Unveiling the Surface Structure of ZnO Nanorods and H₂ Activation Mechanisms with ¹⁷O NMR Spectroscopy

ZnO plays a very important role in many catalytic processes involving H₂, yet the details on their interactions and H₂ activation mechanism are still missing, owing to the lack of a characterization method that provides resolution at the atomic scale and follows the fate of oxide surface species. Here, we apply ¹⁷O solid-state NMR spectroscopy in combination with DFT calculations to unravel the surface structure of ZnO nanorods and explore the H₂ activation process. We show that six different types of oxygen ions in the surface and subsurface of ZnO can be distinguished. H₂ undergoes heterolytic dissociation on three-coordinated surface zinc and oxygen ions, while the formed hydride species migrate to nearby oxygen species, generating a second hydroxyl site. When oxygen vacancies are present, homolytic dissociation of H₂ occurs and zinc hydride species form from the vacancies. Reaction mechanisms on oxide surfaces can be explored in a similar manner.