Theoretically predicted innovative palladium stripe doping cobalt(111) surface with excellent catalytic performance for carbon monoxide oxidative coupling to dimethyl oxalate

Abstract

Pd-based catalysts are extensively employed to catalyze CO oxidative coupling to generate DMO, while the expensive price and high usage of Pd hinder its massive application in industrial production. Designing Pd-based catalysts with high efficiency and low Pd usage as well as expounding the catalytic mechanisms are significant for the reaction. In this study, we theoretically predict that Pd stripe doping Co(111) surface exhibits excellent performance than pure Pd(111), Pd monolayer supporting on Co(111) and Pd single atom doping Co(111) surface, and clearly expound the catalytic mechanisms through the density functional theory (DFT) calculation and micro-reaction kinetic model analysis. It is obtained that the favorable reaction pathway is COOCH3–COOCH3 coupling pathway over these four catalysts, while the rate-controlling step is COOCH3+CO+OCH3→2COOCH3 on Pd stripe doping Co(111) surface, which is different from the case (2COOCH3→DMO) on pure Pd(111), Pd monolayer supporting on Co(111) and Pd single atom doping Co(111) surface. This study can contribute a certain reference value for developing Pd-based catalysts with high efficiency and low Pd usage for CO oxidative coupling to DMO.