Selective Oxidation of Propylene on Cu2O(111) and Cu2O(110) Surfaces: A Systematically DFT Study

Yang-Yang Song; Bo Dong; Shi-Wei Wang; Zhong-Rui Wang; Manjie Zhang; Peng Tian; Gui-Chang Wang; Zhen Zhao

doi:10.1021/acsomega.9b02997

Selective Oxidation of Propylene on Cu₂O(111) and Cu₂O(110) Surfaces: A Systematically DFT Study

ACS Omega. 2020 Mar 22;5(12):6260-6269. doi: 10.1021/acsomega.9b02997. eCollection 2020 Mar 31.

Authors

Yang-Yang Song^{1

2}, Bo Dong¹, Shi-Wei Wang¹, Zhong-Rui Wang³, Manjie Zhang¹, Peng Tian¹, Gui-Chang Wang², Zhen Zhao^{1

4}

Affiliations

¹ Institute of Catalysis for Energy and Environment, College of Chemistry and Chemical Engineering, Shenyang Normal University, Shenyang 110034, P. R. China.
² Key Laboratory of Advanced Energy Materials Chemistry (Ministry of Education) and the Tianjin Key Laboratory and Molecule-Based Material Chemistry, College of Chemistry, Nankai University, Tianjin 300071, P. R. China.
³ QiuShi Honors College, Tianjin University, Tianjin 300071, P. R. China.
⁴ State Key Laboratory of Heavy Oil Processing, College of Science, China University of Petroleum, Beijing 102249, P. R. China.

Abstract

Density functional theory calculations with a Hubbard U correction were used to investigate the selective oxidation of propylene on Cu₂O(111) and Cu₂O(110) surfaces, and the mechanism for the selective oxidation of propylene was discussed. On both surfaces, acrolein can be generated by two H-stripping reactions in the allylic hydrogen stripping path, while propylene oxide (PO), propanal, and acetone can be created through the propylene oxametallacycle intermediates in the epoxidation path. Our calculation results indicated that Cu₂O has a high crystal plane-controlled phenomenon for the selective oxidation of propylene. It was found that the formations of propanal and acetone are unfavorable kinetically and acrolein is the main product on the (111) surface. On the (110) surface, the activation barrier of acrolein formation is too high to produce and PO becomes the favored product, which is different from the case of the (111) surface. Moreover, energetic span model analysis was carried out to discuss the selective oxidation of propylene on these two surfaces and confirm the above calculations. The present study can help people to design the proper crystal plane catalyst to get the target product of PO with high selectivity and activity in the selective oxidation of propylene.