The preparation and properties of La3.5Ru4O13 and La2RuO5

The stability of the La_3.5Ru₄O₁₃ and La₂RuO₅ compounds in the La–Ru–O system in various atmospheres and various temperature ranges was investigated by thermal analysis, X-ray diffraction analysis and electron microscopy. The La_3.5Ru₄O₁₃ compound is stable in oxidizing and neutral atmospheres (N₂ with 10 ppm O₂), while La₂RuO₅ is partially reduced in a neutral atmosphere to form La₂RuO_4.6. In a reducing atmosphere both compounds decompose into metallic Ru and La₂O₃. The thermal expansion coefficients of La₂RuO₅ and La_3.5Ru₄O₁₃ at 800 °C are 11.2 × 10⁻⁶ K⁻¹ and 9.3 × 10⁻⁶ K⁻¹, respectively. The specific electrical resistivity for La_3.5Ru₄O₁₃ is relatively independent of temperature and is 2 × 10⁻² Ω cm at 800 °C, while for La₂RuO₅ it decreases with increasing temperature and is 1 Ω cm at 800 °C.     

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.     

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.     

Effect of La2O3 on Ru/CeO2-La2O3 Catalyst for Ammonia Synthesis

A series of CeO₂-La₂O₃ supported ruthenium catalysts were prepared by co-precipitation method and the as-obtained samples were characterized by N₂ physisorption, X-ray diffraction, CO chemisorption, H₂-TPR, H₂-TPD and XPS. The activity test shows that ammonia concentration of the catalyst with 10% La is 13.9% at 10 MPa, 10,000 h^?1, 450 °C, which is 17% higher than that of Ru/CeO₂. La doping can improve the activity of Ru-ceria catalyst for ammonia synthesis by facilitating the reduction of oxygen which subsists in the cerium oxide surface. In addition, it can be realized that the test of catalyst stability proves the stability performance of Ru/CeO₂-La₂O₃ catalyst within the reaction time of 55 h.     

B117催化剂上一氧化碳中温变换的本征动力学

在常压、５３３￣６７３Ｋ的温度范围内，测定了市售Ｂ１１７型低铬一氧化碳中温变换催化剂的催化活性，通过对实验数据的处理，得到了不同数学模型速率方程及其动力学参数，并得知双曲函数速率方程所含的常数Ａ实际上是温度和转化率的函数。     

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。     

还原温度对CuO-ZnO-ZrO2催化剂的还原度及其低温CO氧化反应性能的影响

采用还原热力学计算、H2-TIR、H2-TPR及活性评价等手段,考察了还原温度对CuO-ZnO-ZrO2催化剂的还原度和低温CO氧化反应性能的影响。研究发现,在CuO-ZnO体系中添加ZrO2,提高了CuO的分散度,使得活性组分CuO更容易还原,在相同还原条件下, 比 更容易进行。H2-TIR结果表明,随着还原活化温度的升高,还原耗氢量增大、还原峰出峰时间前移。通过H2的消耗量计算得到,随着还原温度的升高,还原度依次增大：0 %（100 ℃）< 45.7 %（140 ℃）< 77.3 %（160 ℃）< 86.2 %（200 ℃）。低温CO脱除性能评价表明,较优还原温度（160 ℃）下活化的催化剂具有较高的CO催化氧化活性,在100℃反应温度下,CO转化率达100 %;可将液相丙烯中微量的CO（10ppm）脱除低至0.02ppm,连续反应1500min,稳定性能良好。     

Mechanistic Study of Carbon Oxidation with NO2 and O2 in the Presence of a Ru/Na‐Y Catalyst

The oxidation of model soot by NO₂ and O₂ in the presence of a Ru/Na‐Y catalyst under conditions close to automotive exhaust gas after‐treatment systems is investigated. Isothermal oxidation experiments of a physical mixture of carbon black and catalyst were performed in a temperature range of 300–400 °C. A remarkable increase of the oxidation rate by NO₂ and O₂ in the presence of the Ru/Na‐Y catalyst was observed. An overall mechanism involving oxygen transfer from the Ru catalyst to the carbon surface leading to an increase of C(O) complexes is proposed. These C(O) complexes are destabilized in the presence of NO₂ increasing the carbon oxidation rate.     

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.     

Co-precipitated Copper Zinc Oxide Catalysts for Ambient Temperature Carbon Monoxide Oxidation: Effect of Precipitate Aging Atmosphere on Catalyst Activity

A study of the effect of the aging atmosphere on the activity of co-precipitated copper zinc oxide catalysts for the ambient temperature oxidation of carbon monoxide is described and discussed. Four aging atmospheres are reported: air, N₂, H₂ and CO₂, and both the precipitation and the aging of the precipitate were carried out by flowing these gases through the precipitation cell at constant pH and temperature. For all atmospheres, the surface area of the final CuO-ZnO catalyst increases with aging time and, consequently, the specific activity (mol CO converted/g catalyst/h) also increases. However, the intrinsic activity (mol CO converted/m²/h) initially decreases with aging time before attaining a steady level. The highest activity catalysts were obtained using air as the aging atmosphere and TPR studies indicate that this catalyst is less readily reduced. Catalysts prepared using CO₂ as the aging atmosphere have lower activity, although the surface areas of these catalysts are not markedly lower. The study demonstrates that selection of the appropriate aging atmosphere, as well as the aging time, is an important parameter for the preparation of co-precipitated catalysts.     

CuO-ZnO-ZrO_2催化剂的还原性能及其低温CO催化氧化性能

采用共沉淀法制备得到CuO-ZnO-ZrO2催化剂及对比样品CuO-ZnO,通过XRD、BET、XPS、H2-TIR、H2-TPR等表征,考察了ZrO2的添加对CuO-ZnO-ZrO2催化剂的还原性能及其CO催化氧化性能的影响。与CuO-ZnO相比较,CuO-ZnO-ZrO2催化剂的比表面积增大、CuO和ZnO粒子的平均粒径减小、表面Cu粒子含量增多、还原性能得到显著提高,表明ZrO2的添加有利于提高CuO分散度,存在更多与ZnO相互作用的CuO微粒。TPR的还原动力学研究进一步证实了ZrO2对CuO还原性能的促进作用。在CO催化氧化反应中,CuO-ZnO-ZrO2样品的催化活性最高,并且还原温度对该催化剂的CO催化氧化性能影响显著,在160℃还原活化的催化剂具有77.3%的还原度,表现出较优的CO催化氧化性能。在50℃、3 MPa的反应条件下,CuO-ZnO-ZrO2催化剂可将液相丙烯中体积分数1.0×10-5的CO脱除低至2×10-8,连续反应1 500 min,稳定性能良好。     

Catalytic performance of spinel-type Ni-Co Oxides for Oxidation of Carbon Monoxide and Toluene

Topics in Catalysis - This study aims to investigate the catalytic activity of spinel-type oxides (NixCoyO4) for the oxidation of toluene and carbon monoxide at low temperatures. A series of Ni/Co...     

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.     

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.     

同时测定乙烯中烃类杂质及CO、CO_2方法探讨

采用1台气相色谱仪、双阀双通道、双氢火焰检测器一次进样同时完成乙烯中微量CO、CO2及烃类杂质的全分析。通过考察载气流速、柱温、升温速率、分流比对实验结果的影响,确定了最佳实验条件,同时对该方法进行了精密度、准确度和最小检测限考察。结果表明该方法是乙烯中杂质含量测定的一种简单快捷、准确可靠的分析方法。     

Potassium Titanate: An Alternative Support for Gold Catalyzed Carbon Monoxide Oxidation?

It has been found that gold supported on potassium titanate, KTiO₂(OH) can, under some circumstances, exhibit a superior performance for the oxidation of carbon monoxide, relative to that obtained with titania as a support. It appears that the dispersions of gold on the two types of support are sufficiently similar that other factors are responsible for the improved activity noted. It may be that the higher basic character and/or detailed structural features of the titanate surface plays a role.     

Novel Alumina-Supported PtFe Alloy Nanoparticles for Preferential Oxidation of Carbon Monoxide in Hydrogen

Supported bimetallic PtFe catalyst is one of the most promising candidates for preferential CO oxidation (PROX) in H₂ for fuel cells. We are interested in developing novel PtFe catalysts which have special architectures and are more excellent in catalytic performance for the PROX reaction. In the present study, three kinds of novel alumina-supported PtFe, PtFe₂ and PtFe₃ alloy nanoparticles were prepared from Pt(acac)₂ and Fe(acac)₃ reduced by ethylene glycol in Ar atmosphere at 185 °C. The catalytic experiments showed that the three materials were more active for the PROX reaction under pretreatment both in He and H₂ atmospheres as compared to that of Pt/Al₂O₃ prepared by the same chemical route. Their structural property and iron state were investigated by X-ray diffraction and ⁵⁷Fe Mössbauer spectroscopy. The obtained results proved that the novel as-prepared PtFe/Al₂O₃, PtFe₂/Al₂O₃ and PtFe₃/Al₂O₃ materials are clearly different in the architecture and the oxidation state of iron as compared to the conventionally prepared one.     

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.     

Preparation of Fe-Mn/K/Al2O3 Fischer-Tropsch Catalyst and Its Catalytic Kinetics for the Hydrogenation of Carbon Monoxide

A K promoted iron-manganese catalyst was prepared by sol-gel method, and subsequently was tested for hydrogenation of carbon monoxide to light olefins. The kinetic experiments on a well-characterized Fe-Mn/K/Al₂O₃ catalyst were performed in a fixed-bed micro-reactor in a temperature range of 280-380 ℃, pressure range of 0.1-1.2 MPa, H₂/CO feed molar ratio range of 1-2.1 and a space velocity range of 2000-7200 h^-1. Considering the mechanism of the process and Langmuir-Hinshelwood-Hogan-Watson (LHHW) approach, unassisted CO dissociation and H-assisted CO dissociation mechanisms were defined. The best models were obtained using non-linear regression analysis and Levenberg-Marquardt algorithm. Consequently, 4 models were considered as the preferred models based on the carbide mechanism. Finally, a model was proposed as a best model that assumed the following kinetically relevant steps in the iron-Fischer-Tropsch (FT) synthesis: (1) CO dissociation occurred without hydrogen interaction and was not a rate-limiting step; (2) the first hydrogen addition to surface carbon was the rate-determining steps. The activation energy and adsorption enthalpy were calculated 40.0 and -30.2 kJ·mol^-1, respectively.     

First Principles Analysis of the Electrocatalytic Oxidation of Methanol and Carbon Monoxide

The strong drive to commercialize fuel cells for portable as well as transportation power sources has led to the tremendous growth in fundamental research aimed at elucidating the catalytic paths and kinetics that govern the electrode performance of proton exchange membrane (PEM) fuel cells. Advances in theory over the past decade coupled with the exponential increases in computational speed and memory have enabled theory to become an invaluable partner in elucidating the surface chemistry that controls different catalytic systems. Despite the significant advances in modeling vapor-phase catalytic systems, the widespread use of first principle theoretical calculations in the analysis of electrocatalytic systems has been rather limited due to the complex electrochemical environment. Herein, we describe the development and application of a first-principles-based approach termed the double reference method that can be used to simulate chemistry at an electrified interface. The simulations mimic the half-cell analysis that is currently used to evaluate electrochemical systems experimentally where the potential is set via an external potentiostat. We use this approach to simulate the potential dependence of elementary reaction energies and activation barriers for different electrocatalytic reactions important for the anode of the direct methanol fuel cell. More specifically we examine the potential-dependence for the activation of water and the oxidation of methanol and CO over model Pt and Pt alloy surfaces. The insights from these model systems are subsequently used to test alternative compositions for the development of improved catalytic materials for the anode of the direct methanol fuel cell.