铁活性中心限域催化的分子尺度构建与表征

Confinement effect， as a general phenomenon in heterogeneous catalysis, holds the potential to be utilized as a basic principle to guide the design of novel catalysts, once a molecule-level understanding of confinement could be achieved. Based on our early development of efficient catalyst prototypes with confined iron atoms as the active center (e.g. Pt-FeO, FeN4-graphene, Fe nanoparticles encapsulated in carbon nanotubes and isolated iron atoms on silicon oxide surfaces), this application intends to use surface science approaches to construct the active structures at the atomic-scale and and to assess the elementary reaction steps at the molecule-level. Particularly, the activation process of O2 and CH4 will be investigated in details on these iron-based active structures taking advantage of the precision of surface science approaches. Meanwhile, this application intends to employ computational methods for the high-throughput screening of catalytic materials, establishing BEP relations and building the corresponding volcano curves,based on the structural conformation provided from surface science research. A synergetic interplay between surface science studies and theoretical calculations would achieve a quantitative understanding on the confinement effect at the level of electronic interactions, and also to enable the design of highly efficient and novel active structures.

限域效应作为多相催化中的一个常见现象，有望在加深认识的基础上发展成为一个催化剂设计的基本原则。基于前期本所开发的高效限域铁基催化剂雏形（如Pt-FeO、FeN4-石墨烯、碳纳米管封装的Fe纳米粒子和氧化硅表面的单分散铁原子），本申请拟发挥表面科学在精确构建活性结构和确定反应机理方面的优势，在原子尺度构筑限域活性结构,在分子尺度考察几类铁基活性结构在氧活化和甲烷活化过程中的作用机制；拟利用计算催化在高通量筛选方面的高效优势，根据表面研究确定的结构构象，确立BEP关系和构建相应的火山形曲线，寻找最优结构设计。通过模型表面研究和计算催化的相互反馈合作，实现对限域效应在电子作用尺度的定量认识，并利用限域效应实现新型高效活性结构的设计。

域效应作为多相催化中的一个常见现象，有望在加深认识的基础上发展成为一个催化剂设计的基本原则。基于前期本所开发的高效限域铁基催化剂雏形（如Pt-FeO、FeN4-石墨烯、碳纳米管封装的Fe纳米粒子和氧化硅表面的单分散铁原子），本申请拟发挥表面科学在精确构建活性结构和确定反应机理方面的优势，在原子尺度构筑限域活性结构,在分子尺度考察几类铁基活性结构在氧活化和甲烷活化过程中的作用机制；拟利用计算催化在高通量筛选方面的高效优势，根据表面研究确定的结构构象，确立BEP关系和构建相应的火山形曲线，寻找最优结构设计。通过模型表面研究和计算催化的相互反馈合作，实现对限域效应在电子作用尺度的定量认识，并利用限域效应实现新型高效活性结构的设计。