Carbon Monoxide Oxidation Catalysed by Exotemplated Manganese Oxides

Manganese oxides were synthesized by exotemplating using carbon materials as templates. The catalytic activity for CO oxidation was found to be mainly related with the availability of the lattice oxygen that can react with CO. Loading the materials with Au increased the activity only for the activated carbon exotemplated samples. This is due to the Au low particle size found for these samples, in contrast with others prepared with carbon xerogels.     

纳米催化剂及其在CO催化氧化领域的研究进展

综述了纳米催化剂的研究进展与制备方法，详细介绍了用于CO催化氧化的纳米催化剂的研究概况，指出纳米催化剂的催化活性和选择性大大优于常规催化剂，纳米复合稀土催化剂在汽车尾气控制方面前景诱人。     

Catalytic Carbon Monoxide Oxidation Using Bio-Templated Platinum Clusters

The catalytic properties of highly dispersed, bacterial surface layer supported nanoscale platinum clusters immobilized at alumina particles are studied with respect to carbon monoxide oxidation. Compared to samples prepared from platinum impregnated alumina, the templated metal clusters are catalytically active at lower temperatures. The catalytic behaviour of the samples is discussed with respect to their cluster morphology studied by TEM.     

In situ FTIR Study of Cobalt Oxides for the Oxidation of Carbon Monoxide

A high-valance cobalt oxide, CoO _x , was prepared from cobalt nitrate aqueous solution through precipitation with sodium hydroxide and oxidation by hydrogen peroxide. Further, other pure cobalt oxide species were refined from the CoO _x by temperature-programmed reduction (TPR) to 170, 230 and 300 °C. They were characterized by TPR and X-ray diffraction (XRD). Adsorption of CO and the co-adsorption of CO/O₂ over the cobalt oxides were further tested by in situ FTIR. It was shown that Co₃O₄ is quite active for the oxidation of CO at room temperature in the presence of oxygen, leading to the formation of CO₂. The variation in the oxidation of CO was interpreted with a mechanism involving two kinds of oxygen species, i.e., *-O₂ on the CoO _x surface and *-O_L on the surface of Co₃O₄ spinel structure.     

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.     

铜修饰的石墨氮化碳材料催化甲苯液相氧化反应

采用浸渍-焙烧法制备了铜修饰的石墨氮化碳材料Cu-C_3N_4。用XRD、BET、FT-IR及ICP等手段对催化剂的结构及组成进行了表征。考察了以H_2O_2为氧化剂,Cu-C_3N_4对甲苯氧化反应的催化性能,研究了反应条件对催化甲苯氧化反应的影响。在优化的条件下,甲苯转化率达到18.3%,苯甲醇、苯甲醛及苯甲酸的总选择性达到79.4%。     

Au Catalysts for Acetylene Hydrochlorination and Carbon Monoxide Oxidation

Supported gold nanoparticles can be highly effective as catalysts for a broad range of reactions. Most notably, for reactions such as the hydrochlorination of acetylene and the oxidation of carbon monoxide supported gold nanoparticles show exceptionally high activity. In this paper some of the discussion points raised at the Irsee VI Symposium held in July 2013 will be presented. The preparation of active supported gold nanoparticles will be described for the hydrochlorination of acetylene and the oxidation of carbon monoxide.     

甲苯液相空气催化氧化技术研究进展

介绍了甲苯液相催化氧化的反应机理、反应动力学模型和催化剂的研究进展;叙述了近年来在催化剂的研制、利用纯氧或富氧工艺、强化反应等方面的新技术.认为现有的生产技术有待于进一步改进,使用新型或复合催化剂、开发富氧或纯氧氧化工艺是降低成本、提高产品质量和生产能力的发展方向,并可借鉴其它液相氧化研究中出现新技术.     

堇青石负载非贵金属复合氧化物催化氧化甲苯的性能研究

本文采用浸渍法制备了以MOx(M为Cu、Co、Zn、Fe、Ce)和Mn Ox混合氧化物为活性组分,堇青石蜂窝陶瓷为载体的有机废气催化燃烧催化剂,以甲苯作为探针反应物测定该类催化剂的催化燃烧活性。考察了M与Mn物质的量比等因素对甲苯催化燃烧性能的影响,深入进行了XRD、BET和SEM表征与分析。实验结果表明:Fe/Mn物质的量的比为4∶1,焙烧温度为500℃,催化剂具有最佳的催化燃烧活性。     

Catalytic Activity of Supported Platinum and Metal Oxide Catalysts for Toluene Oxidation

Oxidation of toluene has been investigated over supported platinum as well as over a variety metal oxide (M _x O _y ) catalysts dispersed on high surface area γ-Al₂O₃. Catalysts were characterized with respect to their specific surface area (BET), metal dispersion (selective chemisorption of CO), phase composition and M _x O _y crystallite size (XRD) and reducibility (H₂-TPR). Catalytic performance for the title reaction was investigated in the temperature range of 100–500 °C, using a feed composition consisting of 0.1% toluene in air. For Pt/M _x O _y catalysts, it has been found that catalytic performance depends on the nature of the support, with Pt/CeO₂ being the most active catalyst at low temperatures. The intrinsic reaction rate per surface platinum atom does not depend on Pt loading (0.5–5 wt%), at least for Pt/Al₂O₃. Reducible metal oxides, such as ceria, are active for the title reaction and catalytic performance is improved significantly with increase of specific surface area (SSA). However, the intrinsic reaction rate per unit surface area is invariant with SSA. Dispersion of M _x O _y on high surface area inert supports, such as Al₂O₃, results in materials with relatively high catalytic activity, which seems to correlate well with the reducibility of metal oxides. Catalytic performance of M _x O _y /Al₂O₃ catalysts can be optimized by proper selection of M _x O _y loading. Best performing catalysts of this series include 60% MnO, 90% CeO₂ and 5% CuO on Al₂O₃ which, under the present experimental conditions, are able to completely convert toluene toward CO₂ at temperatures lower than 350 °C. Dispersion of Pt on M _x O _y /Al₂O₃ catalysts improves significantly the catalytic performance of irreducible M _x O _y but does not alter appreciably the activity of reducible M _x O _y /Al₂O₃ catalysts.     

Catalytic Liquid Phase Oxidation of Toluene to Benzoic Acid

The production of benzoic acid from toluene in the liquid phase with pure oxygen was studied. Investigations have been carried out with a view to determining the most suitable reaction conditions with respect to operating variables including oxygen flow rate, reaction temperature, batch time and catalyst loading. In a series of batch experiments carried out at 4 atm, the optimum values of mole ratio of oxygen to toluene, temperature, reaction time, and catalyst loading were found to be 2, 157 °C, 2 h and 0.57 g/L, respectively. In addition, a kinetic study was carried out by taking into consideration the optimum reaction conditions. The model dependent on the formation of benzyl radical was found to be feasible for describing the catalytic oxidation of toluene to benzoic acid in the liquid phase. The activation energy was determined as 40 kJ/mol.     

The Catalytic Synthesis of Hydrocarbons from Carbon Monoxide and Hydrogen

The increasing demand for energy, coupled with the uncertainty and expense of crude oil imports, has renewed interest in the production of fuels and chemicals from hydrogen-deficient materials. These energy sources such as coal, residua, oil shale, and tar sands can be gasified with steam and oxygen to produce a gas containing large quantities of carbon monoxide and hydrogen. Once methane is removed from this CO/H₂ mixture it is purified to remove S poisons and then reacted over a catalyst to produce a variety of organic products. The synthesis of hydrocarbon products, with the exception of methane, is commonly referred to as the Fischer-Tropsch synthesis reaction.     

甲苯液相催化氧化过程模拟与优化

Liquid-phase oxidation of toluene with air has become the main technology for producing benzoic acid in a reactor at present. Based on the kinetic model of the toluene oxidation process obtained from laboratory and mass balance of key component, a novel model is established to simulate the industrial toluene oxidation process, in which the effects of benzaldehyde and benzyl alcohol are considered and the kinetic parameters are revised by industrial data. The simulation results show that the error of benzoic acid yield is within 3.5%. Based on the simulation model, to maximize the benzoic acid yield, an optimization model is proposed to optimize the operating parameters, including toluene feed-in mass flux and temperature. The optimization result indicates that on the allowable operating conditions the maximum benzoic acid yield obtained with the reaction temperature at 167.2 C an the mass flux at 104.1 t·h^- 1 is greater than the current one, which can be used to guide industrial reactor s operation.     

Mechanisms of Carbon Monoxide and Methanol Oxidation at Single-crystal Electrodes

The electrochemical oxidation of carbon monoxide and methanol on single-crystal noble metal electrodes has been studied using cyclic voltammetry, chronoamperometry, in situ FTIR spectroscopy, online electrochemical mass spectrometry, and theoretical methods. The oxidation of CO was found to be enhanced by steps and defects. Furthermore, the surface diffusion rate was found to have a significant influence on the kinetics of the oxidation process: for high diffusion rates, such as the oxidation of CO on platinum, the kinetics can be described by a mean field model, while for low diffusion rates, such as CO oxidation on rhodium in sulfuric acid, a nucleation-and-growth model was found to be more suitable. Voltammetric and mass spectrometric measurements on the oxidation of methanol on platinum indicate that steps enhance the overall reaction rate. In general, the selectivity towards the direct oxidation pathway through soluble intermediates was found to be higher in the absence of strongly adsorbing anions. In both perchloric and sulfuric acid, this selectivity was also found to increase with increasing step density. In sulfuric acid, Pt(111) shows the highest relative contribution for the direct pathway of all surfaces studied in that electrolyte. Based on these results, a detailed reaction scheme for the electrochemical oxidation of methanol is presented.     

超临界CO2中甲苯氧化为苯甲醛的研究

研究了超临界CO2介质中过氧化氢氧化甲苯生成苯甲醛的均相氧化反应。实验考察了无催化剂条件下影响苯甲醛收率的因素。研究发现,在压力25MPa。温度180℃,反应时间4h。过氧化氢与甲苯摩尔比为2．5的条件下,苯甲醛的收率为1．535％,此时的氧化反应可近似为1级反应,反应活化能为21．5KJ／mol。     

稀土催化剂对CO低温氧化研究

采用共沉淀法制备了稀土催化剂,并考察了沉淀剂种类、制备方法、煅烧温度以及稀土对催化效果的影响.试验结果表明:以Na2CO3为沉淀剂,添加稀土Sm,于300℃煅烧4h制得的稀土催化剂能够在0℃左右将CO完全氧化.     

低温CO催化氧化负载型Pd催化剂研究进展

综述了低温CO催化氧化负载型Pd催化剂在制备方法、载体的选用和催化机理等方面的研究进展,并介绍了该类催化剂的最新进展.在文章末对该催化剂领域尚待深入研究的问题进行了探讨.     

二氧化锰/石墨烯臭氧催化氧化甲苯反应性能

采用一步水热合成法,在180℃,12 h条件下制备了30%二氧化锰/石墨烯(MnO2/G)复合材料。实验结果表明:MnO2均匀且较为牢固地锚定于石墨烯表面,同时MnO2的沉积阻止了多层石墨烯的复合,从而使得复合物具有较大的比表面积。相同条件下,MnO2/石墨烯相较于单纯MnO2或石墨烯具有很好的臭氧催化氧化甲苯性能,这可以归结于MnO2和石墨烯间的协同催化作用。