ReO4^—在葡萄糖酸钠介质中还原后的氧化态分布研究

用电位滴定法和萃取法研究了 Ｒｅ Ｏ４－ 在葡萄糖酸钠介质中还原后铼的氧化态分布。实验结果表明,铼氧化态分布主要与酸度和还原剂浓度有关。在 ｐ Ｈ 为 ２０ 的葡萄糖酸钠介质中, Ｒｅ Ｏ４－ 首先被亚锡还原为＋ ５ 价,进一步还原至＋ ４ 价和＋ ３ 价;反应介质的 ｐ Ｈ 值越低, Ｒｅ Ｏ４－ 可被还原至更低价态。     

Processing of Ceramic Based Nanocomposite Using α-Al2O3 Powder and FeCl2 Solution as Starting Materials

Alumina-iron nanocomposite powders were prepared by a two-step process. In the first step, α-Al2O3-FeCl2 powder mixture was formed by mixing α-Al2O3 powders with FeCl2 solution followed by drying. In the second step, the FeCl2 in the dry power mixture was selectively reduced to iron particles. A reduction temperature of 750℃ for 15 min in dry H2 was chosen based on the thermodynamic calculations. The concentration of iron in FeCl2 solution was calculated to be 20 vol. pct in the final composite. Two techniques were used to produce composite bulk materials. The Al2O3 nanocomposite powders were divided to two batches. The first batch of the produced mixture was hot pressed at 1400℃ and 27 MPa for 30 min in a graphite die. To study the effect of oxygen on the Al2O3/Fe interface bonding and mechanical properties of the composite,the second batch was heat treated in air at 700℃ for 20 min to partially oxidize the iron particles before hot pressing. Characterization of the composites was undertaken by conventional density measurements, X-ray diffractometry (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM) and electron probe micro analysis (EPMA). The suggested processing route (mixing, reduction and hot pressing)produces ceramic-metal nanocomposite much tougher than the pure Al2O3. The fracture strength of the produced Al2O3/Fe nanocomposite is nearly twice that of the pure Al2O3. The presence of spinel phase,FeAl2O4, as thick layer around the Fe particles in the Al2O3 matrix has a detrimental effect on interfacial bonding between Fe and Al2O3 and the fracture properties of the composite.     

Effective scheduling strategies for boosting performance on rule-based spam filtering frameworks

Despite the enormous importance of e-mail to current worldwide communication, the increase of spam deliveries has had a significant adverse effect for all its users. In order to adequately fight spam, both the filtering industry and scientific community have developed and deployed the fastest and most accurate filtering techniques. However, the increasing volume of new incoming messages needing classification together with the lack of adequate support for anti-spam services on the cloud, make filtering efficiency an absolute necessity. In this context, and given the extensive utilization and increasing significance of rule-based filtering frameworks for the anti-spam domain, this work studies and analyses the importance of both existing and novel scheduling strategies to make the most of currently available anti-spam filtering techniques. Results obtained from the experiments demonstrated that some scheduling alternatives resulted in time savings of up to 26% for filtering messages, while maintaining the same classification accuracy.     

Unbiased identification of continuous-time parametric models using a time-weighted integral transform

A time-weighted integral transform is presented to identify a continuous SISO or MIMO parametric model based on a single dynamic test under open-loop or closed-loop operation. Moving-horizon algorithms are proposed to obtain unbiased estimates of the model parameters. The off-line algorithm in a least-squares form and the on-line algorithm in a recursive form are provided. An effective technique based on pattern recognition is also developed to determine the system order and time delay from observed data in a simple manner. Furthermore, the proposed method can be easily applied as a model reduction technique that results in an ideal model with delay for any specified order.     

A301型氨合成催化剂还原动力学的研究

在热天平上研究了Ａ３０１型铁基氨合成催化剂的还原动力学，考察了还原条件对Ａ３０１型催化剂还原速率的影响，分析了氢对还原速率的反应级数在还原进行中发生的变化，以及Ａ３０１型和Ａ１１０－２型二种催化剂还原过程中反应级数变化规律不同的内在原因。实验结果表明：Ａ３０１型催化剂具有极易还原的性能，还原速率对温度及氢浓度的变化的敏感性比Ａ１１０－２型催化剂弱，其还原反应动力学方程上。文中（４）式。     

Photocatalytic decoloration of water-soluble azo dyes by reduction based on bisulfite-mediated borohydride

Investigation of the photocatalytic decoloration of nine water-soluble anionic azo dyes widely used for the coloration of textiles was conducted in a photoreactor by a selected reduction based on bisulfite-mediated borohydride. The influence of the irradiation power on their decoloration was discussed in this work. The decoloration processes of two typical azo dyes, Reactive Red MS and C.I. Direct Blue 15 were examined with UV–vis measurement and their decoloration kinetics was also investigated. Moreover, identification of benzidine compounds released from the photoreduction of four direct dyestuffs was undertaken. The results indicated that the reduction of the dyes was significantly enhanced under the increasing irradiation. It was found that the overall degradation followed pseudo-first-order kinetics and two distinct stages were observed in the decoloration processes of Reactive Red MS and C.I. Direct Blue 15. The decay rates at first stage were slightly changed, but the decay rates at second stage were significantly affected by the light intensity. In addition, UV–vis spectra showed that the azo linkages in molecule structure of the dyes were destroyed during the decoloration. Finally, dimethoxyl benzidine or benzidine produced from the photoreduction of four direct dyes was identified as the decoloration products through a rapid spectrophotometric method.     

含锌铅粉尘配碳球团中氧化铁还原动力学

在氮气气氛和１０５０～１３００℃温度范围内，采用化学分析方法研究了还原温度、过量碳及煤粉粒度对含锌铅粉尘配碳球团中氧化铁还原速率的影响．结果表明：还原温度对氧化铁还原速度有显著影响，过量碳和煤粉粒度对还原速率没有影响．在不同还原程度和还原温度下，得出了氧化铁还原的表观活化能，由活化能结果和还原动力学模型对实验结果进行分析，确定了氧化铁在不同还原程度和还原温度下的还原限制性环节．     

复合金属氧化物脱硫剂还原法再生机理

利用热天平测试了ＣＯ、Ｈ２还原饱和脱硫剂微孔内Ｆｅ２（ＳＯ４）３的起始反应温度及还原速率，用Ｘ射线衍射法分析了反应中间产物及最终产物．实验结果表明，脱硫剂还原法再生的反应温度较传统热分解法低约２００℃，ＣＯ作再生脱硫剂的还原气体优于Ｈ２，ＣＯ还原脱硫剂内Ｆｅ２（ＳＯ４）３的反应级数为０．８７，活化能为１４２．９ｋＪ／ｍｏｌ．     

Microstructure of Pd/CeO2 catalyst: Effect of high temperature reduction in hydrogen

The effect of high temperature reduction (HTR) in hydrogen (up to 1180 K) on the microstructure of 9 wt.-% Pd/CeO₂ catalyst was studied by HRTEM and XRD methods. Reduction of the catalyst at or above 973 K caused severe recrystallization of CeO₂ and Pd with simultaneous strong interaction between the two components appearing as three phenomena: epitaxial growth of small Pd particles on CeO₂ (most frequently with [111]Pd[111]CeO₂); decoration of large Pd particles with ordered CeO₂ overlayer and expansion of the lattice parameter of Pd (by 2.1%). The origin of the Pd lattice expansion is discussed and diffusion of Ce species into the Pd lattice seems to be the most probable one. HTR caused also phase transformations in the ceria support. At 973 K and 1100 K, whole CeO₂ was transformed into oxygen deficient CeO_x phase exhibiting the same or similar structure but with expanded lattice parameter (by 2.8%). At 1180 K most ceria was transformed into hexagonal A-Ce₂₃. The CeO_x phase appeared to be stable in hydrogen and in vacuum at room temperature, but upon exposure to air at room temperature it rapidly reoxidised to CeO₂. Ce₂O₃ also reoxidised to CeO₂ but much slower. Another consequence of HTR at or above 773 K was formation of pits in CeO₂ crystallites, mainly on (112)-type crystal faces. The pits (1–10 nm) exhibited well defined walls parallel to CeO₂ lattice fringes and they could possibly constitute nucleation sites for strongly bonded, epitaxial oriented Pd particles.     

Catalytic reduction of no over perovskite-type catalysts

In the present work, we have investigated the reduction of NO by propane over perovskite-type oxides prepared by malic acid method. The catalysts were modified to enhance the activity by substitution of metal into A or B site of perovskite oxides. In addition, the reaction conditions, such as temperature, O₂ concentration, and space velocity have been varied to understand their effects on the catalytic performance. In the LaCoO₃ type catalyst, the partial substitution of Ba and Sr into A site enhanced the catalytic activity in the reduction of NO. For the La_0.6Ba (Sr)_o.4 Co_1−x Fe_xO₃ (x=0-1.0) catalyst, the partial substitution of Fe into B site enhanced the conversion of NO, but excess amount of Fe decreased the conversion of NO. The surface area and catalytic activity of perovskite catalysts prepared by malic acid method showed higher values than those of solid reaction method. The conversion of NO increased with increasing O₂ concentration and contact time. The introduction of water into reactant feed decreased the catalytic activity but the deactivation was shown to be reversible over La_0.6Ba_0.4Co_1−x ,Fe_xO₃ catalyst.