Ultrafiltration of Uranyl Peroxide Nanoclusters for the Separation of Uranium from Aqueous Solution

Wylie, Ernest M.; Peruski, Kathryn; Weidman, Jacob L.; Phillip, William A.; Burns, Peter C.

doi:10.1021/am404520b

Cited by 47 publications

(57 citation statements)

References 21 publications

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“…Because these reactive clusters do not accumulate in the bulk solution and are isolated by crystallization, the state that often results in uncontrolled precipitation of metal hydroxide is avoided. The proposed formation pathway opens new opportunities to explore and augment the composition space and reaction chemistry of (Wylie et al, 2014) and biomedical applications; (Lee et al, 2005) and in crystallization of biomolecules (Bashan and Yonath, 2008). Controlling cluster reactivity has led to breakthroughs in their use as precursors for thin-film deposition (Anderson et al, 2007) and high-resolution nanopatterning (Oleksak et al, 2014).…”

Section: Discussionmentioning

confidence: 99%

Crystallizing Elusive Chromium Polycations

Wang

Fullmer

Bandeira

et al. 2016

Chem

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SUMMARYOxo and oxo-hydroxo metal clusters are commonly isolated from aqueous solutions with capping ligands to prevent precipitation of metal hydroxides. Few simple molecular oxo-hydroxo metal clusters are readily synthesized and isolated without these capping ligands. Yet uncapped clusters are important in metal oxide growth and for applications hindered by auxiliary ligands. Uncapped clusters containing transition metals with partially filled d shells are especially difficult to preparethey rapidly aggregate and precipitate, preventing isolation of the initial cluster form. Herein, we elucidate a cluster self-assembly and crystallization process that has yielded a new uncapped oxo-hydroxo cluster containing Zn 2+ , Al 3+ , and the open-shell transition metal ion Cr 3+ , i.e., [ZnO4Al5.1Cr6.9(OH)24(H2O)12Zn(H2O)3] 8+ . For decades, clusters of Cr 3+ and Zn 2+ have been synthesis targets in polyoxocation chemistry, but they have resisted isolation and crystallization. We control pHdriven hydrolysis by oxidative dissolution of zinc in the reaction solution, rather than by addition of hydroxide. The control gained by Zn dissolution allows metal nitrate concentrations 10× higher than conventional hydroxide addition. Therefore, a high nitrate concentration further suppresses cluster self-assembly in the bulk. Contrary to common cluster growth studies, the fully assembled cluster is not observed spectroscopically in the bulk reaction solution from which the clusters are crystallized. Instead, the reaction solution is dominated by monomeric and dimeric metal species, even while the solution actively grows crystals. Evaporation of the HNO3-H2O azeotrope at the solution surface allows simultaneous cluster self-assembly and crystallization. Because these reactive clusters do not accumulate in the bulk solution and are isolated by crystallization, the state that often results in uncontrolled precipitation of metal hydroxide is avoided. The proposed formation pathway opens new opportunities to explore and augment the composition space and reaction chemistry of compositionally complex oxo-hydroxo clusters, particularly those comprising metals with partially filled d shells. The Bigger PictureAqueous metal-oxide clusters are important in natural processes, in synthesis, and in technology. In nature, they are central to contaminant transport, mineral growth, photosynthesis, and biomineralization. In synthesis, they provide nanometric forms with size dependent properties, and they are pre-assembled building blocks for materials. Fabricating functional metal oxide clusters and cluster-based materials in water minimizes environmental impact. Clusters synthesized and manipulated in water provide understanding of natural processes and inspire biomimetic materials; i.e. for artificial photosynthesis.While synthesis of functional clusters is accomplished with great control in organic solvents; it doesn't offer the simplicity and sustainability of aqueous synthesis. But aqueous syntheses that provide well-controlled cluster and mate...

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Section: Discussionmentioning

confidence: 99%

Crystallizing Elusive Chromium Polycations

Wang

Fullmer

Bandeira

et al. 2016

Chem

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“…This unit is common in uranyl peroxide compounds, although it is typically one of the building units of uranyl peroxide cage clusters. Two such tetramers are linked together through two oxidized EDTAO 2 4− ligands, resulting in novel octamers of uranyl hexagonal bipyramids.…”

Section: +mentioning

confidence: 99%

“…Each uranyl ion in 1 is coordinated by two bidentate peroxo groups and two O atoms provided by either oxalate or EDTAO 2 4− ligands, all of which are arranged at the equatorial vertices of hexagonal bipyramids. There are two crystallo- (Figure 4), as in 1.…”

Section: +mentioning

confidence: 99%

“…1 This affinity is significant in various aspects of the nuclear fuel cycle, including in the mining and purification of uranium and potentially in the reprocessing of used nuclear fuels. 2 Uranyl peroxide solids can be remarkably stable, with the minerals studtite, (UO 2 )(O 2 )-(H 2 O) 2 (H 2 O) 2 , and its lower hydrate, metastudtite, (UO 2 )-(O 2 )(H 2 O) 2 , forming and persisting in natural U deposits due to the buildup of peroxide owing to the alpha radiolysis of water. 3 The synthetic analogues of these minerals are known to form on irradiated nuclear fuel when it interacts with water, 4 as well as on nuclear debris from the Chernobyl accident where it is exposed to the environment.…”

Section: ■ Introductionmentioning

confidence: 99%

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Expanding the Crystal Chemistry of Uranyl Peroxides: Four Hybrid Uranyl-Peroxide Structures Containing EDTA

et al. 2014

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The first four uranyl peroxide compounds containing ethylenediaminetetra-acetate (EDTA) were synthesized and characterized from aqueous uranyl peroxide nitrate solutions with a pH range of 5-7. Raman spectra demonstrated that reaction solutions that crystallized [NaK15[(UO2)8(O2)8(C10H12O10N2)2(C2O4)4]·(H2O)14] (1) and [Li4K6[(UO2)8(O2)6(C10H12O10N2)2(NO3)6]·(H2O)26] (2) contained excess peroxide, and their structures contained oxidized ethylenediaminetetraacetate, EDTAO2(4-). The solutions from which [K4[(UO2)4(O2)2(C10H13O8N2)2(IO3)2]·(H2O)16] (3) and LiK3[(UO2)4(O2)2(C10H12O8N2)2(H2O)2]·(H2O)18 (4) crystallized contained no free peroxide, and the structures incorporated intact EDTA(4-). In contrast to the large family of uranyl peroxide cage clusters, coordination of uranyl peroxide units in 1-4 by EDTA(4-) or EDTAO2(4-) results in isolated tetramers or dimers of uranyl ions that are bridged by bidentate peroxide groups. Two tetramers are bridged by EDTAO2(4-) to form octamers in 1 and 2, and dimers of uranyl polyhedra are linked through iodate groups in 3 and EDTA(4-) in 4, forming chains in both cases. In each structure the U-O2-U dihedral angle is strongly bent, at ∼140°, consistent with the configuration of this linkage in cage clusters and other recently reported uranyl peroxides.

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“…Energy dispersive spectroscopy (EDS, see below) provided an estimated U:W:P atomic ratio of 50:6:22. O)14 ] 23− was synthesized as for U 50 W 6 P 20 , except that an aqueous H 3 PMo 12 O 40 solution (10%, 0.1 mL) was used instead of H 3 PW 12 O 40 and 0.1 mL of H 3 PO 3 solution was used. The initial solution pH was 6.0, and U 44 Mo 2 P 16 clusters crystallized within 2 weeks.…”

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confidence: 99%

Hybrid Uranium–Transition-Metal Oxide Cage Clusters

et al. 2014

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Transition-metal based polyoxometalate clusters have been known for decades, whereas those built from uranyl peroxide polyhedra have more recently emerged as a family of complex clusters. Here we report the synthesis and structures of six nanoscale uranyl peroxide cage clusters that contain either tungstate or molybdate polyhedra as part of the cage, as well as phosphate tetrahedra. These transition-metal-uranium hybrid clusters exhibit unique polyhedral connectivities and topologies that include 6-, 7-, 8-, 10-, and 12-membered rings of uranyl polyhedra and uranyl ions coordinated by bidentate peroxide in both trans and cis configurations. The transition-metal polyhedra appear to stabilize unusual units built of uranyl polyhedra, rather than templating their formation.

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Ultrafiltration of Uranyl Peroxide Nanoclusters for the Separation of Uranium from Aqueous Solution

Cited by 47 publications

References 21 publications

Crystallizing Elusive Chromium Polycations

Crystallizing Elusive Chromium Polycations

Expanding the Crystal Chemistry of Uranyl Peroxides: Four Hybrid Uranyl-Peroxide Structures Containing EDTA

Hybrid Uranium–Transition-Metal Oxide Cage Clusters

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