Insights into the leaching behavior of pollucite glass–ceramics at the initial stage.

Pollucite has been proposed as an ideal candidate material for addressing the critical challenge of the safe trapping of the 137Cs radionuclide. However, its detailed corrosion mechanism remains elusive. In this work, we performed reactive and ab initio molecular simulations to explore the leaching behavior of Cs+ from pollucite glass–ceramics at the initial stage. The nonbridging oxygen ions on the surface are protonated at first, followed by the release of Cs+ associated with these oxygen ions. For the glass phase, the inner Cs+ could leach out due to the interaction with water molecules, whereas only the Cs+ present at the surface leach out for pollucite, confirming its remarkable chemical stability. The hydrolysis of Si/Al–O bonds in pollucite is thermodynamically unfavorable, and Al–O bonds are the weak spots. Moreover, the migration barriers of Cs+ in pollucite were calculated by the climbing image nudged elastic band method, and the high barriers reveal that pollucite immobilizes Cs+ stably. This study paves the way for predicting the long‐term safety of a nuclear waste immobilization repository. [ABSTRACT FROM AUTHOR]