Theoretical investigation of outer-sphere adsorption of hydrated yttrium ion on the basal surfaces of kaolinite: A density functional study

Ion-adsorption deposits (IADs) are important types of REE deposits. Previous studies have found that, in IAD, REE3+ adsorb on the surface of clay minerals in the form of multi-coordinated hydrated complexes, [REE(H2O)8/9]3+, forming exchangeable outer-sphere adsorption complex. Actually, there are two types of basal surfaces in clay minerals, the (001) surface and the (00−1) surface, and it is not clear whether there are differences in the adsorptions on these two types. Additionally, the electron transfer mechanism in the adsorption structures cannot be revealed. To address these issues, we employ first-principles calculations based on density functional study to simulate the outer-sphere adsorption structures of representative Y3+ ion on the two types of basal surface of kaolinite. The study reveals that both the (001) surface and the (00–1) surface can serve as adsorption surfaces, but the (00–1) surface forms more stable adsorption structures with adsorbate-[Y(H2O)8]3+ due to the absence of hydroxyl group repulsion effects. The adsorption process involves electron transfer from the kaolinite basal surface to the adsorbate, forming hydrogen bonds. The primary orbital interaction in this process is between the O-2p orbitals of the adsorbate and the surface O-2p orbitals. This work contributes to a quantum-level understanding of the nature of ion adsorption in ion-adsorption deposit.