CO activation by the heterobinuclear transition metal-iron clusters:A photoelectron spectroscopic and theoretical study

• 作者: Jumei Zhang Zhiling Liu Gang Li Hongjun Fan Ling Jiang Hua Xie
• 来源期刊: 能源化学
• 年，卷（期）: 2021,（12）
• 页码范围: 344-350
• 页数: 7页
• 语种: 英文

摘要

Spectroscopic characterization of CO activation on multiple metal-containing catalysts remains an impor-tant and challenging goal for identifying the structure and nature of active site in many industrial pro-cesses such as Fischer-Tropsch chemistry and alcohol synthesis.Here,we use mass-selected photoelectron velocity-map imaging spectroscopy and quantum chemical calculations to study the reac-tions of CO molecules with several heterobinuclear transition metal-iron clusters M-Fe (M =Ti,V,Cr).The mass spectra reveal the favorable formation of MFe(CO)4 with relatively high thermodynamic stability.The MFe(CO)4-,(M =Ti,V,Cr) complexes are established to have a metal-Fe bonded M-Fe(CO)4 structure with C3v geometry.While the positive charge and unpaired electrons are mainly located on the M atom,the natural charge of Fe(CO)4 is about-2e.The MFe(CO)4-(M =Ti,V,Cr) can be seen as being formed via the interactions between the M+ fragment and the[Fe(CO)4]2-core,which satisfies the 18-electron rule.The CO molecules are remarkably activated in these MFe(CO)4-.These results shed insight into the structure-reactivity relationship of heterobinuclear transition metal carbonyls and would have important implications for understanding of CO activation on alloy surfaces.