Layered Thiostannates with Distinct Arrangements of Mixed Cations for the Selective Capture of Cs+, Sr2+, and Eu3+ Ions.

ABSTRACT

The selective capture of radioactive cesium, strontium, and lanthanides from liquid nuclear waste is of great significance to environmental remediation and human health. Herein, the rapid and selective removal of Cs+, Sr2+, and Eu3+ ions is achieved by two metal sulfides (FJSM-SnS-2 and FJSM-SnS-3). Both structures feature [Sn3S7]n2n- layers with the mixed cations of [CH3NH3]+ and [Bmmim]+ (1-butyl-2,3-dimethylimidazolium) as templates. However, the ratios and arrangements of mixed cations in the interlayered spaces are distinct. It is unprecedented that [CH3NH3]+ and [Bmmim]+ in FJSM-SnS-2 are alternatingly arranged in different interlayered spaces, whereas they in FJSM-SnS-3 are located in the same interlayered spaces. It is the first time that the ionic liquid cation and protonated organic amine have been simultaneously incorporated into metal sulfides. Both compounds show high capacities, rapid kinetics, and a wide pH active range for Cs+, Sr2+, and Eu3+. Even under excess Na+ ions, both show excellent selectivity in capturing trace Sr2+ and Eu3+ ions. FJSM-SnS-3 presents the highest KdEu to date. They still retain high removal efficiency even after intense ß and γ radiation. Moreover, it is first confirmed by the in situ tracking method of mass spectrometry that the large-sized [Bmmim]+ ions are exchangeable. It is found that the arrangement of cations between interlayered spaces is a crucial factor affecting ion exchange performance. This work will likely change the consensus that large-sized organic cations are difficult to be exchanged and thus further highlight the great potential of metal sulfide ion exchangers for radionuclide remediation.