Ionothermal Synthesis of Uranyl Vanadate Nanoshell Heteropolyoxometalates

Kohlgruber, Tsuyoshi A.; Senchyk, Ganna A.; Rodriguez, Virginia; Mackley, Stephanie A.; Bo, Fabrice Dal; Aksenov, Sergey M.; Szymanowski, Jennifer E. S.; Sigmon, Ginger E.; Oliver, Allen G.; Burns, Peter C.

doi:10.1021/acs.inorgchem.0c03765

Cited by 9 publications

(6 citation statements)

References 40 publications

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“…19). 118 {U 8 V 6 } and {U 6 V 3 } could be obtained with different extended structures from an ionic liquid solution containing 1-ethyl-3-methylimidazolium diethyl phosphate (EMIm-Et 2 PO 4 ), UO 2 (NO 3 ) 2 , NaVO 3 , and/or VOSO 4 , and Na 2 WO 4 . The monomer, dimer, and 1D chain of {U 8 V 6 } and 1D chain of {U 6 V 3 } represent a new series of U-oxo-clusters incorporating vanadium atoms.…”

Section: Synthesis and Structure Of U-pomsmentioning

confidence: 99%

Recent advances in uranium-containing polyoxometalates

Yang

2022

Inorg. Chem. Front.

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Section: Synthesis and Structure Of U-pomsmentioning

confidence: 99%

Recent advances in uranium-containing polyoxometalates

Yang

2022

Inorg. Chem. Front.

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“…Due to their ready availability, the ILs used to synthesize uranyl compounds are largely imidazolium based. Earlier studies have produced monomeric and dimeric structures built from uranyl ions, − chains and sheets, − isolated clusters, ,, and a few metal–organic frameworks . Existing methods use complex mixtures of ligands or additional metals in combination with the IL and uranium, which renders the predictability of starting material and product solubility challenging .…”

Section: Introductionmentioning

confidence: 99%

Utilizing Ionic Liquids as Bifunctional Reagents for the Ionothermal Synthesis of Uranyl Compounds

Felton,

Kohlgruber,

Tucker

et al. 2023

Crystal Growth & Design

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The extraction of actinides, specifically uranyl and other actinyl ions, from fission products is a critical aspect of spent nuclear fuel reprocessing. In this study, ionothermal syntheses were conducted to control the formation of uranyl (UO2)2+ salt complexes generated by exposure to a selection of ionic liquids (ILs). The high-thermal stability and ligation potential of ILs were exploited in a multifaceted approach toward uranyl salt complexation by enabling ligation of the IL anionic component while simultaneously providing polar reaction media to promote speciation. Furthermore, an evaluation of uranyl complex templating by the IL cation revealed that small, heterocyclic cationic molecules resulted in more densely packed anionic clusters. The uranium source was also varied to determine the oxidizing effect of nitrate on the ILs and the propensity for nitrate and acetate byproduct formation. Uranyl triflate was found to be the optimal uranium source for the production of pure uranyl complexes. The degree to which nitrate oxidizes the ILs was investigated to determine what oxidation products form and subsequently coordinate to the uranyl ion. Finally, it was shown that a uranyl succinate framework can be synthesized in high yield from an IL that contains succinate as the anion.

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“…The three compounds (mentioned above), reported by Kim and Pope, belong to U-hetero-POMs. Several research groups across the globe have reported U-heterosystems with diverse POMs. − Zheng and Kong and their research groups, in 2021, systematically investigated the temperature-dependent photoluminescence studies of an uranium-containing polyoxometalate “Na@U 6 P 6 ” having a sandwich-like structure . In the recent past, the U-heterosilico-/phospho-tungstate systems have been employed as catalysts for organic syntheses. , On the other hand, the uranium-oxo-clusters are primarily self-assembled uranium-oxo-clusters/uranyl peroxide clusters with a number of uranium in these clusters ranging from U 16 to U 124 including their possible hybrids .…”

Section: Introductionmentioning

confidence: 99%

Electrocatalytic Hydrogen Evolution by a Uranium(VI) Polyoxometalate: an Environmental Toxin for Sustainable Energy Generation

Mulkapuri,

Siddikha,

Ravi

et al. 2023

Inorg. Chem.

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The uranyl ion (UO 2 ) 2+ , a uranium nuclear waste, is one of the serious contaminants in our ecosystem because of its radioactivity, relevant human activities, and highly mobile and complex nature of living cells. In this article, we have reported the synthesis and structural characterization of an uranyl cationi n c o r p o r a t e d p o l y o x o m e t a l a t e ( P O M ) c o m p o u n d , K 10 [{K 4 (H 2 O) 6 }{UO 2 } 2 (α-PW 9 O 34 ) 2 ]•13H 2 O (1), in which the uranyl cations are complexed with an in situ generated [α-PW 9 O 34 ] 9− cluster. Single-crystal X-ray diffraction (SCXRD) analysis of compound 1 reveals that the uranyl−potassium complex cationic species, [{K 4 (H 2 O) 6 }{UO 2 } 2 ] 8+ , is sandwiched by two [α-PW 9 O 34 ] 9− clusters resulting in a Dawson type of POM.Compound 1 was further characterized by inductively coupled plasma optical emission spectroscopy (ICP-OES) analysis and infrared (IR), Raman, electronic absorption, and solid-state photoluminescence spectral studies. IR stretching vibrations at 895 and 856 cm −1 and the Raman signature peak at 792 cm −1 in the IR and Raman spectra of compound 1 primarily confirm the presence of a trans-[O�U�O] 2+ ion. The solid-state photoluminescence spectrum of 1 exhibits a typical vibronic structure, resulting from symmetrical vibrations of [O�U�O] 2+ bands, corresponding to the electronic transitions of S 11 → S 10 and S 10 → S 0 υ (υ = 0−3). Interestingly, title compound 1 shows efficient electrocatalytic hydrogen evolution by water reduction with low Tafel slope values of 186.59 and 114.83 mV dec −1 at 1 mA cm −2 along with optimal Faradaic efficiency values of 82 and 87% at neutral pH and in acidic pH 3, respectively. Detailed electrochemical analyses reveal that the catalytic hydrogen evolution reaction (HER) activity mediated by compound 1 is associated with the U VI /U V redox couple of the POM. The microscopic as well as routine spectral analyses of postelectrode samples and controlled experiments have confirmed that compound 1 behaves like a true molecular electrocatalyst for the HER. To our knowledge, this is the first paradigm of a uranium-containing polyoxometalate that exhibits electrocatalytic water reduction to molecular H 2 . In a nutshell, an environmental toxin (a uranium-oxo compound) has been demonstrated to be utilized as an efficient electrocatalyst for hydrogen generation from water, a green approach of sustainable energy production.

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Ionothermal Synthesis of Uranyl Vanadate Nanoshell Heteropolyoxometalates

Cited by 9 publications

References 40 publications

Recent advances in uranium-containing polyoxometalates

Recent advances in uranium-containing polyoxometalates

Utilizing Ionic Liquids as Bifunctional Reagents for the Ionothermal Synthesis of Uranyl Compounds

Electrocatalytic Hydrogen Evolution by a Uranium(VI) Polyoxometalate: an Environmental Toxin for Sustainable Energy Generation

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