A DFT study and microkinetic analysis of CO oxidation to dimethyl oxalate over Pd stripe and Pd single atom-doped Cu(111) surfaces.

Abstract Developing low amount and high catalytic performance of Pd-based catalysts are vital for the oxidation of CO to dimethyl oxalate (DMO) in industry. In this study, Pd stripe and Pd single atom-doped Cu(111) surfaces are constructed via Pd substituting four striped Cu atoms and single Cu atom of surface layer over the Cu(111) surface, respectively, namely Pd 4 Cu 8 /Cu(111) and Pd 1 -Cu(111) surfaces, and two possible reaction pathways related to DMO synthesis have been studied on two surfaces employing density functional theory (DFT) calculation in combination with microkinetic analysis and subsequently compared with the cases of Pd(111) and Pd ML /Cu(111). The results show that COOCH 3 -COOCH 3 coupling pathway is superior to COOCH 3 -CO on Pd 4 Cu 8 /Cu(111) and Pd 1 -Cu(111). Moreover, the Pd 1 -Cu(111) surface shows highest catalytic activity for DMO generation, followed by the Pd 4 Cu 8 /Cu(111), the Pd(111) and the Pd ML /Cu(111) surface. Additionally, Pd 4 Cu 8 /Cu(111) and Pd 1 -Cu(111) surfaces exhibit high DMO selectivity. Thus, Pd stripe and Pd single atom-doped Cu(111) surfaces are thought to be prospective candidates to improve the catalytic performance of noble Pd and reduce its usage for CO oxidation to DMO. Graphical abstract Unlabelled Image Highlights • The COOCH 3 -COOCH 3 coupling is the optimal route on Pd 4 Cu 8 /Cu(111) and Pd 1 -Cu(111) surfaces. • The activity for DMO formation is in sequence of Pd 1 -Cu(111) > Pd 4 Cu 8 /Cu(111) > Pd(111) > Pd ML /Cu(111). • Pd 4 Cu 8 /Cu(111) and Pd 1 -Cu(111) surfaces are proposed to be prospective candidates for DMO formation. [ABSTRACT FROM AUTHOR]