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。     

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...     

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。     

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.     

Compact Reforming Process Using High-Performance and Long-Lived CO Preferential Oxidation over an Activated Ru/Al2O3 Catalyst for PEFC

Compact natural gas reforming process using high-performance and long-lived CO preferential oxidation (PROX) over an activated Ru/Al₂O₃ catalyst has been developed for residential polymer electrolyte fuel cell (PEFC) systems. The long-term durability of the catalyst was demonstrated for more than 40,000 h. After 40,000 h operation, CO was removed from a reformed gas to below 1 ppm on the activated Ru/Al₂O₃ catalyst at [O₂]/[CO] = 1.5. The high activity and selectivity of the catalyst were maintained for more than 40,000 h. Moreover, the start–stop durability for more than 3,000 cycles of the activated Ru/Al₂O₃ catalyst was also demonstrated without N₂ purge.     

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.     

Characterization of Au/MnO x /TiO2 for Photocatalytic Oxidation of Carbon Monoxide

The Au/MnO _x /TiO₂ catalyst was used for the photocatalytic oxidation of carbon monoxide. The catalytic activity of Au/MnO _x /TiO₂ with low concentration of manganese (3–7 mol%) was much higher than that of Au/TiO₂. The surface of Au/MnO _x /TiO₂ was characterized by XPS and Raman spectroscopy. While the main state of manganese in 13.8 mol% MnO _x /TiO₂ was Mn⁴⁺ species, Mn³⁺ was the dominant species in the samples with below 6.5 mol% manganese. Raman spectroscopy revealed that the interaction between the MnO _x and TiO₂ form Mn–O–Ti species in which the state of manganese was Mn³⁺. The Au particles also interacted with both MnO _x and TiO₂ to modify the surface of them. In the case of the Au species, low loading of manganese produced the metallic Au⁰ and perimeter interfacial Au^δ+, whereas high loading showed the coexistence of three components which were metallic Au⁰, perimeter interfacial Au^δ+, and oxidic Au³⁺. The catalytic active component was the metallic Au⁰ and perimeter interfacial Au^δ+ species, which were dispersed on TiO₂ and Mn³⁺/TiO₂.     

Preparation of High-Performance Co3O4 Catalyst for Hydrocarbon Combustion from Co-Containing Hydrogarnet

Supported Co₃O₄ catalysts were prepared via the calcination of Co-containing hydrogarnet, (Ca_3-x Co _x )Al₂(SiO₄)_{3- y} (OH)_4y , at 400 °C. Such precursors with various extents of substitution were synthesized from the hydrothermal reaction of a stoichiometric mixture of calcium oxide, amorphous silica, alumina sol, and cobalt hydroxide at 200 °C. It was found that the catalyst consisted of Co₃O₄, CaO, and mayenite and exhibited a high activity for the combustion of propylene, benzene, and toluene at temperatures below 300 °C.     

Oxidation of Carbon Monoxide Over SBA-15-Confined Copper,Palladium and Iridium Nanocatalysts

Abstract  

Copper, palladium and iridium nanoparticles were synthesised within the pore channels of selectively grafted mesoporous silica SBA-15. The support and catalysts were characterised by different techniques. The synthesized catalyst were able to catalyse oxidation of carbon monoxide with activity values as high as 7.0 × 10⁻³ mmol g⁻¹ cat s⁻¹ at 353 K. Carbon monoxide conversion was found to increase with decreasing nano particle size.     

Preparation and Oxidation Catalysis of H5PMo10V2O40 Catalyst Immobilized on Nitrogen-Containing Spherical Carbon

Nitrogen-containing spherical carbon (N-SC) with a diameter of ca. 12 μm was synthesized by a hydrothermal method using melamine-formaldehyde resin as a carbon precursor. The N-SC was then modified to have a positive charge, and thus, to provide a site for the immobilization of H₅PMo₁₀V₂O₄₀ (PMo₁₀V₂) catalyst. The PMo₁₀V₂ catalyst was chemically immobilized on the surface-modified N-SC support by taking advantage of the overall negative charge of [PMo₁₀V₂O₄₀]^5?. Characterization results showed that nitrogen in the N-SC support played an important role in forming a nitrogen-derived functional group (amine group) and that PMo₁₀V₂ catalyst was chemically immobilized on the nitrogen-derived functional group of N-SC support. PMo₁₀V₂/N-SC catalyst showed a higher 2-propanol conversion than the unsupported PMo₁₀V₂ catalyst in the vapor-phase 2-propanol conversion reaction. Moreover, the PMo₁₀V₂/N-SC catalyst showed an enhanced oxidation catalytic activity (formation of acetone) and a suppressed acid catalytic activity (formation of propylene and isopropyl ether) than the unsupported PMo₁₀V₂ catalyst. The enhanced oxidation activity of PMo₁₀V₂/N-SC catalyst was due to fine dispersion of [PMo₁₀V₂O₄₀]^5? on the N-SC support formed via chemical immobilization.     

Molecular Simulations in Activated Carbons for Carbon Monoxide Removal From Wet Mixture of Hydrogen and Carbon Monoxide

Activated carbons are porous materials with a high surface area which are widely used in gases separation and catalysis. This work focuses on the understanding of the separation characteristics of activated carbons for purifying hydrogen from the wet mixture of hydrogen and carbon monoxide (in hundreds of ppm). This study would build a basic insight of the separation mechanism of the activated carbon and determine whether activated carbons are suitable for CO removal from the mixture. Systematic Grand Canonical Monte Carlo (GCMC) simulations have been carried out to assess the adsorption properties and selectivity of the activated carbon to the gaseous mixture with different gas phase compositions, temperatures, and pressures. The calculated adsorption isotherms, both for single and multi-component gas mixture, and isosteric heats of adsorption on the activated carbon showed reasonably good agreement with the experimental data available in the literature.