First-principles study of mercaptoundecanoic acid molecule adsorption and gas molecule penetration onto silver surface: an insight for corrosion protection.

Recently, 11-mercaptoundecanoic acid (MUA) molecule has attracted attention as a promising passivation agent of Ag nanowire (NW) network electrode for corrosion inhibition, but the underneath mechanism has not been elaborated. In this work, we investigate adsorption of MUA molecule on Ag(1 0 0) and Ag(1 1 1) surface, adsorption of air gas molecules of HO, HS and O on MUA molecular end surface, and their penetrations into the Ag surface using the first-principles calculations. Our calculations reveal that the MUA molecule is strongly bound to the Ag surface with the binding energies ranging from -0.47 to -2.06 eV and the Ag-S bond lengths of 2.68-2.97 Å by Lewis acid-base reaction. Furthermore, we find attractive interactions between the gas molecules and the MUA@Ag complexes upon their adsorptions and calculate activation barriers for their migrations from the outermost end of the complexes to the top of Ag surface. It is found that the penetrations of HO and HS are more difficult than the O penetration due to their higher activation barriers, while the O penetration is still difficult, confirming the corrosion protection of Ag NW network by adsorbing the uniform monolayer of MUA. With these findings, this work can contribute to finding a better passivation agent in the strategy of corrosion protection of Ag NW network electrode.