Active sites in methanol oxidation on Cu(110) determined by STM and molecular beam measurements

STM has been combined with molecular beam rate measurements to gain an understanding of the oxidative dehydrogenation of methanol to produce formaldehyde, both at the macroscopic and microscopic level. From this a model of the reaction is developed where the methanol initial reacts at very few active oxygen sites located at the short sides of oxygen islands on the Cu(110) surface. Such sites are very much rarer on a surface which is saturated with 0.5 monolayers of oxygen and the reaction rate is initially very low, but shows autocatalytic behaviour, rising in time as vacancies are created in the oxygen layer.     

The mechanism of the poisoning of ammonia synthesis catalysts by oxygenates O2, CO and H2O: an in situ method for active surface determination

The effect of adding an oxygenated poison (O₂, CO or H₂O) to a hydrogen/nitrogen stream producing ammonia over a triply promoted (K₂O, CaO, Al₂O₃) commercial catalyst is not unsurprisingly rapidly to poison the catalyst. However, immediately the oxygenated poison reacts with the catalyst and before total poisoning has occurred, which in these experiments took 10 min, there was an explosive release of ammonia producing concentrations in the gas phase in excess of the equilibrium value. This is thought to be due to a convulsive reorganisation of the surface of the catalyst in forming regions of an oxide overlayer, resulting in the expulsion of the standing surface nitrogen atom coverage as ammonia. However, in contradistinction to the observation of complete poisoning of the triply promoted catalyst shortly after switching the water (2.9%) into the hydrogen/nitrogen stream, when polycrystalline iron was used as the catalyst, after the initial pulse of ammonia was observed, the small quantity of water (2.9%) in the hydrogen/nitrogen stream resulted in an increased rate ( ×3) of ammonia synthesis which declined only slightly over the twenty minute duration of the experiment. The difference in behaviour between the triply promoted catalyst and the polycrystalline iron is thought to be due to the relative ease of reduction of the latter, so that submonolayer quantities of oxide can be stabilised on the surface of the polycrystalline iron. The promoting effect of this oxide overlayer is either structural or electronic; no distinction can be made from these experiments. The technique of injecting either O₂ or CO into a hydrogen/nitrogen stream which is producing ammonia over promoted catalysts in quantities insufficient to cause complete poisoning and measuring the oxygen coverage of the catalyst to a measured decrease in the ammonia synthesis rate, appears to be a ready, in situ method for the determination of the active catalyst area.     

H∞ filtering for discrete-time systems subject to stochastic missing measurements: a decomposition approach

This paper deals with the problem of H_∞ filtering for discrete-time systems with stochastic missing measurements. A new missing measurement model is developed by decomposing the interval of the missing rate into several segments. The probability of the missing rate in each subsegment is governed by its corresponding random variables. We aim to design a linear full-order filter such that the estimation error converges to zero exponentially in the mean square with a less conservatism while the disturbance rejection attenuation is constrained to a given level by means of an H_∞ performance index. Based on Lyapunov theory, the reliable filter parameters are characterised in terms of the feasibility of a set of linear matrix inequalities. Finally, a numerical example is provided to demonstrate the effectiveness and applicability of the proposed design approach.     

A trustworthy QoS-based collaborative filtering approach for web service discovery

Many network services which process a large quantity of data and knowledge are available in the distributed network environment, and provide applications to users based on Service-Oriented Architecture (SOA) and Web services technology. Therefore, a useful web service discovery approach for data and knowledge discovery process in the complex network environment is a very significant issue. Using the traditional keyword-based search method, users find it difficult to choose the best web services from those with similar functionalities. In addition, in an untrustworthy real world environment, the QoS-based service discovery approach cannot verify the correctness of the web services’ Quality of Service (QoS) values, since such values guaranteed by a service provider are different from the real ones. This work proposes a trustworthy two-phase web service discovery mechanism based on QoS and collaborative filtering, which discovers and recommends the needed web services effectively for users in the distributed environment, and also solves the problem of services with incorrect QoS information. In the experiment, the theoretical analysis and simulation experiment results show that the proposed method can accurately recommend the needed services to users, and improve the recommendation quality.     

Nano-sized carbon hollow spheres for abatement of ethylene

In this paper, the ethylene adsorption capacities of the nano-sized carbon hollow spheres (CNB) and active carbon (AC), the Pd (PdCl₂) impregnated CNB or AC (Pd/CNB, Pd/AC) and heat treatment under various conditions, were studied at different ethylene concentrations from 64 to 1060 ppm. The results indicated that AC had a good ethylene adsorption capacity at high ethylene concentration. Pd impregnation decreased the ethylene adsorption capacity of AC. Heat treatment and H₂ activation could increase the ethylene adsorption capacity, but also lowered than AC itself. CNB had lower ethylene adsorption capacity than AC, but heat treatment and H₂ activation could increase its ethylene adsorption capacity markedly. With activating condition from heat treatment in N₂ at 300 °C to activation in H₂/N₂ at 100 °C, to activation in H₂ at 200 °C, and to activation in H₂ at 300 °C, the ethylene adsorption capacity of Pd/CNB was increased regularly. At low ethylene concentration, viz., 64 ppm, the ethylene adsorption quantities (q _a) by Pd/CNB activated in H₂ at 200 or 300 °C were higher than any other adsorbents. So, activated in H₂ atmosphere at higher than 100 °C, Pd/CNB is particularly advantaged for adsorbing low concentration of ethylene. Amongst all the adsorbents used, Pd/CNB activated in H₂ atmosphere at 300 °C for 2 h has the highest ethylene adsorption capacity at lower concentration than 125 ppm. In addition, all the CNB, Pd/CNB, AC, and Pd/AC samples can be easily regenerated in airflow for more than 3 h.     

国内外活性氧化锌的进展

叙述了活性氧化锌的简史，特点、应用、生产方法的进展，活性的测定方法及标准。     

原煤流化床法制脱酚活性炭

以煤为原料，采用流化床一步法制取活性炭，考查了煤种、操作条件和矿物质对煤制活性炭脱酚性能的影响。同时综述了这方面的新成果，以期对该法制活性炭的脱酚性能得到全面了解。     

Understanding heterogeneous catalysis on an atomic scale: a combined surface science and reactivity investigation for the dehydrogenation of ethylbenzene over iron oxide catalysts

In order to study the dehydrogenation of ethylbenzene to styrene, epitaxial iron oxide model catalyst films with Fe₃O₄(111), -Fe₂O₃(0001) and KFe _x O _y (111) stoichiometry were prepared in single crystal quality on Pt(111). They were investigated using surface science techniques before and after atmospheric pressure reaction experiments in a newly designed single crystal flow reactor. As expected from low-pressure measurements, Fe₃O₄(111) is catalytically inactive. The catalytic activity of -Fe₂O₃(0001) starts after an activation period of about 45 min. After that, the surface is essentially clean but shows a high concentration of defects. On the potassium-promoted films, however, the activation period is much longer, the activity then is higher and the surface gets covered completely with carbon and oxygen during reaction. This indicates a different reaction pathway on the promoted films with a carbon–oxygen species as catalytically active species.     

由粗氧化锌制备纳米活性氧化锌的研究

采用碳酸氢铵法由粗氧化锌制备纳米活性氧化锌。研究了用碳酸氢铵法由粗氧化锌制备活性氧化锌的热力学、中间体碱式碳酸锌的主要组成和碱式碳酸锌热分解的温度对形貌的影响;考察了中间体碱式碳酸锌的热分解温度和时间对纳米活性氧化锌的纯度、白度、比表面积和表观密度的影响。碱式碳酸锌焙解生成纳米活性氧化锌适宜的温度和时间分别为600℃和1h时,产品中氧化锌的质量分数为97.6%,粒度<100nm,比表面积50m2/g,表观密度0.21g/cm3。     

锅炉水处理系统除氧器的研制

锅炉和循环水处理系统的氧腐蚀是各种腐蚀中最严重的一种。因此，对给水进行除氧处理应该是最有效的防止腐蚀的方法。本文针对新研制出的新型活性铁除氧剂，又研制出与之相配套的除氧设备。该设备具有理想的除氧效果，常温操作，结构简单，弥补了过去一些除氧设备的不足。