Catalytic reduction of N2O with CH4 and C3H6 over Ag–Rh/Al2O3 bimetallic catalyst in the presence of oxygen

A study of nitrous oxide (N₂O) reduction with methane (CH₄) and propene (C₃H₆) in the presence of oxygen (5%) over Ag/Al₂O₃, Rh/Al₂O₃ and Ag–Rh/Al₂O₃ catalysts, with Ag and Rh loadings of 5 wt% and 0.05 wt% respectively, has been performed. From the results, it was observed that the Ag–Rh bimetallic catalyst was the most active for both nitrous oxide removal (more than 95%) and hydrocarbon oxidation. This high activity seems to be connected with a synergistic effect between Ag and Rh. The findings from X‐ray diffraction and X‐ray photoelectron spectroscopy studies showed also, that there were no strong interactions (eg alloying) between Ag and Rh. Copyright © 2005 Society of Chemical Industry     

Exchange and oxidation of CO on O-predosed Rh---Al2O3 and Rh---CeO2 catalysts

Exchange and oxidation of C¹⁶O were investigated at 450°C on ¹⁸O-predosed Rh and Pt catalysts supported on A1₂O₃, CeO₂ and CeO₂-Al₂O₃. In all cases, a rapid exchange of C¹⁶O with the surface can be observed. CO oxidation leads to C¹⁶O₂, C¹⁶O¹⁸O and C¹⁸O₂. Significant formation of C¹⁶O₂ is due to the relatively high ¹⁶O coverage in reaction resulting from the C¹⁶O exchange and from an exchange between O surface species and ¹⁶O internal atoms. Hydrogen is also formed via a water-gas shift reaction (CO + surface OH) in higher proportion on CeO₂-containing catalysts than on A1₂O₃. Chlorine inhibits all the reactions (exchange, oxidation and WGS) and particularly the internal exchange.     

铂铑包覆钼合金搅拌器的研制

介绍了铂铑包覆钼合金搅拌器的结构与技术要求,以及搅拌器的制作与使用效果。研制结果表明,国产搅拌器达到了日本同类产品的水平。     

Olefins polymerization on titania and titania-supported rhodium

The adsorption of ethene and propene on titania and titania-supported rhodium has been studied, observing a continuous adsorption even after 24 h. The samples have been reduced at 623 or 773 K, but no difference was observed, whichever the reduction temperature or the presence of rhodium, on the amount of gas adsorbed per unit of surface area of the solid. A study of the polymerization has been done following the equal reactivity hypothesis, and it has been concluded that the role played by the rhodium particles is to facilitate adsorption of the gaseous molecule, that is then transfered to the surface of the support, where it polymerizes.     

Reforming of methane with carbon dioxide over supported bimetallic catalysts containing Ni and noble metal: I. Characterization and activity of SiO2 supported Ni–Rh catalysts

Cobalt catalysts supported on silica aerogel have been prepared using sol–gel chemistry followed by drying under supercritical ethanol conditions. Three different loadings of cobalt were synthesized: 2, 6, and 10% by weight. Transmission electron micrographs indicate that the metallic cobalt exists as discrete particles 50–70 nm in diameter for the 2 and 6% loadings. The 10% catalyst shows long needles of cobalt. BET and BJH measurements indicate that the catalysts retain the silica aerogel properties of high surface area (∼800 m²/g), large pore volume (∼5 cm³/g), and an average pore diameter in the mesoporous regime (∼25 nm). The catalysts were evaluated for Fischer–Tropsch activity in a laboratory-scale packed bed reactor. All three catalysts were active with the 10% Co catalyst achieving more than 20% CO conversion which corresponds to a rate of 1.53 g CO per g-cat per hour. The catalysts were selective for the C₁₀₊ hydrocarbons with more than 50% of the carbon contained within this fraction. A significant portion of the C₉–C₁₅ hydrocarbon product was observed as 1-olefins which reflects the enhanced mass transport within the very porous aerogel support.     

Alternative view of anodic surface oxidation of noble metals

The idea of underpotential oxidation of water, taking place on the surface of noble metals in the range of potentials preceding molecular oxygen evolution, is more than 40-years old. Chemisorbed oxygen atom—O_chem is considered to be the main intermediate in the underpotential oxidation of H₂O, leading eventually to chemical oxidation of noble metals and formation of anhydrous surface oxides of MeO type. This concept is still used for the evaluation of the real surface area of the noble metal electrodes and also for the interpretation of new experimental results.The existence of reversible metal-oxide electrodes demonstrated experimentally for Pt, Pd, Rh, Ir and Au electrodes, oxidized anodically in the range of potentials preceding O₂ evolution, shows that noble metals do have electrochemistry of their own. Nanometric layers of amorphous, slightly soluble hydroxides, hydrous oxides or oxides can form electrochemically on the electrode surface during the anodic process and be reduced during the cathodic one. Such alternative concept admits the reversibility of anodic and cathodic processes and changes essentially the understanding and interpretation of the phenomena of anodic oxidation of noble metals.     

铑含量对Pt-Rh-Pd/Al2O3催化剂的氧化还原性能的影响

应用微反应装置研究了铑含量对Pt-Rh-Pd/Al2O3催化剂的催化活性以及吸附性能的影响.结果表明Rh含量在0%～0.015%之间时,催化剂对CO的活性曲线呈波浪形,对NO的活性曲线为增函数;当Rh含量超过0.015%时,增加Rh的量对CO和NO的转化率几乎无影响.在无助的情况下,用Al2O3为载体制作的Pt-Rh-Pd/Al2O3催化剂,其Pt、Rh、Pd之间的最佳比例为15320.Rh含量的增加有利于氧化性气体的吸附,不利于还原性气体的吸附.     

Small-scale hydrogen production from propane

Partial oxidation and oxidative steam reforming of propane were investigated over 0.01 wt.% Rh/Al₂O₃ foam catalysts. High selectivity to hydrogen was obtained for both reactions, but addition of steam to the reactant mixture gave higher selectivity to hydrogen. Stability tests over 7 h revealed that the catalytic activity of Rh was quite stable under partial oxidation conditions. Higher loss in Rh activity was observed when steam was present in the reactant mixture. FE-SEM images showed that Rh particle size and distribution are modified under partial oxidation and oxidative steam reforming conditions. However, these changes were more distinct on the catalyst used for oxidative steam reforming.     

Lewis acidity as an explanation for oxide promotion of metals: implications of its importance and limits for catalytic reactions

Sub-monolayer quantities of metal oxides are found to influence CO hydrogenation, CO₂ hydrogenation, acetone hydrogenation, ethylene hydroformylation, ethylene hydrogenation, and ethane hydrogenolysis over Rh foils. The metal oxides investigated include AlOx, TiOx, VOx, FeOx, ZrOx, NbOx, TaOx, and WOx. Only those reactions involving the hydrogenation of C-O bonds are enhanced by the oxide overlayers. The coverage at which maximum rate enhancement occurs is approximately 0.5 ML for each oxide promoter. Titanium, niobium, and tantalum oxides are the most effective promoters. XPS measurements after reaction show that of the oxides studied titanium, niobium, and tantalum oxide overlayers are stable in the highest oxidation states. The trend in promotion effectiveness is attributed to the direct relationship between oxidation state and Lewis acidity. For the oxide promoters, bonding at the metal oxide/metal interface between the O-end of adsorbed CO and the Lewis acidic oxide is postulated to facilitate C-O bond dissociation and subsequent hydrogenation.     

185nmUV降解水中4-CP、4-NP和RhB的研究

本文以对氯苯酚（4-cP）、对硝基苯酚（4-NP）和罗丹明B（RhB）为模型有机物（以4-CP和4-NP为小分子模型有机物，以RhB为大分子模型有机物），分别研究了185nmUV对水中这3种模型有机物的降解规律、性能和效果．研究结果表明，185nmUV直接对水中4-CP、4-NP和RhB有很好的降解效果．研究内容包括：185nmUV降解模型有机物的浓度、TOC（Totalorganic carbon）浓度、185nmUV降解模型有机物过程中溶液pH及电导率变化、以及降解模型有机物过程中产生的无机离子等几个方面．