Kinetics of the peracetic acid decomposition: Part II: pH effect and alkaline hydrolysis

The effect of pH on the decomposition of peracetic acid in an aqueous solution was studied. It was found that three potential reactions, namely i) the spontaneous decomposition, ii) the hydrolysis and iii) the transition metal catalysed decomposition, are responsible for the consumption of peracetic acid. The spontaneous decomposition reaches its maximum at pH 8.2, while both the hydrolysis and metal ion catalysed decomposition increase as the pH increases. At pH 10.5 and higher, the hydrolysis becomes dominant when the metal ion catalysed decomposition is minimized by the addition of DTMPA. The kinetics of the peracetic acid hydrolysis was developed, which can very well predict the development of peracetic acid and hydrogen peroxide during the decomposition reaction.     

微波作用下天然气水合物分解的研究及应用

介绍了微波和天然气水合物的作用的国内外实验研究进展，说明了微波对天然气水合物的分解有很大的促进作用，分析了用微波加热开采天然气水合物资源、解除天然气输送、开采过程中天然气形成水合物而造成的堵塞等应用的可行性，最后展望了微波在天然气工业中的广泛应用前景。     

一种结合主题模型的推荐算法

针对传统协同过滤推荐算法存在的冷启动、数据稀疏以及相似度度量的准确性问题,基于LDA主题模型对文本隐式主题挖掘的有效性和KL散度在主题分布相似性度量的准确性,提出了结合LDA主题模型的矩阵分解推荐算法。首先,利用改进的LDA算法输出项目-主题分布,并用困惑度作为主题数设置的修正函数;然后分别基于余弦相似度和KL散度计算得到项目相似度矩阵,将得到的相似度矩阵结合原评分训练集输出预评分,再将预评分填充到训练集;最后将训练集输入ALS矩阵分解算法得到推荐结果。通过MovieLens数据集的实验结果表明,该算法在不同隐式参数设定下均能得到比ALS推荐算法以及更小的预测误差,并且最优预测误差小于传统推荐算法。该实验说明了通过集成LDA主题模型的ALS算法效果要优于其他推荐算法。     

交替惩罚三线性分解二阶校正荧光分析法快速测定牛奶中洛美沙星含量

笔者利用化学计量学交替惩罚三线性分解二阶校正算法结合荧光分析,在有干扰药物及牛奶中干扰组分共存下,对牛奶中的洛美沙星进行快速分析测定。当三维荧光数据的预估组分数取4时,所得平均回收率达到99.4%±1.3%,预测方差均方根(RMSP)为2.97nmol/L,预测结果良好。实验结果表明,此法可用于干扰组分共存下牛奶中洛美沙星的快速定量测定。     

Catalytic characteristics of various rubber-reinforcing carbon blacks in decomposition of methane for hydrogen production

Carbon black has recently been reported to act as an effective catalyst for methane decomposition and to exhibit stable catalytic behavior despite carbon deposition, and thus it can be used for CO₂-free production of hydrogen from natural gas. In this work, various carbon blacks with different primary particle size were investigated with respect to methane decomposition under atmospheric pressure from 1123 to 1223 K. Catalytic characteristics, such as activity, activation energy and reaction order, were investigated and compared. It was observed that with decreasing primary particle size (or increasing specific surface area), the specific activity increased and the activation energy decreased. The reaction orders for various pelletized, rubber-reinforcing carbon blacks were 0.6–0.7, about the same regardless of the primary particle size, while they were near 1 for fluffy carbon blacks. Fluffy carbon black showed higher activity and activation energy than the pelletized carbon black of the same primary particle size. Changes of the surface morphology during carbon deposition were observed by TEM. Variations of the number of active sites were discussed in regard of the primary particle size, carbon deposition and binder. The presence of different types of active sites was also suggested.     

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.     

苯甲酸钴的流变相反应法合成及热分解机制研究

用流变相反应合成了苯甲酸钴,通过元素分析、红外光谱和X-射线粉末衍射表征了该配合物,系层状结构,属单斜晶系。用DTA、TG、红外光谱、质谱、X-射线衍射研究了它在氮气气氛中的热分解机理。苯甲酸钴在氮气气氛下,热分解分两步进行:第一步苯甲酸钴分解为碳酸钴和有机化合物,生成的有机化合物成分比较复杂,主要成分是三苯甲烷、二苯甲酮等;第二步碳酸钴进一步分解生成氧化钴和二氧化碳。     

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.     

小型密闭压力容器法中试验条件对分解反应程度的影响

(dp/dt)max是小型密闭压力容器法（MCPVT）中用来表征自反应物质受热分解反应激烈程度的物理量。本文在大量实验的基础上，通过线性回归推导出了X（样品容器容积V、升温速率R及样品质量m）与（dp/dt)max的数学关系式，已知X0时的(dp/dt)max0,就可求得任意X下的（dp/dt)max，与实测值比较，结果表明，利用该关系式计算的结果较为可靠，从而为MCPVT最终成为国际上评价自反应物质受热分解反应激烈程度标准方法奠定了基础。     

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.