LaCoO3表面小分子催化氧化反应动力学过程的第一性原理研究

镧-过渡金属氧化物钙钛矿材料是一类新兴的非贵金属催化材料。本项目拟采用基于密度泛函理论的第一性原理方法，对大气污染治理中常见的CO、NO、CH4和SO2等小分子在LaCoO3材料表面上催化氧化反应动力学过程进行系统性研究，开展如下工作：研究①LaCoO3催化剂的不同曝露晶面，②LaCoO3表面上氧缺陷的浓度和分布，③A/B位元素掺杂，④Co离子的d电子自旋组态等因素对催化反应路径和活性的影响；确定相关反应的机理，找到反应的速控步；通过电子结构分析，找到与催化活性密切关联的物理量、确立构效关系，为催化剂理性设计及相关实验研究提供理论依据和指导。LaCoO3材料是当前国内外研究的热点之一，并且大气污染治理是关系国计民生的重要课题。因此，本项目是一项既具有科学研究价值，又具有应用前景的基础性前沿研究课题。

La-transition-metal-oxide based perovskite materials are one type of new-developed non-noble-metal catalytic materials. In this project, we plan to do systematical researches on reacting processes of the small molecules, which are frequently seen in air pollution control, in the catalytic oxidation reactions on the LaCoO3 surfaces via the first-principles calculations based on density functional theory (DFT) , including CO, NO, CH4, SO2, etc. Many factors that may affect the reaction path and the reactivity will be studied in this project, including ①different oriented LaCoO3 surfaces, ②different concentration and distributions of oxygen vacancies, ③doping on A/B site, ④spin states of d electrons in Co ions, etc. Then the reaction mechanism and the rate limiting step of the certain reaction will be determined. By the analysis on the electronic structure, we plan to find a physical quantity, which correlates to the catalytic reactivity and can be used as the theoretical basis for the rational design of catalyst. LaCoO3 material is one of the hot spots for scientific researches all over the word, while air pollution control is also a major event in people's livelihood. Therefore, this project is an advanced fundamental research with values both in scientific research and practical application.