Cu–O–Ti–O–. The activities of Cu²⁺(II) were much higher than that of Cu²⁺(I), but both species were very unstable in the reaction atmosphere and easily reduced by CO, which accounted for the variable activities of fresh catalysts with increasing reaction temperature. In NO+CO reaction, the redox process was a cycle of Cu⁺–Cu²⁺(I) at low reaction temperature but was a cycle of Cu⁰–Cu⁺ at high reaction temperature. As shown by NO-TPD, high catalytic activities could be attributed to the following factors, e.g. oxygen caves on the catalyst’s surface after pretreatment with H₂ and reduction–reoxidation, formation of Cu⁰ after pretreatment with H₂, and increment of Cu species dispersion and formation of Cu²⁺(II) after pretreatment with reduction–reoxidation.     

Maximization of total surface area of Pt-SnO<Subscript>2</Subscript>/Al<Subscript>2</Subscript>O<Subscript>3</Subscript> catalyst by the Taguchi method

The maximization of the total surface area of Pt-SnO₂/Al₂O₃ catalyst was studied by using the Taguchi method of experimental design. The catalysts were prepared by sol-gel method. The effects of HNO₃, H₂O and aluminum nitrate concentrations and the stirring rate on the total surface area were studied at three levels of each. L₉ orthogonal array leading nine experiments was used in the experimental design. The parameter levels that give maximum total surface area were determined and experimentally verified. In the range of conditions studied it was found that, medium levels of HNO₃ and H₂O concentration and lower levels of aluminum nitrate concentration and stirring rate maximize the total surface area.     

基于中红外QCL的痕量CO气体传感器

为了减少CO爆炸给国民经济造成的巨大损伤,提出了一种能够快速地监测环境空气中痕量CO的气体传感器。由于CO分子基频吸收谱带的吸收线强要比泛频带和组合频带的吸收线强高出2～3个数量级,选择激射中心波长为4.65μm中红外量子级联激光器（QCL）作为光源,同时再配合长光程Herriott气室提高了CO体积分数检测下限。同时,该传感器采用单光源双探测器差分光学结构,消除了电调制光源所带来的不稳定性。实验表明：该传感器CO体积分数检测下限为2×10-6,并且操作人员可以通过替换在不同波长下运行的中红外QCL来测量其它气体。     

Preparation and catalytic performance of Co3O4 catalysts for low-temperature CO oxidation

Without use of any surfactant or oxidant, a series of Co₃O₄ catalysts have been prepared from cobalt nitrate aqueous solution via a very simple liquid-precipitation method with ammonium acid carbonate followed by calcination at various temperatures. The catalytic performance of the Co₃O₄ for CO oxidation has been studied with a continuous flowing laboratory microreactor system. The results show that the CO conversion of all the samples can reach 100% at ambient temperature. The catalyst calcined at 300 °C is able to maintain its activity for CO complete oxidation more than 500 min at 25 °C and about 240 min even at −78 °C. High reaction temperature results in a high catalytic stability, while the catalytic stability decreases with further increasing the reaction temperature. Characterizations with X-ray powder diffraction and transmission electron microscopy suggest that all the samples exist as a pure Co₃O₄ phase with the spinel structure, the samples are apt to aggregate and the specific surface area gradually decreases with increasing the calcination temperature, which directly leads to the decrease of catalytic stability. Furthermore, the amount of active oxygen species measured by CO titration experiments appears to be critical for catalytic performance.