Liu Yun-Zhu, Chen Jiao-Jiao, Li Xiao-Na, He Sheng-Gui
State Key Laboratory for Structural Chemistry of Unstable and Stable Species, Institute of Chemistry, Chinese Academy of Sciences, Beijing 100190, China.
University of Chinese Academy of Sciences, Beijing 100049, China.
J Phys Chem A. 2021 May 6;125(17):3710-3717. doi: 10.1021/acs.jpca.1c02229. Epub 2021 Apr 25.
Laser ablation generated CoCD ( = 0-4) anions were mass selected and then reacted with CO in an ion trap reactor. The reactions were characterized by mass spectrometry and quantum chemical calculations. The experimental results demonstrated that the CoC anion can convert CO into CO. In contrast, the bare Co anion is inert toward CO. Coordinated D ligands can modify the reactivity of CoCD in which CoCD can reduce CO into CO selectively and CoCD can only adsorb CO. The crucial roles of the coordinated C and D ligands to tune the reactivity of CoCD ( = 0-4) toward CO were rationalized by theoretical calculations. Note that the hydrogenation process that is usually observed in the reactions of gas-phase metal hydrides with CO is completely suppressed for the reactions CoCD + CO. This study provides insights into the molecular-level origin for the observations that CO can be selectively generated from CO catalyzed by cobalt-containing carbides in heterogeneous catalysis.
激光烧蚀产生的CoCD（= 0 - 4）阴离子经质量选择后，在离子阱反应器中与CO反应。通过质谱和量子化学计算对反应进行了表征。实验结果表明，CoC阴离子可将CO转化为CO。相比之下，裸Co阴离子对CO呈惰性。配位的D配体可改变CoCD的反应活性，其中CoCD可将CO选择性还原为CO，而CoCD只能吸附CO。通过理论计算阐明了配位的C和D配体对调节CoCD（= 0 - 4）与CO反应活性的关键作用。注意，对于反应CoCD + CO，通常在气相金属氢化物与CO反应中观察到的氢化过程被完全抑制。这项研究为在多相催化中由含钴碳化物催化CO选择性生成CO这一现象的分子水平起源提供了见解。
