Density functional theory study on the adsorption and decomposition of H2O on clean and oxygen-modified Pd (1 0 0) surface

Based on density functional theory together with periodic slab models, the adsorption and the corresponding dehydrogenation reaction of H2O on clean and oxygen modified Pd (1 0 0) have been investigated. The preferential sites for H2O, OH, O, and H were obtained on the surfaces. According to the optimized structural and energetic properties, it was found that H2O prefers to adsorb on the top site with weak adsorption energy (physisorption), whereas O and H atoms are prone to adsorb on the hollow site and OH occupies the bridge site. In addition, this work identified the optimum configurations for the relevant co-adsorption groups. The results confirmed that co-adsorption tends to weaken the adsorbate-substrate interaction due to the existence of oxygen atom, and that the OH group, O and H atoms are less stable on oxygen-covered Pd (1 0 0) surface than on the clean surface. Finally, the transition states and related barrier energies were ascertained to analyze the dehydrogenation mechanism of H2O. Water decomposition was found favorable on O-covered Pd (1 0 0) surface (0.49 eV), in agreement with the experimental observations. This result indicated that the joining of Oads could reduce the barrier energy and facilitate the decomposition of H2O. Besides, the distinct differences over Pd (1 1 1) and Pd (1 0 0) surface implied that water decomposition over Pd-based catalysts is a structure-sensitive reaction.