外电场调控氧金属咔咯/氮杂咔咯选择性活化甲烷C-H键的理论研究

调控化学反应活性与选择性一直是催化化学研究的重点，受到多学科的广泛关注。金属咔咯/氮杂咔咯能直接高效利用空气中的氧气氧化底物，若能通过外电场调控氧金属咔咯/氮杂咔咯高选择性的氧化甲烷将具有重要的理论价值和应用前景。本项目将系统研究不同强度大小和方向的外加电场对不同氧金属咔咯/氮杂咔咯氧化甲烷的影响，筛选出高催化活性与高选择性的氧金属咔咯/氮杂咔咯，以及外加电场对甲烷不同氧化程度进行调控的微观机理与内在因素，以期达到对甲烷不同氧化程度的精准控制。在此基础上，为了拓展其在工业上的应用，将利用桥连基团以及化学吸附方法探索构建具有分子特性的低维纳米催化材料的有效方法，并进一步研究外电场对该材料选择性氧化甲烷的调控因素，以及不同氧金属咔咯/氮杂咔咯与外电场对甲烷选择性氧化的协同调控机制，拟构建甲烷不同氧化程度的完整调控体系，为甲烷以及其它原料的高效经济的应用奠定坚实的理论基础。

Controlling the activity and selectivity of chemical reactions has always been the standing focus of catalytic chemistry, and attracted considerable attention from many disciplines. Metal corrole/corrolazine can directly and efficiently utilize oxygen in the air to oxidize the substrate. It will have important theoretical value and application prospect if external electric fields can regulate the highly selective oxidation of methane by (oxo)metal corrole/corrolazine. The project will systematically study the effects of different magnitudes and directions of external electric fields on the oxidation of methane by different (oxo)metal corrole/corrolazine for screening superior (oxo)metal corrole/corrolazine with the high catalytic activity and high selectivity. And the micro-mechanism and intrinsic factors of external electric fields regulating the oxidation of methane with different degrees are also thoroughly understood for precisely controlling the different oxidation levels of methane. For further expanding its application in industry, bridging groups and chemical absorption methods will be used to explore the effective ways to construct low-dimensional nanomaterials with molecule catalytic properties. Furthermore, the effect of external electric fields on the selective oxidation of methane for these nanomaterials will be investigated. And the synergistic mechanism of different (oxo)metal corrole/corrolazine and external electric fields regulating selective oxidation of methane will also be discussed. A complete regulation system of methane selective oxidation in different degrees will be constructed, which will lay a solid theoretical foundation for efficient and economic application of methane and other raw materials.