Liu Gaoxiang, Zhu Zhaoguo, Marshall Mary, Blankenhorn Moritz, Bowen Kit H
Department of Chemistry, Johns Hopkins University, Baltimore, Maryland 21218, United States.
J Phys Chem A. 2021 Mar 4;125(8):1747-1753. doi: 10.1021/acs.jpca.1c00204. Epub 2021 Feb 23.
Mass spectrometric analysis of the anionic products of interaction between palladium hydride anions, PdH, and carbon dioxide, CO, in a reaction cell shows an efficient generation of the PdHCO intermediate and isolated formate product. Multiple isomers of the PdHCO intermediates are identified by a synergy between negative ion photoelectron spectroscopy and quantum-chemical calculations. It is shown that a direct mechanism, in which the H atom in PdH directly activates and hydrogenates CO, leads to the formation of the formate product. An indirect mechanism, on the other hand, leads to a stable HPdCO structure, where CO is chemisorbed onto the Pd atom.
在反应池中对氢化钯阴离子（PdH）与二氧化碳（CO）相互作用的阴离子产物进行质谱分析，结果表明能高效生成PdHCO中间体和分离出的甲酸盐产物。通过负离子光电子能谱和量子化学计算相结合的方法，鉴定出了PdHCO中间体的多种异构体。结果表明，一种直接机制，即PdH中的H原子直接活化并氢化CO，导致了甲酸盐产物的形成。另一方面，一种间接机制导致形成稳定的HPdCO结构，其中CO化学吸附在Pd原子上。
