Synthesis, characterization, and catalytic properties of polysiloxanes with pendant 4-(3-pyridinyl)butyl and 4-(1-oxypyridin-3-yl)butyl groups

New silane monomers with the pendant 4-(3-pyridine)butyl group have been synthesized by hydrosilation of 3-(3-butenyl)pyridine with Me _n Si(OEt)_3-n H (n=0, 1) using a platinum catalyst. Only -addition products were observed. The products were characterized by elemental analysis, infrared,¹H- and¹³C-NMR spectroscopy, and gas chromatography-mass spectrometry. Hydrolysis-polycondensation of the difunctional monomer with a basic catalyst, Me₄NOH, gave a mixture of cyclic oligomers, principally cyclic tetramer, and linear homopolymer. Under similar reaction conditions, the trifunctional monomer gave crosslinked material which was soluble in common organic solvents. The linear homopolymer and crosslinked polymer were trimethylsilyl end-blocked with hexamethyldisilazane. The cyclic and end-blocked polymers were characterized by elemental analysis and spectroscopic methods. Molecular weights of the polymers were obtained by end-group analysis using¹H-NMR spectral data, size exclusion chromatography, and direct insertion-probe mass spectrometry. The cyclic, linear, and crosslinked materials were N-oxidized withm-chloroperoxybenzoic acid and characterized by spectroscopic methods. The polymeric N-oxide derivatives were shown to be effective transacylation catalysts in the synthesis of mixed carboxylic acid anhydrides in immiscible solvents (H₂O/CH₂Cl₂) under phase-transfer conditions. The implications of the results on the mechanism of catalysis are discussed.     

Characterization and activity in dry reforming of methane on NiMg/Al and Ni/MgO catalysts

Dry reforming of methane has been investigated on two series of catalysts either prepared by co-precipitation: n(Ni_xMg_y)/Al, Ni_xMg_y and Ni_xAl_y or prepared by impregnation: Ni/MgO (mol% Ni = 5, 10). The catalysts, calcined at 600–900 °C, were characterized by different techniques: BET, H₂-TPR, TPO, XRD, IR, and TEM-EDX analysis. The surface BET (30–182 m² g⁻¹) decreased with increasing the temperature of calcination, after reduction and in the presence of Mg element. The XRD analysis showed, for n(Ni_xMg_y)/Al catalysts, the presence of NiAl₂O₄ and NiO–MgO solid solutions. The catalyst reducibility decreased with increasing the temperature of pretreatment. The n(Ni_xMg_y)/Al catalysts were active for dry reforming of methane with a good resistance to coke formation. The bimetallic catalyst Ni_0.05Mg_0.95 (calcined at 750 °C and tested at 800 °C) presents a poor activity. In contrast, the 5% Ni/MgO catalyst, having the same composition but prepared by impregnation, presents a high activity for the same calcination and reaction conditions. For all the catalysts the activity decreased with increasing the temperature of calcination and a previous H₂-reduction of the catalyst improves the performances. The TPO profiles and TEM-EDX analysis showed mainly four types of coke: CH_x species, surface carbon, nickel carbide and carbon nanotubes.     

Low-temperature catalytic combustion of methane over MnO x –CeO2 mixed oxide catalysts: Effect of preparation method

The effect of preparation method on MnO _x –CeO₂ mixed oxide catalysts for methane combustion at low temperature was investigated by means of BET, XRD, XPS, H₂-TPR techniques and methane oxidation reaction. The catalysts were prepared by the conventional coprecipitation, plasma and modified coprecipitation methods, respectively. It was found that the catalyst prepared by modified coprecipitation was the most active, over which methane conversion reached 90% at a temperature as low as 390 °C. The XRD results showed the preparation methods had no effect on the solid solution structure of MnO _x –CeO₂ catalysts. More Mn⁴⁺ and richer lattice oxygen were found on the surface of the modified coprecipitation prepared catalyst with the help of XPS analysis, and its reduction and BET surface area were remarkably promoted. These factors could be responsible for its higher activity for methane combustion at low temperature.     

混凝土小型空心砌块专用混合砂浆的配制

针对混凝土小型空心砌块的特点,配制出专用混合砂浆.该砂浆未添加外加剂,便于建筑施工.实验结果表明该混合砂浆和易性能良好.该配合比可以作为基准配合比供其它工程借鉴、使用.     

基于粗糙集的载体桩质量核心影响因素分析

针对载体桩质量不容易控制的特点,在剖析载体桩承载机理的基础上,分析了影响载体桩质量的各因素,并引入粗糙集理论,建立了影响因素约简模型。以邯郸地区载体桩工程为例,通过模型约简得出最小的影响因素集,从而确立了影响载体桩质量的核心影响因素,为载体桩的质量预测和控制提供理论依据。结果显示该方法克服了目前人们以主观和定性分析为主的缺点,可信度较高。     

阴极材料Ln-Sr(orCa)-Cu-O的制备及电性能

为了降低原料成本和适于工业化生产,以混合稀土取代氧化镧经硝酸溶解后,共沉淀法分别制备了Sr、Ca掺杂阴极材料Ln-Sr(or Ca)-Cu-O(Ln为混合稀土)的前驱体,在优化条件800℃下煅烧3.5 h形成了粉体,XRD证实形成的物相为CeO2立方萤石相与钙钛矿相。当2θ在20°~30°变化时,Sr2+掺杂使Ln0.5Sr0.5CuO3-δ形成的钙钛矿结构衍射峰相对完整;当2θ在30°~45°变化时,Ca2+掺杂却使Ln0.5Ca0.5CuO3-δ钙钛矿结构衍射峰发生扭曲;而2θ在50°~60°时,Ln0.5Ca0.5CuO3-δ和Ln0.5Sr0.5CuO3-δ衍射峰发生了不同程度的偏移和裂变。直流四探针法对合成产物烧结样品的电导率测量结果表明,在相同条件下,Ln0.5Sr0.5CuO3-δ电导率大于Ln0.5Ca0.5CuO3-δ电导率,在420℃时电导率达到最大值,分别为574和559 S/cm。在中温固体氧化物燃料电池工作温度500~800℃,阴极材料电导率超过500 S/cm,满足电池阴极材料电性能的要求。     

非水MDEA混合溶剂对H_2S的选择性脱除

以小型绝热填料吸收和再生塔组合成实验室模拟脱硫装置,综合评价了添加部分有机溶剂时脱硫剂对脱硫效率及选择性因子的影响.以30%(wt)MDEA水溶液为基准,实验筛选了N—甲基吡咯烷酮(NMP)、乙二醇(EG)等9种有机添加溶剂.综合评价可得,以添加合适的有机溶剂替代大部分水而组成的MDEA非水溶剂具有比MDEA水溶液更高的脱硫选择性,但其脱硫效率略低.     

长短桩复合地基设计计算方法探讨

分别从长桩和短桩作用机理两方面阐述了长短桩复合地基的作用机理。以刚性长桩和柔性短桩组合成的长短桩复合地基为例,对常用的长短桩复合地基承载力计算方法之面积加权法和分步叠加法进行了介绍和对比分析,得出两种方法计算结果的一致性,并通过工程实例进行了验证。对长短桩复合地基沉降计算方法之复合模量法和增大系数法进行了介绍,分析了两种计算方法产生误差的原因,给出了一个采用增大系数法计算长短桩复合地基沉降的工程实例,工程实例计算结果与实际观测结果较吻合。建议采用增大系数法计算长短桩复合地基沉降时有必要对加固区桩间土模量增大系数进行适当修正,修正系数的取值范围需通过对大量工程实例进行分析后确定。     

混合交通下右转机动车信号配时方法

为了减少右转机动车与直行自行车之间的干扰,提高交叉口的运行效率,本文分析了两相位信号控制交叉口右转机动车与自行车之间的冲突规律以及自行车交通流的行驶特性,确定设置右转机动车信号的直行自行车流量临界值.以减少冲突和提高交叉口运行效率为目标,确定右转机动车相位绿灯起亮时刻和绿灯时长,并建立了相应的参数标定模型.以实际调查数据为基础,应用VISSIM模拟软件进行模拟验证,结果表明,设置右转机动车信号后,右转机动车延误和机非冲突明显减少.     

Ti/RuO_2-Co_3O_4阳极析氧性能

为制备高性能析氧电极,采用热分解法在400℃温度下制备Ti/RuO2(x)-Co3O4(1-x)(0≤x≤1,x为Ru的摩尔分数)复合氧化物电极,通过电极开路电压、循环伏安曲线及极化曲线等分析其在1.0mol/LKOH溶液中的析氧催化活性及析氧动力学.结果表明,摩尔分数为10%的RuO2使电极催化活性急剧变化,摩尔分数为50%的RuO2复合氧化物电极具有最大的伏安电荷(429.63mC.cm-2)、最高的表面粗糙度(1786),其析氧性能最佳;Ti/Co3O4在高、低过电位区域电极对OH-的反应级数分别近似为1.0和2.0,含RuO2电极反应级数均为1.0.