Characterization and Catalytic Oxidation of Carbon Monoxide Over Supported Cobalt Catalysts

Three types of supported cobalt catalysts (CoO_x/SiO₂, CoO_x/TiO₂ and CoO_x/Al₂O₃) were prepared by incipient wetness impregnation with aqueous Co(NO₃)₂·6H₂O solution. The phase composition and the interactions of cobalt with supports under different calcined temperatures were investigated using thermogravimetry (TG), N₂-adsorption at −196 °C, X-ray diffraction (XRD), temperature-programmed reduction (TPR) and diffuse reflectance spectroscopy (DRS). Their catalytic activities towards the CO oxidation were further studied in a continuous flow micro-reactor. The results showed that the interaction of cobalt oxide with supports was much stronger in the kinds of Al₂O₃ and TiO₂, while no conclusive evidence of any interaction was found for SiO₂. Besides the crystalline Co₃O₄ which was formed in three supported catalysts, both high-temperature phases CoAl₂O₄ and CoTiO₃ spinel were also detected under XRD, DRS and TPR analysis. The degree of interaction between cobalt oxide and the support not only affected the surface area and reduction behavior of the catalysts, the catalytic activity toward the CO oxidation also affected simultaneously. As the CoAl₂O₄ and CoTiO₃ spinel formed, both the surface area and catalytic activity decreased significantly.     

SiO2负载氧化钴催化对二甲苯氧化制对甲苯甲酸的研究

报道了经高温焙烧的SiO2负载氧化钴催化剂,常压液相催化分子氧氧化对二甲苯,表现出了较好的催化活性和稳定性.经350 ℃焙烧的含钴量0.12 mmol·g-1的Co-O/SiO2,120 ℃催化氧化对二甲苯5.5 h,转化率47.4 %,对甲基苯甲酸的收率39.8 %.催化剂重复使用4次活性基本不变,并进行了IR、XRD表征.     

In-Situ Reduction of Promoted Cobalt Oxide Supported on Alumina by Environmental Transmission Electron Microscopy

Abstract  

Reduction of 12wt.%Co/0.5wt.%Re/α-Al₂O₃ Fischer–Tropsch catalyst has been studied in-situ in an environmental transmission electron microscope. Reduction of Co₃O₄ to metallic cobalt was observed dynamically at 360 °C under 3.4 mbar H₂. Structural and morphological changes were observed by high resolution transmission electron microscopy and scanning transmission electron microscopy imaging. The cobalt particles were mainly face centred cubic while some hexagonal close packed particles were also found. Reoxidation of the sample upon cooling to room temperature, still under flowing H₂, underlines the reactivity of the nanoparticles and the importance of controlling the gas composition and specimen temperature during this type of experiment. Similar behaviour was observed for a non-promoted catalyst. Imaging and analysis of the promoted sample before and after reduction indicated a uniform distribution of the promoter.     

In situ FT-IR Spectroscopic Studies on the Mechanism of the Catalytic Oxidation of Carbon Monoxide over Supported Cobalt Catalysts

Three types of supported cobalt catalysts (5% as metal Co loading on SiO₂, Al₂O₃ and TiO₂) were prepared by incipient wetness impregnation with aqueous Co(NO₃)₂·6H₂O solution. Then, all catalysts were calcined in air at 400 °C (assigned as 5Co/Si C400, 5Co/Al C400 and 5Co/Ti C400). Their catalytic activities towards the CO oxidation were studied in a continuous flow micro-reactor. Adsorption of carbon monoxide (CO) and the co-adsorption of CO/O₂ over cobalt oxide were further tested under in situ FT-IR. The results showed that both 5Co/Si C400 and 5Co/Al C400 had higher activity than 5Co/Ti C400. The T₅₀ (50% conversion) for both 5Co/Si C400 and 5Co/Al C400 was reached at temperatures as low as ambient temperature. According to the in situ FT-IR analysis, the variation in oxidation of CO was interpreted with different mechanisms, i.e., the reaction between adsorbed CO and lattice oxygen of cobalt oxide, and part of CO₂ formation via carbonates on 5Co/Si C400; both types of carbonates are formed on 5Co/Al C400 to promote the CO oxidation; while both strong adsorption of CO on TiO₂ and CO₂ on cobalt oxide for 5Co/Ti C400 leads to affect the activity.     

Vapour Phase Oxidation of Cumene by Molecular Oxygen over MCM-41 Supported Cobalt Oxide Catalyst

Si-MCM-41 and Al-MCM-41 supported cobalt oxide catalysts were prepared and characterized by XRD. The surface area, pore size and wall thickness was calculated by applying BET equation and BJH method using nitrogen sorption technique. DR UV-VIS confirm the presence of cobalt oxide as isolated particle in the framework positions of the MCM-41 mesostructure. The vapour phase oxidation of isopropyl benzene with CO₂-free air as the oxidant was studied over cobalt oxide supported unwashed and washed Si-MCM-41 and Al-MCM-41 catalyst. Isopropyl benzene conversion increased with increase in temperature from 200 to 300 °C, but at 325 °C it decreased. Formation of coke was noted at all the temperatures. Cumenehydroperoxide, 1,2-epoxyisopropylbenzene, acetophenone and styrene were the products observed in this reaction. Of the products cumenehydroperoxide was found to be more selective over all the catalysts. Both unwashed and washed catalysts were found to have nearly the same activity. Due to more dispersion, the active sites in the latter catalysts compensates its low cobalt oxide content in producing activity equal to the former catalysts. The study of time on stream indicated decrease in conversion due to coke formation.     

一种Ti3Al基高温合金的氧化行为研究

本文采用OM、XRD和SEM,研究了Ti-24Al-14Nb-3V-0.5Mo( at％)合金在700～900℃的氧化行为.合金氧化层主要由TiO2和Al2O3组成.随着氧化温度的升高和时间的延长,TiO2和A12O3颗粒逐渐长大,氧化层逐渐增厚.结果表明,随着温度的升高,合金氧化激活能明显降低.700℃～800℃之间的氧化激活能为205 kJ/mol,800℃～900℃之间的氧化激活能为119 kJ/mol.合金在700℃时具有良好的抗氧化性,800℃和900℃时抗氧化性能大幅降低.     

An Investigation of the Reduction and Reoxidation of Isolated Vanadate Sites Supported on MCM-48

The reduction and subsequent reoxidation of isolated vanadate species supported on silica was investigated using temperature-programmed reduction and oxidation, along with in-situ XANES and Raman spectroscopy. Approximately 70–80% of the vanadium was reduced to V³⁺ after reduction in H₂ at temperatures up to 923 K. Upon reduction, the vanadyl oxygen was removed and the three remaining V–O bonds are lengthened by 0.2 Å. The vanadate species are rapidly reoxidized when exposed to O₂, with the amount of oxygen uptake matching well with the amount removed during reduction. In-situ Raman spectroscopy during reoxidation in ¹⁸O₂ showed that significant scrambling occurs between gas phase oxygen and surface oxygen species during the reoxidation of the vanadate species.     

Oxidation of Sintered Cobalt Oxide

The kinetics and mechanism of the oxidation of sintered pellets of CoO and Co_0.5Mg_0.5O in air at high temperatures were investigated to find stable heat sources containing ⁶⁰Co. The initial stages of oxidation of both materials were nuclei-growth-controlled, i.e. In [1/(1-X)] =kt^m. The reaction rate constant for CoO decreased at 800° to 960°C, the temperature where the cobalt oxide spinel decomposed. The reaction-rate constant for decomposition of the mixed oxide was maximum at 700°C and decreased at higher temperatures. This decrease confirmed the validity of the nuclei-growth solid-state reaction-rate equations.     

Nanocatalysis on Supported Oxides for CO Oxidation

Active gold and palladium nanoparticles supported on a variety of oxides (CeO₂, ZrO₂, Al₂O₃, SiO₂, MgO and ZnO) were synthesized using laser vaporization and microwave irradiation methods. The catalytic activities for CO oxidation on the nanoparticle catalysts were evaluated and compared among different oxide supports. The effect of shape on the catalytic activity is demonstrated by comparing the activities of the Au and Pd catalysts deposited on MgO nanocubes and ZnO nanobelts. The Au/CeO₂ nanoparticles deposited on MgO nanocubes exhibit high catalytic activity and stability. The enhanced catalytic activity is attributed to the presence of a significant concentration of the corner and edge sites in MgO nanocubes. The Au- and Pd-doped Mn₂O₃ nanoparticles show promising results for the low temperature CO oxidation. Several approaches for incorporating the Au and Pd nanocatalysts within mesoporous oxide supports are presented and discussed.     

Supported Heteropolyacids for NOx Storage and Reduction

TiO₂ and SnO₂ were studied as possible supports for HPW in order to produce a new type of sorbent for NO _x trap applications. SnO₂ was synthesised by various inorganic methods while TiO₂ was purchased commercially. The sorption capacities and efficiencies depend upon the BET surfaces. Best performances were obtained with support with large pores where the crystalline structure of HPW is maintained. The optimal loading of HPW is ca. 50% with BET surface in the range 20–80 m²g^–1.     

新癸酸钴中不同氧化态钴的分离及测定

研究新癸酸钴中不同氧化态钴分离及测定的方法。根据二价钴和三价钴与乙酰丙酮形成的配合物溶解性的不同,实现不同氧化态钴的有效分离;根据配合物稳定常数的不同,利用络合滴定法,测定新癸酸钴中二价钴含量。用本方法对自制及市售新癸酸钴样品的进行分离及测定取得满意的效果。     

Rate of Oxidation of a Cobalt Catalyst in Water and Water/Hydrogen Mixtures: Influence of Platinum as a Reduction Promoter

The effect of a reduction promoter, platinum, on the oxidation of a cobalt catalyst was studied. An induction period was observed for the unpromoted catalyst which was absent for the Pt-promoted catalyst. The rate of oxidation was similar for both the Pt-promoted and unpromoted catalyst in the range of degrees of reduction between 50 and 10%. The rate of oxidation of the remainder of metallic cobalt was, however, faster for the platinum promoted catalyst.     

络合还原法制备Pd/C催化剂及甲酸电催化氧化性能

分别以硼氢化钠和乙二醇为还原剂,经络合还原法制备了炭载钯(Pd/C)催化剂。透射电镜(TEM)和X射线粉末衍射谱(XRD)结果表明,以乙二醇为还原剂制备的Pd/C催化剂中Pd粒子具有较小的粒径、均匀的粒径分布和较大的相对结晶度,Pd粒子的平均粒径和相对结晶度分别为(4.2±2)nm和1.88。电化学测试结果显示,Pd/C催化剂具有较大的电化学活性面积,对甲酸氧化表现出较高的电催化活性和稳定性。     

纳米CeO_2载体对Au-Pd催化剂性能的影响

采用十六胺和不同铈前驱体(硝酸铈铵或硝酸亚铈)分别合成了纳米CeO2(H4和H3),考察了纳米CeO2载体的织构性质对Au-Pd催化剂甲醇部分氧化制氢(POM)性能的影响,用HRTEM、N2吸附、XRD和TPR等对样品进行了表征。结果表明,铈前驱体对载体的性能有较大的影响,以硝酸铈铵为前驱体所制H4载体具有较小的粒径(约5 nm)和平均孔径(5.3 nm)、较大的比表面积(243 m2/g),而硝酸亚铈所制H3载体具有较大的平均孔径(7.9 nm)。POM结果表明,纳米CeO2负载的Au-Pd催化剂具有较好的催化性能,300℃时,Au-Pd/H3的活性和H2选择性分别达100%和59.7%。低温时催化剂的活性和H2选择性为:Au-Pd/H3>Au-Pd/H4,而高温时顺序相反,这是由于低温时催化剂的孔径对反应物和产物的扩散影响较大,高温时催化剂的比表面积和活性组分分散度起主要作用。     

Effect of Zirconia Content on the Oxidation Behavior of Silicon Carbide/Zirconia/Mullite Composites

The oxidation of hot-pressed SiC-particle (SiC_p)/zirconia (ZrO₂)/mullite composites with various ZrO₂ contents, exposed in air isothermally at 1000° and 1200°C for up to 500 h, was investigated; an emphasis was placed on the effects of the ZrO₂ content on the oxidation behavior. A clear critical volume fraction of ZrO₂ existed for exposures at either 1000° or 1200°C: the oxidation rate increased dramatically at ZrO₂ contents of >20 vol%. The sharp transition in the oxidation rate due to the variation of ZrO₂ content could be explained by the percolation theory, when applied to the oxygen diffusivity in a randomly distributed two-phase medium. Morphologically, the composites with ZrO₂ contents greater than the critical value showed a large oxidation zone, whereas the composites with ZrO₂ contents less than the critical value revealed a much-thinner oxidation zone. The results also indicated that the formation of zircon (ZrSiO₄) at 1200°C, through the reaction between ZrO₂ and the oxide product, could reduce the oxidation rate of the composite.