Surface-Dependent Isotopic Adsorption of CO on α-Al2O3: Role of Weak Interactions and Zero-Point Energy.

Carbon isotopes, particularly ¹³C, are critical for applications in food authentication, biomedical diagnostics, and metabolic research; however, their efficient separation remains challenging due to their low natural abundance. This study investigates the adsorption behavior of ¹²CO and ¹³CO on various low-index α-Al₂O₃ surfaces as a strategy for isotope separation. Density functional theory (DFT) calculations with D3 (BJ) dispersion corrections were employed to optimize surface models for five representative α-Al₂O₃ facets. Nine adsorption configurations were systematically evaluated by optimizing geometric structures, computing adsorption enthalpies with zero-point energy corrections, and performing Bader charge and charge density difference analyses to elucidate interfacial interactions. The results reveal that CO preferentially adsorbs in a vertical configuration via its carbon end at Al sites, with the (0001) surface exhibiting the lowest surface energy and most favorable adsorption characteristics. Furthermore, we found that facets with lower surface energy not only facilitate stronger CO adsorption but also demonstrate pronounced adsorption enthalpy differences between ¹²CO and ¹³CO, driven by vibrational zero-point energy disparities. These findings highlight the potential of low adsorption enthalpy surfaces, particularly (0001), (011¯2), and (112¯0), for enhancing isotope separation efficiency, providing valuable insights for the design of advanced separation materials.