CH4/CO2 重整过程中炭材料催化剂表面含氧官能团生成调控及演化行为

Previous studies of Natural Science Foundation of China have found that oxygen functional groups，as carbonaceous catalyst active substance, which can be recycled generation during the CH4/CO2 reforming reaction. There is no doubt that the finding is very important to the understanding of the structure of the catalyst surface. Based on the characteristics of oxygen functional groups of carbonaceous catalyst, the research on the controlled generation and evolution of oxygen functional groups on the surface of carbonaceous catalyst during CH4/CO2 reforming was carried out. Take the oxygen functional groups of carbonaceous catalyst as a research object, based on oxygen functional groups oriented carbonaceous catalyst preparation, this project will investigate controlled generation and regulation of oxygen functional groups of carbonaceous catalyst. In order to find the oxygen functional groups transition states and intermediates in reforming process, explore the adsorption and activation mode of different oxygen functional groups for CH4 and CO2, reaction path and the microscopic changes of oxygen functional groups is optimize by the experiment research and thermodynamics analysis. The different reaction pathways of oxygen functional groups during CH4-CO2 reforming were established according to the dynamic changes of the catalytic active sites theory. The formula of different oxygen functional groups of carbonaceous catalyst with the catalytic performance will be developed in the final. Through the research, the process of CH4/CO2 reforming was deepened the understanding over carbonaceous catalyst, and greatly enriched the development of the science of carbon. Provide the theoretical basis of design and development to the oriented anti-coke carbonaceous catalyst.

在前期的青年基金研究中发现，作为CH4/CO2重整炭材料催化剂活性物质的氧官能团可在反应过程中循环再生。这个发现无疑对催化剂表面结构的认识有重要意义。本项目针对炭材料的这一特性，开展CH4/CO2 重整过程中炭材料催化剂表面含氧官能团生成调控及演化行为研究。以炭材料中所含氧官能团为研究对象，以结构导向性氧官能团炭材料催化剂的制备为基础，考查炭材料氧官能团的控制生成及调控规律。根据催化活性中心的动态变化理论，结合热力学支持的反应路径和反应过程氧官能团微观化学结构变化的分析，寻找合理的过渡态和中间体，探索重整转化过程中不同氧官能团对CH4和CO2吸附、活化模式，建立不同氧化物对CH4-CO2重整的反应途径；获得炭材料不同氧官能团与催化性能的关联式。该研究结果不仅可以加深对炭催化CH4-CO2重整的认识，而且可以极大的丰富炭材料学科的发展，为导向性抗积碳高效炭材料催化剂的设计、开发提供理论依据。

CO2是主要的温室气体，但也是宝贵的资源，其在一般条件十分稳定，催化CO2重整转化是解决该难题的有效途径之一。CO2资源化利用和减排已成为21世纪化学和催化学科的世界性难题。认识CO2催化活性的作用机理是实现CO2高效转化利用的基础。本课题组在前期的研究过程中发现，作为CH4/CO2重整炭材料催化剂活性物质的氧官能团可在反应过程中循环再生。本项目针对炭材料的这一特性，开展了CH4/CO2 重整过程中炭材料催化剂表面含氧官能团生成调控及演化行为研究。针对项目申请书中的研究目标，本项目采用不同的导向剂，设计和制备出不同结构导向的氧官能团炭材料催化剂，获得了炭材料氧官能团的控制生成及调控规律；通过考察不同导向剂改性催化剂的氧官能团，结合催化剂表征结果，明晰了重整过程中催化活性物质的过渡态和中间体，揭示了重整转化过程中不同氧官能团对CH4和CO2吸附、活化模式，阐明了不同导向剂改性后得到的氧化物对CH4-CO2重整催化的反应途径。上述关于高效催化剂的制备和改性等关键问题的探讨和研究，对进一步开发新型炭材料高效催化CH4-CO2重整反应催化剂至关重要，在理论上也是一种有意的探讨，同时为今后催化剂分子设计，以及催化剂制备方法和处理条件的选择，提供了有价值的参考数据。项目执行期间，共计发表相关科研论文25篇，其中SCI/EI 收录16篇，取得授权专利9项。2017年获得了侯德榜化工科技青年奖。