氮掺杂石墨烯整体式催化剂设计制备及其在丙烷氧化脱氢反应中的应用  

Preparation of Nitrogen Doped Graphene Monolithic Catalysts and Their Application in Oxidative Dehydrogenation of Propane

作　　者：刘为杰 曹天龙 代雪亚 齐伟[1] LIU Weijie;CAO Tianlong;DAI Xueya;QI Wei(Institute of Metal Research,Chinese Academy of Sciences,Shenyang 110016,China)

机构地区：[1]中国科学院金属研究所,辽宁沈阳110016

出　　处：《化学反应工程与工艺》2022年第1期41-47,67,共8页Chemical Reaction Engineering and Technology

基　　金：国家自然科学基金(22072163,21761132010,91645114)。

摘　　要：以吡啶、吡咯和尿素为含氮元素前驱体,通过水热自组装结合热处理法制备了氮掺杂的石墨烯整体式催化剂,考察了其催化丙烷氧化脱氢反应的活性。催化剂结构表征和反应活性测试结果表明:以吡啶为前驱体很难有效地引入较高含量的氮原子;以吡咯为前驱体时能够一定程度地增加氮原子的掺杂量,但对石墨烯表面氧物种含量的调控并不明显,对石墨烯催化活性的改善比较有限;尿素分子具有一定的还原性,在水热过程中能与石墨烯表面的氧官能团发生化学反应。尿素前驱体不仅能作为氮源被引入到石墨烯的结构中,而且能有效提升石墨烯整体式催化剂中活性氧物种的数量,进而显著改善了石墨烯整体式催化剂的性能,使丙烷转化率和丙烯产率明显提高。这一优化策略对杂原子调控石墨烯整体式材料的催化性能和构效关系研究以及新型高效碳基整体式催化剂的设计制备具有指导意义。Nitrogen-doped graphene monolithic catalysts were prepared by hydrothermal self-assembly method using pyridine,pyrrole and urea as dopants respectively.Their catalytic performance in oxidative dehydrogenation reaction of propane were investigated.The results of catalyst structure characterization and reaction activity test showed that it is difficult to introduce high content of nitrogen atoms effectively by taking pyridine as precursor.When pyrrole was used as dopant,a certain amount of nitrogen was introduced but the oxygen species in graphene did not change significantly,and the catalytic activity was slightly improved after pyrrole doping.Urea molecule could react with oxygen functional groups on the surface of graphene in hydrothermal process because of its certain reducibility,so urea precursor could be introduced into the structure of graphene as a nitrogen source and the number of active oxygen species effectively increased in graphene monolithic catalyst,which significantly improved the catalytic performance of the urea doped sample and increased propane conversion and propylene yield.This work has guiding significance for the research on the structure-activity relationship and catalytic performance of heteroatom regulated graphene monolithic materials and the designed preparation of new high-efficiency carbon based monolithic catalysts.

关 键 词：石墨烯整体式催化剂 氮掺杂 丙烷氧化脱氢 水热自组装 

分 类 号：O643.38[理学—物理化学]