表面辅助的无受体脱氢反应研究

Dehydrogenation reactions are considered to be one of the most fundamental and important types of reactions. Removal of hydrogen atoms from organic compounds can usually be accomplished by the introducing of excess molar amounts of oxidants or sacrificial hydrogen acceptors. However, both of the two strategies lead to wasteful by-product generation. Alternatively, acceptorless dehydrogenation (AD) reactions lead to liberation of hydrogen gas, thus are considered to be environment-friendly. In this project, we focus on the acceptorless dehydrogenation reactions on metal surfaces, studied by scanning tunneling microscopy and X-ray photoemission spectroscopy. In particular, we are interested in: 1,the regio- selectivity and mono-/di- selectivity of the surface assisted AD reactions, which are quite difficult to be achieved in solution. 2, synthesis unified reaction products through pre-self-assembly of the reaction precursors before the AD reactions on metal surfaces. 3, demonstrate how the interaction between the reactants and the metal surfaces influence the AD reactions and their selectivities mechanically.

脱氢反应是化学中最基本和最重要的反应之一，其通常通过氧化剂氧化或氢受主辅助得以实现。然而这两类反应均对环境有污染，不符合可持续发展的国家战略。无受主脱氢技术，由于其只产生氢气作为副产物，因此被认为是清洁的、环境友好的反应方法，近年来成为有机化学的研究热点之一。在本项目中，申请人拟通过表面在位化学技术，系统地研究表面辅助的无受主脱氢反应。结合扫描隧道显微镜、X射线光电子能谱和密度泛函计算等技术，申请人将阐明衬底与反应物的相互作用对无受主脱氢反应及其选择性的影响。此外，基于前期对表面反应中动力学因素的研究，申请人拟通过表面预组装的方法抑制反应物分子在表面的迁移，实现无受主脱氢反应产物的单一化。

在本项目中，申请人通过表面在位化学技术，系统地研究表面催化的无受主脱氢反应。结合扫描隧道显微镜、X射线光电子能谱和第一性原理计算等多种方法，申请人阐明衬底与反应前驱体间的相互作用对无受主脱氢反应及其选择性的影响机制，发现了分子表面迁移能力对反应路径的调控作用，研究了所获产物的电子特性，获得了一系列原创性的科研成果。在此面上项目的资助下，申请人共发表高水平SCI文章9篇，分别为2篇J. Am. Chem. Soc.，1篇Angew. Chem. Int. Ed.，3篇J. Phys. Chem. Lett.和3篇J. Phys. Chem. C。项目执行期间，共毕业博士研究生3名，毕业硕士研究生5名。项目参与人林海平（讲师）在项目执行期间晋升为教授。