【作者】 张晓丰；

【导师】 杨胥微；

【作者基本信息】 吉林大学 ， 物理化学， 2007， 硕士

【摘要】 本论文致力于微分吸附量热技术的研究和对利用微分量热技术在固体酸碱性表征上的应用,以此来获得固体表面酸碱性的定量结果。第一部分介绍了微分吸附量热技术对固体酸碱催化剂表面酸位或碱位的数量、强度的表征方法,以及在酸碱催化剂研究中的重要性和必要性。第二部分介绍了本论文完成过程中所使用的试剂和装置,该套装置是吉林大学第一套建立起来的吸附量热装置。同时介绍了铬酸钴系列催化剂、固态胺树脂和NH2-SBA-15的制备方法。第三部分介绍了铬酸钴系列催化剂进行XRD、红外的实验结果,并对不同Zn/Co条件合成的Zn_xCo_1-xCr₂O₄进行了吸附量热分析。主要从吸附量热的角度考察了不同Zn/Co条件下合成的Zn_xCo_1-xCr₂O₄差别。在苯酚和甲醇邻位烷基化反应中Zn_xCo_1-xCr₂O₄催化剂都表现出了很好的催化活性。通过微量吸附量热分析可以得出Zn_0.5Co_0.5Cr₂O₄催化剂样品表面酸碱位分布比较均匀,酸中心强度较弱但数量较多,碱中心数量较多和强度较大的特点,催化苯酚和甲醇邻位烷基化反应的产率最高。第四部分介绍了不同胺源的固态胺树脂的吸附量热结果以及与NH2-SBA-15相比良好的CO2吸附能力。从定量的角度测量了固体表面的碱中心的数量、强度和分布情况。本论文详细的阐述了不同样品在微分吸附量热方面的酸碱中心的定量分析,从中可以得出论证:吸附量热方法可以作为催化剂表征的一个重要的手段,对催化剂的酸（碱）性和酸（碱）量测定得到很好的定量结果。也可以作为催化剂条件筛选的一个非常实用的监测手段。该论文的创新点即在于用微量吸附量热的方法精确测出了固体表面酸碱中心的定量结果。更多还原

【Abstract】 The number and intension of surface acids and bases are very important parameters when characterizing surface Acidity/Basicity of solid Catalyst. At present, we can acquire the related information by lots of methods, such as TPD, indicator Hamett, IR-Py and microcalorimetric adsorption technique. However, of which,only using the last one can measure the number and intension of surface acid/base sites,quantificationally. Thus, microcalorimetric adsorption technique is useful for characterization of surface Acidity/Basicity of solid Catalyst. We can acquire lots of information to conclude the activity of catalyst, such as the properties of adsorption force, the types of adsorption bond, the reciprocity between degree of consistency and adsorption molecule on the surface of solid, and the intension and number of catalyst activity sites by both measuring and studying microcalorimetric adsorption. Therefore, the data of microcalorimetric adsorption are very important to not only the preparation, characterization and screening of catalyst but also the discussion of it’s mechanism.The microcalorimetric adsorption equipment in this study is established with the help of doctor Shen, Nanjing University, recently. The system is composed of vacuum part and microcalorimetric adsorption part. We can measure differential heat and adsorptive capacity using it, respectively. We perform 1-2μmol sample adsorpted per time using right probe molecule at the optimal temperature, and stop until the sample adsorption is saturated. Finally, we can find that the capacity of microcalorimetric adsorption is changed following the degree of coverage and acquire the information which is about intensity distribution of adsorption centers on the surface of catalyst. In the present study, I operate the quantitive characterization of acidity and basicity sites on the surface of solids using microcalorimetric technique mainly: I have found that that the sites of acidty and basicity are distributed uniformly on the surface of Zn_xCo_1-xCr₂O₄, the strong acid L number is the biggest, meanwhile, there are also a few of the strongest base sites from the microcalorimetric adsorption characterization of Zn_xCo_1-xCr₂O₄ series catalyst. The optimum ratio of Zn and Co is 1. From the acid-base analysis of Zn_xCo_1-xCr₂O₄ series Catalyst using microcalorimetric adsorption technique, we find that the activity sites of ortho alkylation reaction of phenol and methyl alcohol on the suface of Zn_xCo_1-xCr₂O₄ series catalyst should be formed by synergic action. Because there are enough methanol, and carbon ions are provided by a number of bases, the character of strong acid L can determine activities of ortho alkylation reaction of phenol and methyl alcohol （conversion, selectitity and yield）.The microcalorimetric adsorption experimental results of solid amine resin A, solid amine resin B and NH₂-SBA-15 show that solid amine resin A is one of CO₂ absorbing agents, which can be used longly. Comparing with solid amine resin A, the repetitive utilization ratio of solid amine resin B can be arrived at 97%. Moreover, the CO2 adsorbability of solid amine resin B is better, and the repetitive utilization ratio of the base cores is higher. In addition, comparing with NH₂-SBA-15, the acid /base cores of the two solid amine resins are distributed uniformly and closely, the number is bigger, the CO₂ adsorbability is stronger and the distribution of base sites on surface is more reasonable. The number of solid amine resin base core is higher than which of NH₂-SBA-15 shows that the former has advantages of CO2 adsorbability.It is set forth the microcalorimetric adsorption quantitative analysis of acidity and basicity sites of different samples. The results show that microcalorimetric adsorption technique is one of the important methods of catalyst characterization. It is useful to measure the acidity/basicity quantificationally. Moreover, it also can serve as an inspection method of catalyst condition screening.The innovation of the thesis is that the quantitive data of acidity/basicity sites on the suface solid have been measured accurately using microcalorimetric adsorption technique.更多还原