Decomposition of nitric oxide over perovskite oxide catalysts: effect of CO2, H2O and CH4

Direct nitric oxide decomposition over perovskites is fairly slow and complex, its mechanism changing dramatically with temperature. Previous kinetic study for three representative compositions (La_0.87Sr_0.13Mn_0.2Ni_0.8O_3−δ, La_0.66Sr_0.34Ni_0.3Co_0.7O_3−δ and La_0.8Sr_0.2Cu_0.15Fe_0.85O_3−δ) has shown that depending on the temperature range, the inhibition effect of oxygen either increases or decreases with temperature. This paper deals with the effect of CO₂, H₂O and CH₄ on the nitric oxide decomposition over the same perovskites studied at a steady-state in a plug-flow reactor with 1 g catalyst and total flowrates of 50 or 100 ml/min of 2 or 5% NO. The effect of carbon dioxide (0.5–10%) was evaluated between 873 and 923 K, whereas that of H₂O vapor (1.6 or 2.5%) from 723 to 923 K. Both CO₂ and H₂O inhibit the NO decomposition, but inhibition by CO₂ is considerably stronger. For all three catalysts, these effects increase with temperature. Kinetic parameters for the inhibiting effects of CO₂ and H₂O over the three perovskites were determined. Addition of methane to the feed (NO/CH₄=4) increases conversion of NO to N₂ about two to four times, depending on the initial NO concentration and on temperature. This, however, is still much too low for practical applications. Furthermore, the rates of methane oxidation by nitric oxide over perovskites are substantially slower than those of methane oxidation by oxygen. Thus, perovskites do not seem to be suitable for catalytic selective NO reduction with methane.     

Prediction of Experimental Methanol Decomposition Rates on Platinum from First Principles

A microkinetic model for methanol decomposition on platinum is presented. The model incorporates competitive decomposition pathways, beginning with both O–H and C–H bond scission in methanol, and uses results from density functional theory (DFT) calculations [Greeley and Mavrikakis, J. Am. Chem. Soc. 124 (2002) 7193, Greeley and Mavrikakis, J. Am. Chem. Soc. 126 (2004) 3910]. Results from reaction kinetics experiments show that the rate of H₂ production increases with increasing temperature and methanol concentration in the feed and is only nominally affected by the presence of CO or H₂ with methanol. The model, based on the values of binding energies, pre-exponential factors and activation energy barriers derived from first principles calculations, accurately predicts experimental reaction rates and orders. The model also gives insight into the most favorable reaction pathway, the rate-limiting step, the apparent activation energy, coverages, and the effects of pressure. It is found that the pathway beginning with the C–H bond scission (CH₃OH→H₂COH→HCOH→CO) is dominant compared with the path beginning with O–H bond scission. The cleavage of the first C–H bond in methanol is the rate-controlling step. The surface is highly poisoned by CO, whereas COH appears to be a spectator species.     

Photocatalysts using hexa- and octa-titanates with different tunnel space for water decomposition

Photocatalytic activities for water decomposition were examined for photocatalysts using hexa- and octa-titanates and TiO2(B) with different tunnel space in the structure. Using RuO2 as promoter, M2Ti6O13 (M = Li, Na, K, Rb) showed the stoichiometric production of Hz and O₂ except for Li, whereas H₂Ti₈O₁₇ and TiO₂(B) had very low activity producing only hydrogen as a product. The effects of promoters on Na₂Ti₆O₁₃ showed that the activity increased in the order of RuO₂ > RuO₂ + IrO₂ > IrO₂ > RuO₂ + Pt > MnO₂. These effects along with other related ones are discussed: it emerges that the presence of the tunnels is important for the achievement of high photocatalytic activity.     

Decomposition of timed automata for solving scheduling problems

A decomposition algorithm for scheduling problems based on timed automata (TA) model is proposed. The problem is represented as an optimal state transition problem for TA. The model comprises of the parallel composition of submodels such as jobs and resources. The procedure of the proposed methodology can be divided into two steps. The first step is to decompose the TA model into several submodels by using decomposable condition. The second step is to combine individual solution of subproblems for the decomposed submodels by the penalty function method. A feasible solution for the entire model is derived through the iterated computation of solving the subproblem for each submodel. The proposed methodology is applied to solve flowshop and jobshop scheduling problems. Computational experiments demonstrate the effectiveness of the proposed algorithm compared with a conventional TA scheduling algorithm without decomposition.     

钛酸铝材料研究进展及应用

钛酸铝是一种优异的高熔点、低膨胀无机非金属材料。主要阐述了钛酸铝材料的微观结构，以及热分解、热膨胀及其影响因素。简述了钛酸铝材料的制备方法。讨论了合成的工艺条件及添加剂对钛酸铝材料性能的影响，并对其应用作了简单介绍。最后提出了改善钛酸铝材料性能的技术途径。     

城市径流总量控制指标分解及实现路径探索与实践

针对海绵城市径流总量控制目标,提出一种在城市规划体系中控制性详细规划和修建性详细规划阶段分解落实年径流总量控制率的方法。在控制性详细规划阶段分解径流总量控制指标时,分步骤先后确定各项低影响开发措施的面积率和下沉深度;在修建性详细规划阶段,配合径流总量控制指标分解结果,给出适宜的各项低影响开发措施的技术实施导则,以保证各单项指标的正确实施,并以某项目为例介绍了技术实施导则的构建方法。     

A study of PtRuO2 catalysts thermally formed on titanium mesh for methanol oxidation

Platinum-based catalysts, for the electro-oxidation of methanol, have been made by thermal decomposition of chloride precursors onto titanium mesh. The catalysed electrodes were successfully operated in acidic methanol electrolytes. Electrochemical characterisation has been carried out using cyclic voltammetry, electrochemical impedance spectroscopy and galvanostatic polarisations. A complete analysis of the electrochemical results showed that the preliminary performance of the catalysed titanium mesh was comparable to that achieved with carbon-supported PtRu catalysts. The catalysts formed on titanium mesh by thermal decomposition also exhibited dimensional stability. Catalysed titanium mesh therefore appears to be a promising alternative to carbon-supported catalysts for certain fuel cell applications.     

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。     

固体推进剂燃烧机理诊断方法的研究进展

介绍和评述了诊断含能材料热分解和推进剂燃烧波结构的方法、仪器和研究进展,以及含能材料和推进剂热分解和燃烧波结构的研究结果,探讨了燃烧机理研究方法的发展方向。提出需要不断完善和更新推进剂燃烧的诊断方法,以获得更为全面的接近真实条件下推进剂燃烧的有效信息。附参考文献14篇。     

Ammonia Decomposition on Ir(100): From Ultrahigh Vacuum to Elevated Pressures

Ammonia decomposition on Ir(100) has been studied over the pressure range from ultrahigh vacuum to 1.5 Torr and at temperatures ranging from 200 to 800 K. The kinetics of the ammonia decomposition reaction was monitored by total pressure change. The apparent activation energy obtained in this study (84 kJ/mol) is in excellent agreement with our previous studies using supported Ir catalysts (Ir/Al₂O₃ 82 kJ/mol). Partial pressure dependence studies of the reaction rate yielded a positive order (0.9±0.1) with respect to ammonia and negative order (–0.7 ±0.1) with respect to hydrogen. Temperature-programmed desorption data from clean and hydrogen co-adsorbed Ir(100) surfaces indicate that ammonia undergoes facile decomposition on both these surfaces. Recombinative desorption of N₂ is the rate-determining step with a desorption activation energy of 63 kJ/mol. Co-adsorption data also indicate that the observed negative order with respect to hydrogen pressure is due to enhancement of the reverse reaction (NH _x + H NH _x+1, x=0–2) in the presence of excess H atoms on the surface.