Lu Liu This email address is being protected from spambots. You need JavaScript enabled to view it.1, Peng Gong1, Guangcai Shao1, Pengfei Liu2,3, Junfeng Wang1 

1 School of Energy and Power Engineering, Jiangsu University, Zhenjiang 212013, China
2 Institute of High Energy Physics, Chinese Academy of Sciences (CAS), Beijing 100049, China
3 Spallation Neutron Source Science Center (SNSSC), Dongguan 523803, China

Received: November 13, 2021
Revised: December 20, 2021
Accepted: December 20, 2021

 Copyright The Author(s). This is an open access article distributed under the terms of the Creative Commons Attribution License (CC BY 4.0), which permits unrestricted use, distribution, and reproduction in any medium, provided the original author and source are cited.

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Cite this article:

Liu, L., Gong, P., Shao, G., Liu, P., Wang, J. (2022). Density Functional Theory plus U Study of Methanol Adsorption and Decomposition on CuO Surfaces with Oxygen Vacancy. Aerosol Air Qual. Res. 22, 210253.


  • CH3OH adsorption occurs on Cu top site by binding with OMeOH.
  • The adsorption on Cu3C sites is more stable than on Cu4C sites.
  • Dissociative adsorption is observed on CuO with and without oxygen vacancy.
  • Oxygen vacancy enhances CH3OH adsorption and H-O bond scission.
  • Binding energy of CH3O is higher than CH3OH, especially on defected surface.


The adsorption and decomposition of methanol (CH3OH) and methoxy radical (CH3O) on CuO(111) were investigated via density functional theory calculations with a Hubbard U correction. The configurations and electronic structures of CH3OH and CH3O adsorbed on CuO(111) surfaces were analyzed. CH3OH molecules were preferentially adsorbed on Cu top sites with OMeOH atoms and H-O3C bonds formed simultaneously. Adsorption on Cu3C sites was more stable than on Cu4C sites, with higher binding energy and shorter Cu-OMeOH and H-OCuO bonds. Stable configurations were also achieved with OMeOH-H bond scission, which were only found on Cu3C and O3C sites. On surfaces with oxygen vacancies, adsorption configurations did not change a lot, while there was increased adsorption energy with shorter bond lengths of Cu-OMeOH and H-OCuO and longer bond lengths of H-OMeOH, indicating the formation of oxygen vacancies enhanced the CH3OH adsorption and H-OMeOH bond scission, and thus accelerated CH3OH decomposition. The dissociative adsorption configuration MeOH-ov3C5 had the highest adsorption energy, at –0.71 eV, with the H-OCuO bond length at 1.00 Å and H-OMeOH at 1.70 Å. Compared with CH3OH, the adsorption energy of CH3O was much higher and reached –1.52 eV in MeO-3C2. The Cu-OMeO and C-OMeO bond distances were 1.80 Å and 1.40 Å, respectively, which were both shorter than CH3OH adsorption. The formation of oxygen vacancies significantly enhanced CH3O adsorption, as CH3O moved to a vacancy and bound with three Cu atoms by OMeO, whose adsorption energy increased to –3.19 eV. Other configurations had OMeO binding with two Cu3C atoms and formed a bridging bond, with adsorption energies of –2.53 and –2.61 eV.

Keywords: CuO, Methanol, Adsorption, Decomposition, Density functional theory

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