AbstractThe detailed information on the surface structure and binding sites of oxide nanomaterials is crucial to understand the adsorption and catalytic processes and thus the key to develop better materials for related applications. However, experimental methods to reveal this information remain scarce. Here we show that ¹⁷O solid-state nuclear magnetic resonance (NMR) spectroscopy can be used to identify specific surface sites active for CO₂ adsorption on MgO nanosheets. Two 3-coordinated bare surface oxygen sites, resonating at 39 and 42 ppm, are observed, but only the latter is involved in CO₂ adsorption. Double resonance NMR and density functional theory (DFT) calculations results prove that the difference between the two species is the close proximity to H, and CO₂ does not bind to the oxygen ions with a shorter O···H distance of approx. 3.0 Å. Extensions of this approach to explore adsorption processes on other oxide materials can be readily envisaged.