前过渡金属氮化物团簇结构及反应活性

项目名称： 前过渡金属氮化物团簇结构及反应活性

项目编号： No.21503015

项目类型： 青年科学基金项目

立项/批准年度： 2016

项目学科： 数理科学和化学

项目作者： 马嘉璧

作者单位： 北京理工大学

项目金额： 21万元

中文摘要： 前过渡金属氮化物是一类替代贵金属催化剂的理想材料，被称为“准铂催化剂”。以原子团簇为模型，可以从分子层次理解前过渡金属氮化物表面活性位的结构和性质，探究反应机理。目前，关于前过渡金属氮化物团簇的反应活性及构效关系的研究非常少。本项目拟研究前过渡金属氮化物团簇的结构及其与碳氢化合物和H2（及N2）等的反应。利用（1）密度泛函理论或其它量子化学方法，对氮化物团簇的结构及反应机理进行研究；（2）在理论结果的指导下，采用碰撞诱导解离、光电子速度成像、线性离子阱反应等手段研究团簇的结构并测量其反应通道和速率，结合理论预测结果，得到前过渡金属氮化物团簇的成键特点及构效关系。为实际应用前过渡金属氮化物代替贵金属催化剂提供理论基础；从分子水平理解无氧条件下，碳氢化合物和H2（及N2）等活化转化的机理。本项目申请人过去几年一直开展过渡金属氧化物团簇结构与活性的研究，积累的方法和经验为本项目提供了良好的基础。

中文关键词： 原子团簇；氮化物；量子化学计算；质谱

英文摘要： Early transition metal nitrides (ETMNs) are a promising replacement of expensive precious metal catalysts, and known as “platinum-like catalysts”. Studying ETMN clusters is an alternative way to understand nature of active sites of catalysts and obtain mechanisms of activation and transformation of stable molecules at a molecular level. So far, the studies of reactivities of ETMN clusters and the relationship between structures and reactivities are very limited in literature. Herein, we propose to investigate structures of ETMN clusters and reactions toward small molecules including hydrocarbons, H2, (and N2) etc. Two aspects will be addressed: (1) Study structures and reactivities of ETMN clusters by applying density functional theory or other quantum chemical calculations. (2) Collision-induced dissociation, photoelectron imaging spectroscopy, and linear ion trap reactor will be used to investigate the structures of ETMN clusters and reactions toward small molecules. By means of the combination of theoretical predictions and experimental results, information about the bonding character and the relationship between structures and reactivities of ETMN clusters can be obtained. This project can provide fundamental basis in practice for replacement of expensive precious metal catalysts by ETMNs and mechanistic insights in hydrocarbons and H2 (also including N2) activation under oxygen-free conditions. The applicant of this project has investigated the structures and reactivities of transition metal oxide clusters in the past few years and gained computational and experimental experiences that can be used in this study.

英文关键词： atomic clusters;nitrides;quantum chemistry computations;mass spectrometry