二氧化碳气氛中纳米碳材料非金属催化烷烃氧化脱氢的研究

Recently, nanocarbon materials as catalysts attracted a growing interest for researchers. Lots of studies indicated that nanocarbon materials show good activity,selectivity and stability in catalytic oxidative dehydrogenation of hydrocarbon reactions, which shows great potential application of nanocarbon catalysts in chemical industry to replace traditional metal catalysts. However, There are still lots of problems in this catalytic system, especially to develop the new green oxidant to replace the O2. This project is mainly focused on studying the nano-carbon materials catalytic oxidative dehydrogenation of hydrocarbon under CO2. We want to employ CO2 as a mild oxidant, suppressing the generation of by-product and promoting the selectivity of alkene. Besides, CO2 can prevent the over-oxidation of the nano-carbon materials during the reaction, which can enhance the using life of nano-carbon catalysts. Combining by studying the typical nanocarbon materials and using in-situ characterization methods, we want to explore the influences of structure, adulterate element and oxygen-group to the catalytic oxidative dehydrogenation of hydrocarbon under CO2.If CO2 as green house gas can be effectively utilized in this process, CO2 assisted nanocarbon material oxidative dehydrogenation of hydrocarbon will be recognized as a green-chemistry route.

近年来纳米碳材料非金属催化烷烃氧化脱氢已经成为研究的焦点，然而针对该催化体系还有许多问题有待于我们进一步研究，尤其是探索新型绿色的氧化剂。本项目在CO2气氛中研究纳米碳材料催化烷烃氧化脱氢反应，希望利用工业废气CO2作为一种活性较为温和的氧化剂, 通过抑制反应中间产物的深度氧化, 在高温反应时获得更高的烯烃产物。同时，还可以抑制氧化脱氢时纳米碳催化剂的深度氧化，增加纳米碳催化剂的使用寿命。通过选取典型的纳米碳材料，结合原位表征手段，考察在CO2气氛下，纳米碳材料的结构，杂原子掺杂和表面含氧官能团对烷烃氧化脱氢的性能影响；为开发具有高活性、高选择性的纳米碳材料绿色催化烷烃氧化脱氢新工艺打下坚实的理论基础。

系统的比较不同碳材料（纳米金刚石，纳米碳管，活性炭，氮掺杂的纳米碳管）的二氧化碳气氛下乙苯脱氢性能，发现纳米金刚石表现出最优的活性和选择性；利用电镜，EELS等手段，发现纳米金刚石的活性结构为石墨烯为壳纳米金刚石为核的核壳结构;系统考察不同P修饰量对纳米碳催化烷烃脱氢的活性和选择性影响，深入理解了P与纳米碳表面活性官能团的作用规律；开发了纳米金刚石基的整体式和复合催化剂，为纳米金刚石作为非金属催化剂用于烷烃脱氢的工业应用奠定了基础。