CO2 adsorption on the copper surfaces: van der Waals density functional and TPD studies

Fahdzi Muttaqien; Yuji Hamamoto; Ikutaro Hamada; Kouji Inagaki; Yuichiro Shiozawa; Kozo Mukai; Takanori Koitaya; Shinya Yoshimoto; Jun Yoshinobu; Yoshitada Morikawa

doi:10.1063/1.4994149

CO₂ adsorption on the copper surfaces: van der Waals density functional and TPD studies

J Chem Phys. 2017 Sep 7;147(9):094702. doi: 10.1063/1.4994149.

Affiliations

¹ Department of Precision Science and Technology, Graduate School of Engineering, Osaka University, 2-1, Yamada-oka, Suita, Osaka 565-0871, Japan.
² The Institute for Solid State Physics, The University of Tokyo, 5-1-5, Kashiwanoha, Kashiwa, Chiba 277-8581, Japan.

PMID: 28886627
DOI: 10.1063/1.4994149

Abstract

We investigated the adsorption of CO₂ on the flat, stepped, and kinked copper surfaces from density functional theory calculations as well as the temperature programmed desorption and X-ray photoelectron spectroscopy. Several exchange-correlation functionals have been considered to characterize CO₂ adsorption on the copper surfaces. We used the van der Waals density functionals (vdW-DFs), i.e., the original vdW-DF (vdW-DF1), optB86b-vdW, and rev-vdW-DF2, as well as the Perdew-Burke-Ernzerhof (PBE) with dispersion correction (PBE-D2). We have found that vdW-DF1 and rev-vdW-DF2 functionals slightly underestimate the adsorption energy, while PBE-D2 and optB86b-vdW functionals give better agreement with the experimental estimation for CO₂ on Cu(111). The calculated CO₂ adsorption energies on the flat, stepped, and kinked Cu surfaces are 20-27 kJ/mol, which are compatible with the general notion of physisorbed species on solid surfaces. Our results provide a useful insight into appropriate vdW functionals for further investigation of related CO₂ activation on Cu surfaces such as methanol synthesis and higher alcohol production.