Interaction of SO2 with the Platinum (001), (011), and (111) Surfaces: A DFT Study

Abstract

Given the importance of SO2 as a pollutant species in the environment and its role in the hybrid sulphur (HyS) cycle for hydrogen production, we carried out a density functional theory study of its interaction with the Pt (001), (011), and (111) surfaces. First, we investigated the adsorption of a single SO2 molecule on the three Pt surfaces. On both the (001) and (111) surfaces, the SO2 had a S,O‐bonded geometry, while on the (011) surface, it had a co‐pyramidal and bridge geometry. The largest adsorption energy was obtained on the (001) surface (Eads = −2.47 eV), followed by the (011) surface (Eads = −2.39 and −2.28 eV for co‐pyramidal and bridge geometries, respectively) and the (111) surface (Eads = −1.85 eV). When the surface coverage was increased up to a monolayer, we noted an increase of Eads/SO2 for all the surfaces, but the (001) surface remained the most favourable overall for SO2 adsorption. On the (111) surface, we found that when the surface coverage was θ > 0.78, two neighbouring SO2 molecules reacted to form SO and SO3. Considering the experimental conditions, we observed that the highest coverage in terms of the number of SO2 molecules per metal surface area was (111) > (001) > (011). As expected, when the temperature increased, the surface coverage decreased on all the surfaces, and gradual desorption of SO2 would occur above 500 K. Total desorption occurred at temperatures higher than 700 K for the (011) and (111) surfaces. It was seen that at 0 and 800 K, only the (001) and (111) surfaces were expressed in the morphology, but at 298 and 400 K, the (011) surface was present as well. Taking into account these data and those from a previous paper on water adsorption on Pt, it was evident that at temperatures between 400 and 450 K, where the HyS cycle operates, most of the water would desorb from the surface, thereby increasing the SO2 concentration, which in turn may lead to sulphur poisoning of the catalyst.