Consecutive C–C Coupling of CH4 and CO2 Mediated by Heteronuclear Metal Cations CuTa+

作者：Yuan Yang, Lijiao Zhang, Xiaoli Wang, Rui Wang, Yan‐Xia Zhao, Sheng‐Gui He, Shuang‐Quan Zang · 发表于：Journal of the American Chemical Society · 年份：2024 · DOI：10.1021/jacs.4c10819 · 被引用次数：21 · 研究领域：Carbon dioxide utilization in catalysis、CO2 Reduction Techniques and Catalysts、Catalysts for Methane Reforming

The conversion of methane and carbon dioxide to form C 2 products is of great interest but presents a long-standing grand challenge due to the significant obstacle of activating the inert C–H and C═O bonds as well as forming the C–C bonds. Herein, the consecutive C–C coupling of CH 4 and CO 2 was realized by using heteronuclear metal cations CuTa +, and the desorption of H 2 C═C═O molecules was evidenced by state-of-the-art mass spectrometry. The CuTa + reaction system is significantly different from the homonuclear metal systems of Cu 2 + and Ta 2 + . On the basis of density functional theory calculations, we identified that Cu can modulate the charge distribution and reduce the energy difference of crucial orbitals for the C–C coupling of CH 2 and CO units that are from the activation of CH 4 and CO 2, respectively. The crucial role of the Cu atom is of substantial importance to understand the process of the C–C coupling reaction in Cu-based heterogeneous catalytic systems. This study not only provides a promising paradigm for the design of non-noble metal species in direct conversion of CH 4 and CO 2 under mild conditions but also reveals a new molecular-level mechanism of consecutive C–C coupling for the production of H 2 C═C═O, a crucial intermediate during carbonylation reactions.