New insights into the radiolytic stability of metal() phosphonate hybrid adsorbent materials

Stable metal( iv ) phosphonate hybrids are a promising class of materials for the critical issue of nuclear waste cleanup. However, to be of practical use, adsorbent materials must demonstrate radiolytic stability and this property remains poorly understood. Therefore, the radiolytic stabilities of post-functionalised mesoporous zirconium titanate and zirconium phosphonate coordination polymers were compared. For the first time, solid-state 31 P MAS-NMR was used to probe the radiolytic degradation of metal( iv ) phosphonates and provide mechanistic insight. Polyphosphonate-functionalized hybrids were more stable than monophosphonate hybrids, as the monophosphonate readily detached from the oxide surface. The zirconium phosphonate coordination polymer (Zr-ATMP) demonstrated the greatest radiolytic stability, attributed to its high ligand loading and intimately mixed structure. Zr-ATMP maintained highly efficient sorption from strongly acidic solutions even after receiving doses of gamma radiation up to 2.9 MGy. The dependence of radiolytic stability on both the organic and inorganic components of hybrid materials is explained.