"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.

High-capacity recovery of Cs+ ions by facilely synthesized layered vanadyl oxalatophosphates with the clear insight into remediation mechanism.

Radiocesium remediation is of great significance for the sustainable development of nuclear energy and ecological protection. It is very challenging for the effective recovery of 137Cs from aqueous solutions due to its strong radioactivity, solubility and mobility. Herein, the efficient recovery of Cs+ ions has been achieved by three layered vanadyl oxalatophosphates, namely (NH4)2[(VO)2(HPO4)2C2O4]·5 H2O (NVPC), Na2[(VO)2(HPO4)2C2O4]·2 H2O (SVPC), and K2.5[(VO)2(HPO4)1.5(PO4)0.5(C2O4)]·4.5 H2O (KVPC). NVPC exhibits the ultra-fast kinetics (within 5 min) and high adsorption capacity for Cs+ (qmCs = 471.58 mg/g). It also holds broad pH durability and excellent radiation stability. Impressively, the entry of Cs+ can be directly visualized by the single-crystal structural analysis, and thus the underlying mechanism of Cs+ capture by NVPC from aqueous solutions has been illuminated at the molecular level. This is a pioneering work in the removal of radioactive ions by metal oxalatophosphate materials which highlights the great potential of metal oxalatophosphates for radionuclide remediation.

Highly Efficient Uptake of Cs+ by Robust Layered Metal-Organic Frameworks with a Distinctive Ion Exchange Mechanism.

137Cs with strong radioactivity and a long half-life is highly hazardous to human health and the environment. The efficient removal of 137Cs from complex solutions is still challenging because of its high solubility and easy mobility and the influence of interfering ions. It is highly desirable to develop effective scavengers for radiocesium remediation. Here, the highly efficient uptake of Cs+ has been realized by two robust layered metal-organic frameworks (MOFs), namely [(CH3)2NH2]In(L)2·DMF·H2O (DMF = N,N'-dimethylformamide, H2L= H2aip (5-aminoisophthalic acid) for 1 and H2hip (5-hydroxyisophthalic acid) for 2). Remarkably, 1 and 2 hold excellent acid and alkali resistance and radiation stabilities. They exhibit fast kinetics, high capacities (q m Cs = 270.86 and 297.67 mg/g for 1 and 2, respectively), excellent selectivity for Cs+ uptake, and facile elution for the regeneration of materials. Particularly, 1 and 2 can achieve efficient Cs+/Sr2+ separation in a wide range of Sr/Cs molar ratios. For example, the separation factor (SF Cs/Sr) is up to ∼320 for 1. Moreover, the Cs+ uptake and elution mechanisms have been directly elucidated at the molecular level by an unprecedented single-crystal to single-crystal (SC-SC) structural transformation, which is attributed to the strong interactions between COO- functional groups and Cs+ ions, easily exchangeable [(CH3)2NH2]+, and flexible and robust anionic layer frameworks with open windows as "pockets". This work highlights layered MOFs for the highly efficient uptake of Cs+ ions in the field of radionuclide remediation.

Highly selective cesium(I) capture under acidic conditions by a layered sulfide.

Radiocesium remediation is desirable for ecological protection, human health and sustainable development of nuclear energy. Effective capture of Cs+ from acidic solutions is still challenging, mainly due to the low stability of the adsorbing materials and the competitive adsorption of protons. Herein, the rapid and highly selective capture of Cs+ from strongly acidic solutions is achieved by a robust K+-directed layered metal sulfide KInSnS4 (InSnS-1) that exhibits excellent acid and radiation resistance. InSnS-1 possesses high adsorption capacity for Cs+ and can serve as the stationary phase in ion exchange columns to effectively remove Cs+ from neutral and acidic solutions. The adsorption of Cs+ and H3O+ is monitored by single-crystal structure analysis, and thus the underlying mechanism of selective Cs+ capture from acidic solutions is elucidated at the molecular level.