丙烯酸甲酯/乙烯基吡啶共聚物铑配合物的配体空间结构对甲醇羰基化反应催化性能的影响

针对共聚物配体聚合的随机性及其共聚结构单元的复杂性 ,运用XPS及红外光谱等分析手段 ,探讨了共聚物铑配合物微观结构对催化性能的影响 ;研究了丙烯酸甲酯 2-乙烯基吡啶和丙烯酸甲酯 4-乙烯基吡啶两种共聚物与铑的不同配比的配合物的活性,考察了相同配比的共聚物配合物结构单元、温度等因素对消化活性的影响 ,为催化剂结构的合理设计提供了理论参考.     

可再分散乳胶粉对抗裂抹面砂浆的影响

通过对含有不同掺量可再分散乳胶粉的抗裂抹面砂浆的试验,得出相应的抗裂抹面砂浆的拉伸粘结强度,绘制出可再分散乳胶粉掺量变化时拉伸粘结强度的变化曲线,得出了抗裂抹面砂浆的拉伸粘结强度和可再分散乳胶粉掺量的变化规律,研究结果为配制不同应用要求的抗裂抹面砂浆提供了一些基础试验数据和参考.     

N-[2-(2-吡啶)乙基]苯胺及其COCl_2配合物的晶体结构及配体的构象研究

本文制备了二氯[N-(2-吡啶乙基)苯胺]钴配合物,并用 X 射线衍射法测定了配合物及配体的晶体结构。结合 EHMO 和 DPCILO 计算,从能量角度,跟踪配体从构象1(配体的晶态构象)变至构象2(配体在配合物中的晶态构象)的变化过程。     

气相色谱的定量分析方法Ⅰ.以空气作标准的热导池气相色谱定量方法的研究

本文在相对灵敏度理论基础上,提出以空气作相对标准的气相色谱定量方法,并引进空气标定因子作为应用这一方法的定量参数.有关气体在热导池检测器中的空气标定因子,根据Novák提出的相对克分子响应关系式 [1] 计算得到的结果,其准确度可以满足一般情况下热导池气相色谱定量分析的精度要求.     

2—乙烯基吡啶—甲基丙烯酸甲酯共聚物的链结构与其铑络合物对烯烃催化加氢性能的关系

本工作定量测定了2-乙烯基吡啶-甲基丙烯酸甲酯-铑络合物的烯烃催化加氢性能与共聚物配体序列结构的关系。同时根据共聚物的微结构三元组分布数据对催化剂的络合状态进行了探讨。实验结果证明,催化剂的活性随共聚物配体中以甲基丙烯酸甲酯为中心的三元组F_(MMM),F_(MMV+)含量增加而提高。而稳定性则随以2—乙烯基吡啶为中心的三元组F_(VVV),F_(VVM+)含量增加而提高。     

A catalyst for the carbonylation of methanol to acetic acid in gaseous phase

A novel Rh/Ys catalyst for the carbonylation of methanol to acetic acid in gaseous phase is reported. The porous carbon beads (Ys) prepared from the carbonation of poly(vinylidene chloride) were used as the support. This catalyst has a specific surface area of 1 000 m2/g, high mechanical strength and thermal stability. The average diameter of the pore is in the range of 0.8 - 1.2nm. Experimental evidence showed that this catalyst was of high activity and selectivity, which could compare to those of the homogeneous catalyst from Monsanto. The catalytic rate could get to 900 g AcOH/g Rh·h during the carbonylation of methanol to acetic acid. The fine spreading of Ph over the Ys surface is the key factor for the activity.     

Kinetic studies on vapor phase carbonylation of methanol to acetic acid over Rh/Ys catalyst

A novel catalyst Rh/Ys for the carbonylation of methanol to acetic acid with CH3I as the promoter shows excellent activity and selectivity.The reaction is kinetically controlled.The reaction rate is in proportion to the concentration of Rh and CH3I but has nothing to do with those of CH3OHH and CO.The surface active energy is Ea ~51.02 kJ/mol.A mechanism is also proposed.     

含未配位原子的铑配合物的催化活性及其稳定性研究

合成一种有特殊稳定性的新的铑配合物 ,通过对其结构及表征数据的研究 ,发现含未配位原子是其高稳定性的主要原因所在。因为中心原子铑和它附近的未配位原子能发生分子内取代反应从而避免了铑由于失去羰基造成的分解损失。为了证实 ,同时用一种和它结构相似但没有未配位原子的铑配合物进行了对比。结果证实 ,未配位原子的存在增加了催化甲醇羰基化的配合物的稳定性。     

介孔ZnO/SiO2复合材料的合成与性能表征

通过原位合成的方法,以[Zn(OH)x]-(x-2)(x＞2)为锌源、正硅酸乙酯(TEOS)为硅源,合成了孔壁为ZnO/SiO2复合结构的MCM-48型有序介孔分子筛,并通过XRD、XPS、N2吸附-脱附等温线等手段对样品进行了表征,结果表明,锌以正二价离子的形式均匀的分布在MCM-48分子筛的孔壁结构中.另外,适量掺锌所合成的Zn-MCM-48介孔材料仍然保持立方介孔的有序结构,具有较高的比表面积、较高的孔容和较宽的孔径分布.     

Relationship between surface microstructure and properties of supported catalyst Rh/Ys

The inner structure of Rh/Ys,a novel high efficiency supported catalyst,and the spreading of Rh on the Ys surface were analyzed through electron transmission microscopy and scanning tunnel microscopy.The relationship between the distribution of Rh over the support and the preparation temperature of th catalyst was determined.The formation of Rh-C bond was confirmed by XPS and far-IR spectra.The loss of Rh from the surface of the support and the catalytic activity under different preparation conditions have been compared.The internal factors for the high activity and high stability of the novel Rh/Ys catalyst have been discussed.