含氮碳材料双碱性位与催化脱氯化氢合成偏二氯乙烯性能研究

The development of catalytic dehydrochlorination process of 1,1,2-trichloroethane into vinylidene chloride in gas phase is most wanted to replace the present process of stoichiometric reaction with sodium or calcium hydroxides. In this project, it is proposed to study the dehydrochlorination of 1,1,2-trichloroethane into vinylidene chloride on the acid-proof basic sites, which are composed of nitrogen-containing groups and oxygen-containing species on the surface of N-doped carbon materials. Using the modern characterization methods of catalyst properties and evaluation technology of catalytic performances, study the construction mechanism and matching principle of nitrogen containing group with oxygen containing species for the acid-proof basic sites on the surface of N-doped carbon materials, and also study their physicochemical properties and catalytic dehydrochlorination reaction mechanism. Furthermore, it will be investigated that how to improve the catalytic activity, the selectivity to vinylidene chloride, and the catalyst stability of N-doped carbon materials significantly. The relationship between the properties and catalytic performance of N-doped carbon material will be studied, which is helpful to know the effect of the oxygen-containing species on the properties of nitrogen-containing groups and catalytic performance of N-doped carbon materials. It is necessary to study the reaction kinetics and kinetic parameters of 1,1,2-trichloroethane into vinylidene chloride in gas phase on the N-doped carbon materials catalyst in order to the foundation for the industrial catalyst technology breakthrough and its industrial application. At the same time, the theory results will provide enlightenments for the applications of N-doped carbon materials in catalysis.

原子利用率100%的1,1,2-三氯乙烷气相脱氯化氢制备偏二氯乙烯的催化技术，替代化学计量的碱解（皂化）工艺，意义重大。本项目是在申请者前期研究发现的基础上，提出含氮碳材料中碱性氧物种和含氮基团组成抗酸的碱性位的学术构想，研究两者之间的共构机制和匹配原则；以含氮碳材料催化合成偏二氯乙烯为研究对象，利用现代催化剂表征手段结合催化性能评价技术；研究建立含氮材料催化剂的性质与催化性能之间的关系，优化C/N前驱体和碳化条件；揭示抗酸的碱性位显著提高含氮碳材料的催化活性、选择性、尤其是稳定性的机理，阐明氧物种对含氮基团的性质及其催化性能影响的规律；探证含氮碳材料催化剂的"双分子消去反应"机理和活化模型，发展进一步改善其催化性能的有效途径；研究催化反应历程及条件对反应速率的影响，建立催化反应动力学方程；为该工业催化技术的突破与应用奠定基础。同时，理论上也将为拓宽含氮碳材料在催化中的应用提供启示。

原子利用率100%的1,1,2-三氯乙烷气相脱氯化氢制备偏二氯乙烯的催化技术，替代化学计量的碱解（皂化）工艺，意义重大。本项目在申请者前期研究发现的基础上，提出含氮碳材料中碱性氧物种和含氮基团组成抗酸的碱性位的学术构想，研究两者之间的共构机制和匹配原则；以含氮碳材料催化合成偏二氯乙烯为研究对象，利用现代催化剂表征手段结合催化性能评价技术；研究建立含氮材料催化剂的性质与催化性能之间的关系，优化C/N前驱体和碳化条件；揭示抗酸的碱性位显著提高含氮碳材料的催化活性、选择性、尤其是稳定性的机理，阐明氧物种对含氮基团的性质及其催化性能影响的规律；探证含氮碳材料催化剂的“双分子消去反应”机理和活化模型，发展进一步改善其催化性能的有效途径；研究催化反应历程及条件对反应速率的影响，建立催化反应动力学方程；为该工业催化技术的突破与应用奠定基础。同时，理论上也将为拓宽含氮碳材料在催化中的应用提供启示。