Integrated DFT and experimental study on Co3O4/CeO2catalyst for direct synthesis of dimethyl carbonate from CO2

Document Type

Article

Publication Title

Journal of CO2 Utilization

Abstract

The oxygen deficient site on the catalyst has a strong impact on the activation of CO2for the synthesis of dimethyl carbonate (DMC). The Co3O4/CeO2catalyst exhibits multiple reduction behavior as cobalt metal species differ in the strength of their interaction with CeO2. This causes the surface reduction from Ce4+to Ce3+in solid solution Co-O-Ce. The dispersion of Co3O4enhanced the formation of oxygen deficient site as revealed by XPS, CO2-chemisorption and TPR. The non-precious Co3O4/CeO2nanorod was recognized as a potential catalyst for promoting Ce4+to Ce3+for CO2activation and dimethyl carbonate synthesis (81.5% of yield). Energetics of oxygen vacancy formation of low index surfaces of CeO2was determined with first-principles calculations based on DFT. Results disclosed the Ce4+to Ce3+formation energy of CeO2due to Co substitution and corroborated the experimental results. Further, calculations provide the details of the effect of Co substitution on the electronic structure of reduced CeO2surfaces. Estimated CO2adsorption energy indicates (110) as the most active surface for activation of CO2

DOI

10.1016/j.jcou.2022.102323

Publication Date

1-1-2023

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