"Ion-imprinting" strategy towards metal sulfide scavenger enables the highly selective capture of radiocesium.

Highly selective capture of radiocesium is an urgent need for environmental radioactive contamination remediation and spent fuel disposal. Herein, a strategy is proposed for construction of "inorganic ion-imprinted adsorbents" with ion recognition-separation capabilities, and a metal sulfide Cs2.33Ga2.33Sn1.67S8·H2O (FJSM-CGTS) with "imprinting effect" on Cs+ is prepared. We show that the K+ activation product of FJSM-CGTS, Cs0.51K1.82Ga2.33Sn1.67S8·H2O (FJMS-KCGTS), can reach adsorption equilibrium for Cs+ within 5 min, with a maximum adsorption capacity of 246.65 mg·g-1. FJMS-KCGTS overcomes the hindrance of Cs+ adsorption by competing ions and realizes highly selective capture of Cs+ in complex environments. It shows successful cleanup for actual 137Cs-liquid-wastes generated during industrial production with removal rates of over 99%. Ion-exchange column filled with FJMS-KCGTS can efficiently treat 540 mL Cs+-containing solutions (31.995 mg·L-1) and generates only 0.12 mL of solid waste, which enables waste solution volume reduction. Single-crystal structural analysis and density functional theory calculations are used to visualize the "ion-imprinting" process and confirm that the "imprinting effect" originates from the spatially confined effect of the framework. This work clearly reveals radiocesium capture mechanism and structure-function relationships that could inspire the development of efficient inorganic adsorbents for selective recognition and separation of key radionuclides.

All-in-one treatment: Capture and immobilization of 137Cs by ultra-stable inorganic solid acid materials HMMoO6·nH2O (M = Ta, Nb).

Capture and immobilization of 137Cs is urgent for radioactive contamination remediation and spent fuel treatment. Herein, an effective all-in-one treatment method to simultaneously adsorb and immobilize Cs+ without high-temperature treatment is proposed. According to the strategy of incorporating high-valency metal ions into molybdates to increase the material stability and affinity towards radionuclides, layered HMMoO6·nH2O (M = Ta (1), Nb (2)) are prepared. Both materials exhibit excellent acid resistance (even 15 mol/L HNO3). They maintain remarkable adsorption capacity for Cs+ in 1 mol/L HNO3 solutions and can selectively capture Cs+ under excessive competitive ions. Furthermore, they show successful cleanup for actual 137Cs-liquid-wastes generated during industrial production. In particular, adsorbed Cs+ can be firmly immobilized in interlayer spaces of materials due to the highly stable anionic framework. The removal mechanism is attributed to ion exchange between Cs+ and interlayer H+ by multiple characterizations. Study of the structure-function relationship shows that the occurrence of Cs+ ion exchange is closely related to plate-like layered structure. This work develops an efficient all-in-one treatment method for capturing and immobilizing radiocesium by ultra-stable inorganic solid acid materials with low energy consumption and high safety for radionuclide remediation.