Ab initio atomistic thermodynamics study on the sulfur tolerance mechanism of the oxygen-enriched yttria-stabilized zirconia surface

The first-principles method based on density functional theory (DFT) is used to investigate the reaction mechanism for the adsorption of H2S on the oxygen-enriched yttria-stabilized zirconia (YSZ + O) (111) surface. It is found that the H2S dissociation processes have low energy barriers (< 0.5 eV) and high exothermicities (2.5 eV), and the dissociative S atoms may result in the poisoning of the YSZ + O surface by forming the SO and the hyposulfite (SO22 −) species with very strong bonds to the surface. In addition, using the ab initio atomistic thermodynamics method, the surface regeneration or de-sulfurization process of a sulfur-poisoned (i.e. sulfur-covered) YSZ + O(111) surface is studied. According to the phase diagram, the adsorbed atomic sulfur can be oxidized to SO2 and removed from the YSZ + O surface by introducing oxidizing reagents, e.g. O2 and H2O.