Interaction of H2O with the Platinum Pt (001), (011), and (111) Surfaces: A Density Functional Theory Study with Long-Range Dispersion Corrections

Platinum is a noble metal that is widely used for the electrocatalytic production of hydrogen, but the surface reactivity of platinum toward water is not yet fully understood, even though the effect of water adsorption on the surface free energy of Pt is important in the interpretation of the morphology and catalytic properties of this metal. In this study, we have carried out density functional theory calculations with long-range dispersion corrections [DFT-D3-(BJ)] to investigate the interaction of H 2 O with the Pt (001), (011), and (111) surfaces. During the adsorption of a single H 2 O molecule on various Pt surfaces, it was found that the lowest adsorption energy ( E ads ) was obtained for the dissociative adsorption of H 2 O on the (001) surface, followed by the (011) and (111) surfaces. When the surface coverage was increased up to a monolayer, we noted an increase in E ads /H 2 O with increasing coverage for the (001) surface, while for the (011) and (111) surfaces, E ads /H 2 O decreased. Considering experimental conditions, we observed that the highest coverage was obtained on the (011) surface, followed by the (111) and (001) surfaces. However, with an increase in temperature, the surface coverage decreased on all the surfaces. Total desorption occurred at temperatures higher than 400 K for the (011) and (111) surfaces, but above 850 K for the (001) surface. From the morphology analysis of the Pt nanoparticle, we noted that, when the temperature increased, only the electrocatalytically active (111) surface remained.