Improved electrochemical redox performance of 2,5-dimercapto-1,3,4-thiadiazole by poly(3-methoxythiophene)

High electrocatalytic activity of an electropolymerized film of poly(3-methoxythiophene) (PMOT) is reported toward the redox reaction of 2,5-dimercapto-1,3,4-thiadiazole (DMcT) as a promising cathode material for the lithium ion battery. Cyclic voltammetry showed improved electrochemical performance of DMcT on PMOT-coated Pt electrode, indicating accelerated redox kinetics. Moreover, charge-discharge tests exhibited higher discharge capacity and slower capacity fading of the PMOT-doped DMcT composite cathode compared with pure DMcT.     

纤维增强刚玉耐火材料制备及其显微结构

采用国产硅酸铝纤维和多晶莫来石纤维，利用传统的工艺制备了纤维增强氧化铝基耐火材料。研究了纤维的种类、加入量对其性能的影响，进行了显微结构的初探。结果表明，纤维引入耐火基质中能显著地提高材料的强度，且随着纤维加入量的增加试样强度大幅度增加。试样中的纤维经1500℃烧后仍交错分散在基质中。     

Heterogeneous asymmetric reactions. 23. Enantioselective hydrogenation of ethyl pyruvate over cinchonine- and α-isocinchonine-modified platinum catalysts

The enantioselective hydrogenation of ethyl pyruvate to (S)-ethyl lactate over cinchonine- and -isocinchonine-modified Pt/Al₂O₃ catalysts was studied as a function of modifier concentration and reaction temperature. The maximum enantioselectivities obtained under the applied mild conditions were 89% ee using cinchonine (0.014 mmoldm^–3, 1 bar H₂, 23°C, 6% AcOH in toluene), and 76% ee in the case of -isocinchonine (0.14 mmoldm^–3, 1 bar H₂, –10°C, 6% AcOH in toluene). Since -isocinchonine of rigid structure exists only in anti-open conformation these data provide additional experimental evidence to support the former suggestion concerning the dominating role of anti-open conformation in these cinchona-modified enantioselective hydrogenations.     

Electrical properties of V2O5–WO3/TiO2 EUROCAT catalysts evidence for redox process in selective catalytic reduction (SCR) deNOx reaction

Electrical conductivity measurements on EUROCAT V₂O₅–WO₃/TiO₂ catalyst and on its precursor without vanadia were performed at 300°C under pure oxygen to characterize the samples, under NO and under NH₃ to determine the mode of reactivity of these reactants and under two reaction mixtures ((i) 2000 ppm NO + 2000 ppm NH₃ without O₂, and (ii) 2000 ppm NO + 2000 ppm NH₃ + 500 ppm O₂) to put in evidence redox processes in SCR deNO_x reaction.It was first demonstrated that titania support contains certain amounts of dissolved W⁶⁺ and V⁵⁺ ions, whose dissolution in the lattice of titania creates an n-type doping effect. Electrical conductivity revealed that the so-called reference pure titania monolith was highly doped by heterovalent cations whose valency was higher than +4. Subsequent chemical analyses revealed that so-called pure titania reference catalyst was actually the WO₃/TiO₂ precursor of V₂O₅–WO₃/TiO₂ EUROCAT catalyst. It contained an average amount of 0.37 at.% W⁶⁺dissolved in titania, i.e. 1.07 × 10²⁰ W⁶⁺ cations dissolved/cm³ of titania. For the fresh catalyst, the mean amounts of W⁶⁺ and V⁵⁺ ions dissolved in titania were found to be equal to 1.07 × 10²⁰ and 4.47 × 10²⁰ cm⁻³, respectively. For the used catalyst, the mean amounts of W⁶⁺ and V⁵⁺ ions dissolved were found to be equal to 1.07 × 10²⁰ and 7.42 × 10²⁰ cm⁻³, respectively. Since fresh and used catalysts have similar compositions and similar catalytic behaviours, the only manifestation of ageing was a supplementary progressive dissolution of 2.9 × 10²⁰ additional V⁵⁺ cations in titania.After a prompt removal of oxygen, it appeared that NO alone has an electron acceptor character, linked to its possible ionosorption as NO⁻ and to the filling of anionic vacancies, mostly present on vanadia. Ammonia had a strong reducing behaviour with the formation of singly ionized vacancies. A subsequent introduction of NO indicated a donor character of this molecule, in opposition to its first adsorption. This was ascribed to its reaction with previously adsorbed ammonia strongly bound to acidic sites. Under NO + NH₃ reaction mixture in the absence of oxygen, the increase of electrical conductivity was ascribed to the formation of anionic vacancies, mainly on vanadia, created by dehydroxylation and dehydration of the surface. These anionic vacancies were initially subsequently filled by the oxygen atom of NO. N^o atoms, resulting from the dissociation of NO and from ammonia dehydrogenation, recombined into dinitrogen molecules. The reaction corresponded to

Full-size image

. In the presence of oxygen, NO did not exhibit anymore its electron acceptor character, since the filling of anionic vacancies was performed by oxygen from the gas phase. NO reacted directly with ammonia strongly bound on acidic sites. A tentative redox mechanism was proposed for both cases.     

常温电沉积Fe—P—Al2O3复合镀层新工艺的研究

研究确定了常温下获得Fe-P-Al_2O_3复合电镀层的新工艺,获得的镀层光亮、致密、无裂纹,Al_2O_3颗粒的含量为5％～35％(vol),镀层显微硬度Hv=800～1100N/mm~2,耐磨性能比低温镀铁层提高5～10倍。     

HCl-NH3双组分催化正硅酸乙酯快速制备SiO2气凝胶

以正硅酸乙酯(TEOS)为原料,水和乙醇为溶剂,盐酸和氨水为催化剂,采用溶胶-凝胶法制备了SiO2气凝胶.研究了水和乙醇及催化剂对制备SiO2气凝胶反应速度、凝胶时间的影响.结果表明HCl和NH3·H2O作为催化剂大大加速了溶胶和凝胶反应速度,使凝胶时间减少至几分钟甚至更短,所制备的SiO2气凝胶具有纳米多孔结构(骨架颗粒为15～20nm,孔洞尺寸为10～30 nm).     

Electrical properties of (Bi3.5La0.5)Ti3O12 thin-films prepared by liquid source misted chemical deposition

The ((Bi_3.5La_0.5)Ti₃O₁₂(BLT) thin-films used in this study were fabricated on a Pt(111)/SiO₂/Si(100) substrate by a Liquid Source Misted Chemical Deposition (LSMCD) technique. X-ray diffraction patterns showed that the BLT films were crystallized and no other phases were observed when annealed above 650 ‡C. Grain size and remnant polarizations increased with increase in the annealing temperature, while leakage current densities decreased. The remnant polarizations (Pr) increased from 2.0 to 4.8 and 19.0 μC/cm2 with increase in the annealing temperature from 650 to 700 and 750 ‡C, respectively. The BLT films annealed at 700 ‡C in O₂ showed a good fatigue resistance of reduced polarization by 10% after 10⁹ switching cycles when 9 V of bipolar voltage was applied at a frequency of 40 kHz.     

海上溢油漂移扩散的数值模拟

该文基于三维自由水面垂向分层动网格的Euler-Lagrangian模式,采用VC方式(Vertex-Centered)的非结构化有限体积方法离散三维浅水方程,模拟渤海的潮汐水流运动过程。以此为水动力背景场,采用油、水分离的Lagrangian粒子追踪模型,对渤海海域发生的溢油漂移扩散问题进行模拟。其油品的蒸发、乳化和溶解等风化作用以引入综合衰减系数的方式考虑。模型对油膜的漂移路径、厚度和面积进行了实时模拟和预测,用多个测站的同步连续实测值对水动力模式进行了参数率定与模型验证,油膜输运扩散的计算结果也与相关报告数据进行了对比,均吻合良好,说明模型具有较高的可靠性与重现性。     

三维激光扫描技术在引水隧洞检修中的应用

三维激光扫描技术是国际上近年发展的一项集光、电和计算机技术于一体的新技术,利用该技术可以快速、精确地获取空间数据。锦屏二级水电站引水隧洞放空检修时发现少数洞内存在混凝土破损情况,但受时间与费用等因素限制,难于以采用常规手段详细检查混凝土表面缺陷与变形等问题。通过采用三维激光扫描技术对隧洞进行全断面扫描,及时探查了混凝土表面的缺陷并进行了处理,确保了工程安全运行;同时,还得到混凝土表面的三维坐标信息,建立了混凝土表面缺陷基准数据库,可为后续进一步分析混凝土表面缺陷的变化情况提供参考。     

潮汐双向流条件下丁坝水流特性研究

以长江口南支河段为原型,概化并建立水槽数学模型,研究径潮双向流条件下丁坝附近的水流结构。研究表明:丁坝一侧河岸,丁坝下游潮差远大于上游,在丁坝上游潮差小于对岸侧,下游潮差大于对岸侧;落潮时,丁坝回流区与壅水区长度大于涨潮,转流时刻,丁坝坝头附近流速相对较大;河床底部剪切应力变化在涨落急时刻最大,且落潮大于涨潮,转流时刻坝头及坝身迎水侧剪切应力增加明显。