The Uptake of Hazardous Metal Ions into a High-Nuclearity Cluster-Based Compound with Structural Transformation and Proton Conduction

Abstract

The discovery of novel high-nuclearity oxo-clusters considerably promotes the development of cluster science. We report a high-nuclearity oxo-cluster-based compound with acid/alkali-resistance and radiation stabilities, namely, (H3O)7[Cd7Sb24O24(l-tta)9(l-Htta)3(H2O)6]·29H2O (FJSM-CA; l-H4tta = l-tartaric acid), which features a two-dimensionally anionic layer based on the largest Sb-oxo-clusters with 28-metal-ion-core [Cd4Sb24O24]. It is challenging to efficiently capture Sr2+, Ba2+ (analogue of 226Ra), and [UO2]2+ ions from aqueous solutions due to their high water solubility and environmental mobility, while it is unprecedented that a novel Sb-oxo-cluster-based framework material FJSM-CA can efficiently remove these hazardous ions accompanied with intriguing structural transformations. Especially, it shows fast ion-exchange abilities for Sr2+, Ba2+, and [UO2]2+ (reaches equilibrium within 2, 10, and 20 min, respectively) and high exchange capacity (121.91 mg/g), removal rate R (96%), and distribution coefficient K d U (2.46 × 104 mL/g) for uranium. Moreover, the underlying mechanism is clearly revealed, which is attributed to strong electrostatic interactions between exchanged cations and highly negative-charged frameworks and the strong affinity of (COO)− groups for these cations. Proton conduction of the pristine and Sr2+, Ba2+, [UO2]2+-loaded products was investigated. This work highlights the design of new oxo-cluster-based materials for radionuclide remediation and proton conduction performance.

Ligand Induced Double-Chair Conformation Ln12 Nanoclusters Showing Multifunctional Magnetic and Proton Conductive Properties

“…It should be noted that the proton conductivity of Ln 12 was greater than those of most reported Ln-based proton conductive materials (Table S7). Two general mechanisms have been used to explain proton conduction: the Grotthuss and vehicular mechanisms, which can be distinguished via activation energy (Ea) (Grotthuss mechanisms <0.4 eV; vehicular mechanisms >0.4 eV). − The activation energy (Ea) of Dy 12 and Gd 12 can be roughly estimated via the Arrhenius equation. The calculated values of Dy 12 and Gd 12 were 0.55 and 0.41 eV, respectively, demonstrating that the vehicular mechanism (>0.4 eV) is appropriate.…”

Structural investigation of the efficient capture of Cs+ and Sr2+ by a microporous Cd–Sn–Se ion exchanger constructed from mono-lacunary supertetrahedral clusters

“…38,71 In contrast, the q Sr m of CdSnSe-1 exceeds those of the oxide adsorbents, e.g. clay (39.7 mg g −1 ), 65 Na 2 V 6 O 16 ·3H 2 O (96.4 mg g −1 ), 72 SZ-4 (117.9 mg g −1 ), 73 and FJSM-CA (21.3 mg g −1 ), 74 and even ranks CdSnSe-1 ahead of some of the best metal chalcogenides like KMS-1 (77 mg g −1 ), 35 KMS-2 (86.89 mg g −1 ), 36 KTS-3 (102 mg g −1 ), 37 NaTS (80 mg g −1 ), 43 InS-1 (105.35 mg g −1 ), 40 and ZnSnS-1 (124.2 mg g −1 ), 39 and very close to FJSM-SnS-4 (141.22 mg g −1 ) 75 and the record-holder InS-2 (143.29 mg g −1 ). 41…”

Structural Evolution and Properties of Praseodymium Antimony Oxochlorides Based on a Chain-like Tertiary Building Unit

“…Metal–oxo cluster-based crystalline compounds have attracted increasing attention for their intriguing structural characteristics and properties [ 9 , 10 , 11 , 12 , 13 , 14 , 15 ]. Various types of metal–oxo clusters with tunable composition, size, and symmetry, such as polyoxometalate cluster [ 16 , 17 , 18 ], 3d–4f oxide cluster [ 19 , 20 ], and lanthanide oxide cluster [ 21 , 22 ], have been developed as SBUs to construct cluster-based crystals with complex structures.…”