一碳分子活化机制研究和全新催化剂设计

项目名称： 一碳分子活化机制研究和全新催化剂设计

项目编号： No.21473070

项目类型： 面上项目

立项/批准年度： 2015

项目学科： 数理科学和化学

项目作者： 李吉来

作者单位： 吉林大学

项目金额： 88万元

中文摘要： 甲烷和二氧化碳是众所周知的温室气体，也是重要的C1资源。如何实现甲烷和二氧化碳的直接有效转化，是研究的焦点。本研究中，采用先进的理论方法深入细致研究甲烷、二氧化碳活化及二氧化碳重整甲烷机理。通过仔细探索研究催化剂活性位点的三维结构、电荷、配体效应、溶剂环境以及它们之间的耦合作用，结合电子态、pKa值、氧化还原电势以及反应焓变(动力学和热力学信息)等，归纳影响催化剂的反应活性的内在因素与金属离子价态、自旋态、催化剂尺寸、配体的推拉电子作用、溶剂极性等的函数关系；推导出催化作用的微观、内在本质。另一方面，开展系统的方法校验以期获得可靠结果并建立不受用户喜好影响的方法选择规则。最终，用实验来检验理论预测的最有潜力的催化剂。该研究的最终目标是为合成有效的工业催化剂提供理论线索。本研究可为研发新型低分子量的绿色全新催化剂设计提供理论依据，这对一碳利用具有重要意义。

中文关键词： 一碳分子；甲烷；二氧化碳；催化剂；活性

英文摘要： Today, the energy crisis and environmental problems are increasingly serious. Methane (CH4) and carbon dioxide (CO2) are well known?greenhouse gases, and the conversion of these two C1-building?blocks into useful fuels and chemicals is therefore a subject of great?importance. In this proposal, detailed and deep mechanistic study on the fundamental CH4, and CO2 activation and CO2 reforming of methane (CRM) would be performed by state-of-the-art theoretical methods. By careful exploration the 3D structure of catalysts' active sites, ligand effect, state of charge, solvation environment, and their coupling as well, the various interactions among the catalysis can be characterized definitely. Combining the structural parameters, the electronic configuration, pKa value, redox potential, and reaction enthalpy (kinetic and thermodynamic information), etc., the influence factor of the catalyst reactivity can be established as a function of metal ionic state, spin state, size of catalyst, ligand of electron denoting/withdrawing, solvent polarity, and so on. The deep analysis could results in the microscopic and inherent nature of the targeted catalysis. On the other hand, a wide-range and systematic method benchmark would be carried out in order to obtain reliable results, to establish method selection rules without user-favorite directed bias on transition metal involved catalysis. Finally, the most potential catalysts predicted by theory would be tested by experiments. The ultimate aim of this proposal is obtain a couple of promising molecules for widespread industrial applications. It is expected to provide theoretical proofs for the low-molecular-weight green de novo catalyst design in the future, and it is of very important for the implementation of C1 utilization.

英文关键词： C1 molecule;methane;carbon dioxide;catalyst;reactivity