A predicted new catalyst to replace noble metal Pd for CO oxidative coupling to DMO

• Published in: Catalysis science & technology 2022-04, Vol.12 (8), p.2542-2554
• Main Authors: Zhao, Juan, Yin, Li-Fei, Ling, Li-Xia, Zhang, Ri-Guang, Fan, Mao-Hong, Wang, Bao-Jun
• Format: Article
• Language: English
• Subjects: Carbon monoxide; Catalysts; Catalytic activity; Copper; Coupling; Density functional theory; Monolayers; Noble metals; Palladium; Reaction mechanisms; Selectivity; Synergistic effect
• ISSN: 2044-4753; 2044-4761
• DOI: 10.1039/D1CY01631H

The reaction mechanisms of CO oxidative coupling to dimethyl oxalate (DMO) on different β-Mo 2 C(001) based catalysts have been studied by the density functional theory (DFT) method. The activity and selectivity of DMO formation on Mo termination of β-Mo 2 C(001) are poor, and its C termination has no catalytic activity. After loading a Cu monolayer, the Cu ML /Mo 2 C(001)–Mo catalyst shows poor activity for the CO oxidative coupling reaction, but on Cu ML /Mo 2 C(001)–C, the CO oxidative coupling reaction can occur owing to the synergistic effect between the Cu monolayer and Mo 2 C(001), and it is expected to be a catalyst to replace precious metal Pd in DMO generation. Furthermore, the d-orbital state density of the Cu monolayer on Cu ML /Mo 2 C(001)–C is most similar to that of the Pd monolayer of Pd(111), which is the reason why Cu ML /Mo 2 C(001)–C has high activity and selectivity to DMO on the CO oxidative coupling reaction.