氧化钛负载脱硝催化剂的碱中毒过程：氧化钒的保留和氧化钨的牺牲

V2O5-WO3/TiO2催化剂目前已广泛用于电厂和工业锅炉燃烧废气脱硝,但燃烧原料煤及石油中含有的杂质元素碱金属与碱土金属元素可吸附在催化剂上,不仅会减少催化剂酸性位的数量,还会与催化活性元素结合生成惰性物种,导致催化剂失活。因此,已有许多有关钒钨钛催化剂碱中毒的研究,从催化剂的氧化还原能力、酸性位损失及表面孔结构等方面进行了讨论。但这些研究大多集中在碱中毒对活性组分V2O5的影响及中毒催化剂的活性变化,很少涉及催化剂中WO3的作用,也缺乏有关不同活性元素与钾盐反应的实验证据。本文采用过量浸渍法制备了不同钒和钨含量的钒钨钛催化剂,研究了氯化钾对其氨法选择性催化还原(NH3-SCR)活性的失活效应。利用感应耦合等离子体、N2吸附、拉曼光谱、H2程序升温还原、NH3吸附红外光谱和NH3氧化活性等手段对新鲜和中毒催化剂的性质进行了表征,特别探讨了V2O5和WO3对催化剂抗碱中毒能力的贡献。
　　催化剂活性测试结果表明, V2O5含量越高,活性温度窗口越宽,而且含有WO3的三元催化剂活性高于V2O5/TiO2二元催化剂。催化剂的BET比表面积和孔结构取决于TiO2载体,随活性组分配比变化不大,说明催化剂物理结构性质并非影响活性的主要因素。原位红外光谱及H2程序升温还原测试结果表明,随V2O5含量提高,催化剂表面Br?nsted酸性位数量及氧化还原能力提高。作为反应的主要活性物种, V2O5在碱中毒处理后变成惰性的偏钒酸钾KVO3,使催化剂中Br?nsted酸性位减少,热稳定性下降,并削弱了催化剂的氧化还原能力,因此低钒含量的催化剂容易严重中毒失活。在高钒负载量(3%)时,部分V2O5在碱中毒后得以保留,从而使催化剂保持了一定的脱硝催化活性。
　　另外, WO3能给催化剂表面提供热稳定的酸性位,虽然WO3自身的氧化还原能力差,但其能改善V2O5的分散性,从而提高V2O5-WO3/TiO2催化剂的活性。除此之外, WO3在催化剂碱中毒过程中还能扮演牺牲剂,与钾反应生成钨酸钾(K2WO4),即在V2O5与钾离子结合形成KVO3的同时,部分WO3也会与钾反应形成K2WO4,可以使三元催化剂保留更多的活性V物种。因此,在所研究的催化剂中,高钒负载量的V2O5-WO3/TiO2催化剂表现出最好的抗碱中毒能力。
　　活性影响因素分析表明,对于新鲜催化剂,其表面吸附的NH3量足够多,催化剂活性与表面酸性相关度不大,脱硝效率主要取决于催化剂的氧化还原能力。但是,对于碱中毒处理后的催化剂,其表面吸附NH3的能力大大削弱,这时脱硝效率除了受催化剂氧化还原能力影响,在很大程度上也依赖于催化剂的表面酸性。     

Synthesis and Thermal Performance of Polyurea Microcapsulated Phase Change Materials by Interfacial Polymerization

Microencapsulated phase change materials with paraffin as the core material were synthesized by interfacial polymerization of isophorone diisocyanate with diethylene triamine. The particle size and particle size distribution, morphology, thermal performance and the encapsulation efficiency of the prepared materials were investigated. The results of Fourier transform infrared spectrometer and X-ray photoelectron spectroscopy suggested that the paraffin core was well encapsulated by the polyurea resin. The particle size of the prepared materials decreased and its distribution became narrow with the increase of the emulsification time, stirring speed and emulsifier amount. The thermal gravimetric analysis indicated that the prepared materials exhibited good thermal stability, while the differential scanning calorimetry their high encapsulation efficiency.     

The Influence of Moduli Slope of a Linearly Graded Matrix on the Bulk Moduli of Some Particle- and Fiber-Reinforced Composites

The stored energy functional of a homogeneous isotropic elastic body is invariant with respect to translation and rotation of a reference configuration. One can use Noether's Theorem to derive the conservation laws corresponding to these invariant transformations. These conservation laws provide an alternative way of formulating the system of equations governing equilibrium of a homogeneous isotropic body. The resulting system is mathematically identical to the system of equilibrium equations and constitutive relations, generally, of another material. This implies that each solution of the system of equilibrium equations gives rise to another solution, which describes the reciprocal deformation and solves the system of equilibrium equations of another material. In this paper we derive conservation laws and prove the theorem on conjugate solutions for two models of elastic homogeneous isotropic bodies – the model of a simple material and the model of a material with couple stress (Cosserat continuum). This revised version was published online in August 2006 with corrections to the Cover Date.     

高质量高取向(100)面金刚石膜的可控性生长

应用微波等离子体化学气相沉积技术, 在低气压下对(100)晶面金刚石膜的表面形貌、质量、取向和生长率进行了可控性生长研究. 结果表明: 基片温度与甲烷浓度对(100)晶面金刚石膜的生长存在耦合规律. 为了获得表面形貌相似的(100)晶面金刚石膜, 在沉积过程中, 增加碳源浓度的同时需要同时升高基片温度; 当甲烷浓度为3.0%, 基片温度从740 ℃上升至1100 ℃ 的过程中, 金刚石膜的晶面取向变化可分为五个阶段, 其中当基片温度在860 ℃至930 ℃时, 很适合高取向(100)晶面金刚石膜生长; 另外, 金刚石膜的质量和生长速率分别与基片温度和甲烷浓度成正比. 为了获得高质量高取向(100)晶面金刚石膜, 应当选择合适的基片温度和甲烷浓度.     

Blocking group-directed diastereoselective total synthesis of (±)-α-noscapine

A new approach for the diastereoselective synthesis of (±)-α-noscapine, a phthalide tetrahydroisoquinoline alkaloid exhibiting several biological activities, is described. The strategy features a blocking group-directed Bischler-Napieralski reaction followed by diastereoselective reduction (α/β>23:1). One of the key intermediates, phthalide-3-carboxylic acid, could be efficiently prepared from simple benzoic acid derivative and glyoxylic acid in one-pot.     

IRAP: An efficient retrotransposon-based electrophoretic technique for studying genetic variability among geographical isolates of Schistosoma japonicum

In the present study, a inter-retrotransposon-amplified polymorphism (IRAP) technique, based on retrotransposons, was used to examine genetic variability among Schistosoma japonicum isolates from different provinces in mainland China. Of the 15 primers screened, 5 produced highly reproducible IRAP patterns. Using these primers, 54 discernible DNA fragments were generated with 40 (74.07%) being polymorphic, indicating considerable genetic variation among the examined S. japonicum isolates. The primer LTR-11 was found to be able to differentiate male and female parasites, producing one constant specific band for female S. japonicum isolates. The percentages of polymorphic bands (PPB) among all parasites, among isolates from mountainous provinces and among those from the lake/marshland areas were 74.07, 48.15, and 66.67%, respectively. UPGMA analysis revealed that the IRAP profiles could group S. japonicum isolates in mainland China into two clades (mountainous and lake/marshland types), and samples from the same geographical origins clustered together. These results demonstrated that the IRAP technique is suitable for studying genetic diversity and population structures, and also provides an effective technique for studying sex differentiation of S. japonicum.     

Adsorption and dissociation of NH3 on clean and hydroxylated TiO2 rutile (110) surfaces: a computational study

The adsorption and dissociation of NH(3) on the clean and hydroxylated TiO(2) rutile (110) surfaces have been investigated by the first-principles calculations. The monodentate adsorbates such as H(3)N-Ti(a), H(2)N-Ti(a), N-Ti(a), H(2)N-O(a), HN-O(a), N-O(a) and H-O(a), as well as the bidentate adsorbate, Ti-N-Ti(a) can be formed on the clean surface. It is found that the hydroxyl group enhances the adsorption of certain adsorbates on the five-fold-coordinated Ti atoms (5c-Ti), namely H(2)N-Ti(a), HN-Ti(a), N-Ti(a) and Ti-N-Ti(a). In addition, the adsorption energy increases as the number of hydroxyl groups increases. On the contrary, the opposite effect is found for those on the two-fold-coordinated O atoms (2c-O). The enhanced adsorption of NH(x) (x = 1-2) on the 5c-Ti is due to the large electronegativity of the OH group, increasing the acidity of the Ti center. This also contributes to diminish the adsorption of NH(x) (x = 1-2) on the two-fold-coordinated O atoms (2c-O) decreasing its basicity. According to potential energy profile, the NH(3) dissociation on the TiO(2) surface is endothermic and the hydroxyl group is found to lower the energetics of H(2)N-Ti(a)+H-O(a) and HN-Ti(a)+2{H-O(a)}, but slightly raise the energetic of Ti-N-Ti(a)+3{H-O(a)} compare to those on the clean surface. However, the dissociation of NH(3) is found to occur on the hydroxylated surface with an overall endothermic by 31.8 kcal/mol and requires a barrier of 37.5 kcal/mol. A comparison of NH(3) on anatase surface has been discussed. The detailed electronic analysis is also carried out to gain insights into the interaction nature between adsorbate and surface.     

Applying magnetic soft mold imprint technology with ultraviolet light‐emitting‐diode array on the fabrication of microlens arrays

This study proposed a novel technology, which uses exposed technology with ultraviolet light‐emitting‐diode (UV‐LED) arrays and the polydimethylsiloxane (PDMS) magnetic flexible soft mold imprint technology, to develop exposed equipments with UV‐LED arrays. This study used magnetic soft mold imprint technology to replicate the structure of microlens, providing a more effective alternative for imprint technology and application. The measurement results showed that PDMS with magnetic iron powder can precisely cast mold to replicate the structures of microlens. Electromagnetic plates were used to control even imprinting with magnetic force, in order to fill the mold of micro‐structure of the photo‐resist. Magnetic iron powder was added to PDMS to produce composite material, which can effectively avoid the transformation of pure PDMS during soft mold imprinting, and increase mechanical strength. Magnetic PDMS soft mold is easy to make, and the casting time is short, so that costs can be effectively reduced. Also with advantages of less free energy on its surface, and unlikely to adhere to the photo‐resist during imprinting, it can be combined with electromagnetic plates evenly to control the magnetic soft mold. This imprinting technology is a big advantage to the production process of micro‐structures during imprinting. Copyright © 2009 John Wiley & Sons, Ltd.     

EXISTENCE AND GLOBAL ATTRACTIVITY OF ALMOST PERIODIC SOLUTION TO A DELAYED DIFFERENTIAL EQUATION

A new fixed point theorem is presented and sufficient conditions are obtained for the existence, uniqueness and global attractivity of a positive almost periodic solution to a delayed differential equation with almost periodic factors.