Du Shihu, Liu Xuegang, Liu Zhiling, Li Gang, Fan Hongjun, Xie Hua, Jiang Ling
State Key Laboratory of Molecular Reaction Dynamics, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023, China.
School of Mathematics and Physics, Hebei University of Engineering, Handan 056038, China.
JACS Au. 2023 May 15;3(6):1723-1727. doi: 10.1021/jacsau.3c00143. eCollection 2023 Jun 26.
Nitrogen activation is a significant but difficult project in the chemical area. Photoelectron spectroscopy (PES) and calculated results are used to investigate the reaction mechanism of the heteronuclear bimetallic cluster FeV toward N activation. The results clearly show that N can be fully activated by FeV at room temperature, forming the FeV(μ-N) complex with the totally ruptured N≡N bond. Electronic structure analysis reveals that the activation of N by FeV is achieved by the electron transfer of bimetallic atoms and electron back-donation to the metal core, which demonstrates that heteronuclear bimetallic anionic clusters are very important to nitrogen activation. This study provides important information for the rational design of synthetic ammonia catalysts.
氮活化是化学领域一个重要但具有挑战性的课题。光电子能谱（PES）和计算结果被用于研究异核双金属簇FeV对氮活化的反应机理。结果清楚地表明，在室温下FeV能够完全活化N，形成N≡N键完全断裂的FeV(μ-N)配合物。电子结构分析表明，FeV对N的活化是通过双金属原子的电子转移以及电子回授到金属核来实现的，这表明异核双金属阴离子簇对氮活化非常重要。该研究为合成氨催化剂的合理设计提供了重要信息。
