Chemistry and Physics of Alkali Metals on MoS2 Surfaces

The interaction of alkali metal with surfaces has been of great interest to the community of catalysis since alkali metal can play an important role as a promoter. On alkali-doped MoS₂, such a promotion effect of alkali metal has been exemplified in the direct synthesis of linear alcohols from CO and H₂, where the alkali-doping switches the catalyst selectivity from methanation to alcohol synthesis. This paper reviews recent high-resolution X-ray photoelectron spectroscopy experiments that have provided direct observation of electron transfer from alkali metals to a model single crystal MoS₂ and the capture of the supra-valence electrons in the subsequent oxidation reactions.     

天然气制液态烃新工艺

丰富的天然气资源,特别是边远地区分散的中小天然气田和油气共生的油气田的天然气,由于产量达不到管线长输的规模效益,又远离消费市场,很难开发利用.为此,作者在天然气两段催化氧化制合成气和费-托合成研究的基础上,提出了一种流程较短、投资和操作费用较低的天然气合成液态烃新工艺,可将丰富的天然气资源,特别适合将边远地区分散的中小天然气田的天然气转化为无硫、无氮、无芳烃、无重金属污染和便于输运的优质石蜡基液态产品.该产品可经轻度加氢改质得到高品质的柴油掺合组分、润滑油基础油高等附加值产品.该工艺副产的燃料气可用于发电,或作为燃料气使用.     

Effect of Particle Size on Monometallic and Bimetallic (Au,Pd)/C on the Liquid Phase Oxidation of Glycerol

The influence of metal particle size of monometallic and bimetallic supported catalysts (Au, Pd, Au–Pd)/C was studied using as a model reaction the liquid phase oxidation of glycerol. By tuning the metal particle size from 2 to 16 nm a progressive decrease of activity and simultaneously an increase in the selectivity to sodium glycerate was observed. Moreover, the influence of the temperature was studied and it was found that by increasing the temperature, only with a large particle size the formed glycerate was retained and not over-oxidized to tartronate.     

A novel laboratory bench for practical evaluation of catalysts useful for simultaneous conversion of NOx and soot in diesel exhaust

This study deals with the development of a laboratory bench for the practical evaluation of catalysts that are useful for the direct conversion of NO_x and soot in the exhaust of diesel engines. The employed model exhaust is generated by using a diffusion burner with additionally dosing some gaseous components to the burner gas to obtain a realistic feed composition. The produced soot is extensively characterized by employing thermogravimetry, transmission electron microscopy, N₂ physisorption and temperature programmed techniques. The results of the different characterization methods show that the present soot is suitable for the intended catalytic investigations. The simultaneous conversion of NO_x and soot is examined like in practice, i.e. the soot is separated from the tail gas by a diesel particulate filter (DPF) that is coated with the catalyst. The deposited soot is then catalytically converted by NO_x and O₂ to form N₂ and CO₂. The conversions of NO_x and soot are measured by exclusively applying gas analysers, whereby a special experimental procedure is developed to determine the soot removal. Hence, additional soot related analytics are not required. To show the suitability of the constructed bench a Pt/Fe₂O₃/β-zeolite sample is taken as test catalyst that is reported to be very active in NO_x/soot reaction. The measurements performed with and without catalyst clearly show the effect of the used sample in simultaneous NO_x/soot conversion. We therefore consider the constructed laboratory bench to be a useful tool for testing and ranking catalytic materials.     

Promising alloys for intermediate-temperature solid oxide fuel cell interconnect application

The formation of a low Cr-volatility and electrically conductive oxide outer layer atop an inner chromia layer via thermal oxidation is highly desirable for preventing chromium evaporation from solid oxide fuel cell (SOFC) metallic interconnects at the SOFC operation temperatures. In this paper, a number of ferritic Fe–22Cr alloys with different levels of Mn and Ti as well as a Ni-based alloy Haynes 242 were cyclically oxidized in air at 800 °C for twenty 100-h cycles. No oxide scale spallation was observed during thermal cycling for any of these alloys. A mixed Mn₂O₃/TiO₂ surface layer and/or a (Mn, Cr)₃O₄ spinel outer layer atop a Cr₂O₃ inner layer was formed for the Fe–22Cr series alloys, while an NiO outer layer with a Cr₂O₃ inner layer was developed for Haynes 242 after cyclic oxidation. For the Fe–22Cr series alloys, the effects of Mn and Ti contents as well as alloy purity on the oxidation resistance and scale area specific resistance were evaluated. The performance of the ferritic alloys was compared with that of Haynes 242. The mismatch in thermal expansion coefficient between the different layers in the oxide scale was identified as a potential concern for these otherwise promising alloys.     

Catalyst instabilities during the liquid phase partial oxidation of methane

A promising catalytic system for the low temperature oxidation of methane to a methanol derivative has been investigated under both batch and semi-continuous operation in two different reactor types. The system comprises of a bimetallic palladium and copper(II) chloride catalyst contained in a trifluoroacetic acid (TFA) and an aqueous phase. Methane, oxygen and a co-reductant carbon monoxide constitute the gas phase. Typical operating conditions were a temperature of 85 °C and a pressure of 83 bar.

The yields of the methyl trifluoroacetate product observed in this present work were less than those obtained in other batch autoclave works, which employed only 4 ml of liquid phase, compared with 50 ml in this study. Furthermore, an encouraging initial product formation rate of ca. 40 mol/m³ h, quickly decreased after the first hour, and came to an apparent end after only 2 h. This observation had not been reported previously.

Work performed in a semi-continuous porous tube reactor (300 ml of re-circulating liquid phase) also showed the same reaction characteristics as in the batch reactor. Thus, the deteriorating product formation rate cannot be attributed to gaseous reactant depletion (batch operation). The results suggest problems associated with catalyst instabilities, e.g. with the previously elucidated Wacker chemistry.     

固载于SBA-15分子筛中的同双核金属配合物催化剂

合成了3种同双核金属配合物[M2LCl3]Cl(L代表配体三亚乙基四胺,M代表Co,Cu,Cr),采用微波加热法合成了SBA-15分子筛,采用浸渍法将3种同双核金属配合物分别固载在表面官能化的SBA-15分子筛(SBA-15-NH2分子筛)中制得负载型催化剂。傅里叶变换红外光谱、X射线衍射、紫外可见光谱和热分析表征结果表明,同双核金属配合物被固载后,其结构仍保持完整。以环己烷氧化反应为探针反应,考察了[Co2LCl3]Cl/SBA-15-NH2,[Cu2LCl3]Cl/SBA-15-NH2,[Cr2LCl3]Cl/SBA-15-NH2催化剂的活性,环己烷转化率分别为11.0%,49.5%,57.9%;对于[Cr2LCl3]Cl/SBA-15-NH2催化剂,当分别以乙睛、丙酮和冰醋酸为溶剂时,环己烷转化率分别为57.9%,52.1%,34.2%,3次重复实验的环己烷转化率分别为57.9%,47.8%,46.5%,表明该催化剂具有较好的活性和重复使用性。     

Selective oxidation of alcohols using octahedral molecular sieves: influence of synthesis method and property–activity relations

Manganese oxides having a tunnel structure (OMS-2) have been utilized as selective catalysts for alcohol oxidation. In this study manganese oxide catalysts were synthesized in different media and modified by exchanging the tunnel cation by H⁺, using acid treatment or exchanging with NH₄⁺ followed by thermolysis. Various alcohol oxidations were performed using these catalysts to ascertain the influence of synthesis method on their activity. A correlation is made between lattice oxygen instability and activity of the catalysts, which indicates involvement of the lattice oxygen in the mechanism. The exchange of the tunnel cation with the smaller H⁺ ions leads to weakening of the Mn–O bond, as verified by temperature programmed desorption (TPD) results. Only the chemisorbed oxygen on the surface (O⁻) and the lattice oxygen in the layers close to the surface is involved in the oxygen transfer during the reaction.     

One-step oxidation of cyclohexane to adipic acid

Liquid-phase oxidation of cyclohexane with Co(III) catalyst and gaseous oxygen was found to be influenced by reaction temperature, catalyst concentration and the duration. Maximum adipic acid product selectivity (77%) with about 85% cyclohexane conversion was attained at 100°C using catalyst: cyclohexane molar ratio 0·08. Under these conditions more than 80% cyclohexane was converted in the first hour, although selectivity to adipic acid continued to increase for the next 5 h. Cyclohexyl acetate and cyclohexyl monoadipate were identified as important intermediates. This study supports the mechanism proposed by Schultz, J. G. D. and Opchenko, A., J. Org. Chem., 38 (21) (1973) 3729.     

Oxidation of Silicon Carbide in Environments Containing Potassium Salt Vapor

At high temperatures in clean oxidizing environments, SiC forms a very protective SiO₂ film, but, in environments containing low levels of gaseous alkali salt contaminants or where condensed salts may deposit on the surface, the resistance of the film is significantly reduced. Oxidation kinetics of SiC were measured by continuous thermogravimetric analysis in a controlled environment containing CO₂, H₂O, and O₂ plus low levels of potassium-containing salts. Potassium was found to be incorporated into the SiO₂ scale and to significantly change its transport properties and its morphology. The rate of scale formation was found to increase directly in proportion to K in the scale. A change in mechanism was observed when water vapor was added to the reacting gas stream.