Reinvestigating oxygen adsorption on Ag(111) by using strongly constrained and appropriately normed semi-local density functional with the revised Vydrov van Voorhis van der Waals force correction

Abstract

While density functional theory (DFT) at the generalized gradient approximation (GGA) level has made great success in catalysis, it fails in some important systems, such as the adsorption of the oxygen molecule on the Ag(111) surface. Previous DFT studies at the GGA level revealed theoretical inconsistencies on the adsorption energies and dissociation barriers of O2 on Ag(111) in comparison with the experimental conclusion. In this study, the SCAN-rVV10 method at the meta-GGA level with the non-local van der Waals (vdW) force correction was used to reinvestigate the adsorption properties of O2 on the Ag(111) surface. The SCAN-rVV10 results successfully confirm the experimental observation that both molecular and dissociative adsorption can exist for oxygen on Ag(111). The calculated adsorption energy for the physisorption state and the relevant dissociation energy barrier are close to the experimental data. It demonstrates that SCAN-rVV10 can outperform functionals at the GGA level for O2/Ag(111). Therefore, our findings suggest that SCAN-rVV10 can be the desired method for systems where the correct description of intermediate ranged vdW forces are essential, such as the physisorption of small molecules on the solid surface.

The Role of Steps on Silver Nanoparticles in Electrocatalytic Oxygen Reduction

“…The dissociation barriers of both pathways are much lower than on the flat Ag(111) surface, which is 1.22 eV [8]. The significantly lower energy barriers on the stepped Ag(322) surface demonstrated that the surface morphology played a crucial role with its larger reactive surface area and varying CN.…”

“…and between the second and third layers (Δ23) are reduced by 19.58% and 4.55%, respectively. Conversely, the interlayer relaxation in the Ag(111) surface is negligible [8]. The large relaxation in Ag(322) is influenced by its unique morphology.…”

“…Our previous study demonstrated its excellent non-local vdW and close-range predictions [8]. Both SCAN and rVV10 have been shown individually to work around the self-interaction error and replicate an accurate oxygen dissociation energy barrier for Ag(111) [8,39]. Therefore, this method could be useful for further studies involving O 2 adsorption.…”

“…The hydrogen fuel cell is the primary technology that converts this gas into electricity and is the pathway to a 100% renewable economy [4,5]. Unfortunately, this technology is held back by the kinetically poor cathodic oxygen reduction reaction (ORR) [6][7][8][9]. Moreover, expensive Pt-based catalysts are necessary for commercial hydrogen fuel cells.…”

“…However, the SCAN-rVV10 method overcomes these limitations [37,38]. Our previous study demonstrated its excellent non-local vdW and close-range predictions [8]. Both SCAN and rVV10 have been shown individually to work around the self-interaction error and replicate an accurate oxygen dissociation energy barrier for Ag(111) [8,39].…”