Aqueous Bismuth Titanium–Oxo Sulfate Cluster Speciation and Crystallization

Molina, P.; Kozma, Károly; Santala, Melissa K.; Falaise, Clément; Nyman, May

doi:10.1002/ange.201709539

Cited by 10 publications

(4 citation statements)

References 47 publications

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“…12 Similar SAXS features were recently identified and modeled as small (average of three units) bismuth sulfate chains. 63 Taken together, the optical spectra and SAXS data point to a distribution of species that exist between lower-order ligandbridged oligomers and hexamers. The absence of significant scattering in the reaction solutions is consistent with our hypothesis that the ligand-decorated hexamers do not exist to an appreciable extent in solution because of both the availability of the ligand that may limit the formation of the hexamer and the propensity of the ligand-decorated units to precipitate upon formation, leaving smaller oligomers in solution, which is evident in the SAXS data.…”

Section: ■ Experimental Methodsmentioning

confidence: 89%

Solution and Solid State Structural Chemistry of Th(IV) and U(IV) 4-Hydroxybenzoates

et al. 2018

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Organic ligands with carboxylate functionalities have been shown to affect the solubility, speciation, and overall chemical behavior of tetravalent metal ions. While many reports have focused on actinide complexation by relatively simple monocarboxylates such as amino acids, in this work we examined Th(IV) and U(IV) complexation by 4-hydroxybenzoic acid in water with the aim of understanding the impact that the organic backbone has on the solution and solid state structural chemistry of thorium(IV) and uranium(IV) complexes. Two compounds of the general formula [AnO(OH)(HO)(4-HB)]· nHO [An = Th (Th-1) and U (U-1); 4-HB = 4-hydroxybenzoate] were synthesized via room-temperature reactions of AnCl and 4-hydroxybenzoic acid in water. Solid state structures were determined by single-crystal X-ray diffraction, and the compounds were further characterized by Raman, infrared, and optical spectroscopies and thermogravimetry. The magnetism of U-1 was also examined. The structures of the Th and U compounds are isomorphous and are built from ligand-decorated oxo/hydroxo-bridged hexanuclear units. The relationship between the building units observed in the solid state structure of U-1 and those that exist in solution prior to crystallization as well as upon dissolution of U-1 in nonaqueous solvents was investigated using small-angle X-ray scattering, ultraviolet-visible optical spectroscopy, and dynamic light scattering. The evolution of U solution speciation as a function of reaction time and temperature was examined. Such effects as well as the impact of the ligand on the formation and evolution of hexanuclear U(IV) clusters to UO nanoparticles compared to prior reported monocarboxylate ligand systems are discussed. Unlike prior reported syntheses of Th and U(IV) hexamers where the pH was adjusted to ∼2 and 3, respectively, to drive hydrolysis, hexamer formation with the HB ligand appears to be promoted only by the ligand.

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Section: ■ Experimental Methodsmentioning

confidence: 89%

Solution and Solid State Structural Chemistry of Th(IV) and U(IV) 4-Hydroxybenzoates

et al. 2018

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“…17−19 Among them, TOCs are very attractive for their roles as prenucleation clusters and as molecular analogues of TiO 2 . 20,21 They are also used as building blocks for the construction of titania-based organic−inorganic hybrid assemblies 22,23 and in studying structures and electronic/photocatalytic properties of titania. 24,25 Recently, we have isolated a few novel TOCs from highly acidic aqueous solutions of Ti IV .…”

Section: Introductionmentioning

confidence: 99%

Preparation of Porous TiO₂ from an Iso-Polyoxotitanate Cluster for Rechargeable Sodium-Ion Batteries with High Performance

et al. 2019

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By aerobic calcination of a new titanium-oxide cluster (TOC) isolated from water, that is, [Ti6O8(OH2)20]·(2,7-NDS)4·2HCl·14H2O (Ti 6 -NDS; 2,7-NDS = 2,7-naphthalenedisulfonate), porous anatase TiO2 was facially prepared. The sample obtained at 400 °C exhibited a surface area of 108 cm3 g–1 and an average pore diameter of 16 nm. When used as an anode material for a sodium-ion battery (SIB), it showed larger specific capacity and far superior rate performance than the other TiO2 samples, including those prepared from another three TOCs under the same conditions or from Ti 6 -NDS under different conditions and the one obtained from a commercial source. The mechanistic study indicates that the hierarchical structure surrounding the Ti-oxide cores of Ti 6 -NDS is pivotal for the formation and the SIB performance of the porous TiO2. This surfactant-free and catalyst-free strategy for the fabrication of TiO2 materials with special morphologies by thermal transformation of a TOC provides a new optional protocol for the preparation of promising materials stable and efficient in SIBs.

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“…Since Ti 4+ ion is susceptible to hydrolysis, inorganic aqueous TOCs are difficult to obtain. Using vacant POMs as multidentate inorganic ligands to stabilize TOCs and further make TOCsubstituted POMs is full of meaning and challenge, 10 which is due to the terminal hydroxyl oxygens of the Ti atoms easily forming Ti−O−Ti bonds by intermolecular dehydration; therefore, Ti-substituted POMs are prone to generate oligomeric constructions. 11 Ti-containing POMs as an important area have drawn immense attention in the past few decades.…”

Section: ■ Introductionmentioning

confidence: 99%

A New Hepta-Nuclear Ti-Oxo-Cluster-Substituted Tungstoantimonate and Its Catalytic Oxidation of Thioethers

Chen

Yin

et al. 2018

Crystal Growth & Design

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A neoteric hepta-nuclear Ti-oxo-cluster-substituted tetrameric tungstoantimonate [H2N(CH3)2]22Na18{Ti7O6(SbW9O33)4}2·124H2O (1) has hydrothermally been synthesized and tested by single-crystal/powder X-ray diffraction, IR spectra, and thermal analysis. The glamorous feature of this tetrameric polyoxoanion is an uncommon hepta-nuclear Ti-oxo-cluster octahedron [Ti7O6]16+ enclosed in four [B-α-SbW9O33]9– building units. As a heterogeneous catalyst, the investigation on catalytic oxidation with H2O2 for multiple thioethers indicated that 1 possesses high conversion and remarkable selectivity. Additionally, 1 exhibits good stability and excellent recyclability.

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Aqueous Bismuth Titanium–Oxo Sulfate Cluster Speciation and Crystallization

Cited by 10 publications

References 47 publications

Solution and Solid State Structural Chemistry of Th(IV) and U(IV) 4-Hydroxybenzoates

Solution and Solid State Structural Chemistry of Th(IV) and U(IV) 4-Hydroxybenzoates

Preparation of Porous TiO₂ from an Iso-Polyoxotitanate Cluster for Rechargeable Sodium-Ion Batteries with High Performance

A New Hepta-Nuclear Ti-Oxo-Cluster-Substituted Tungstoantimonate and Its Catalytic Oxidation of Thioethers

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Aqueous Bismuth Titanium–Oxo Sulfate Cluster Speciation and Crystallization

Cited by 10 publications

References 47 publications

Solution and Solid State Structural Chemistry of Th(IV) and U(IV) 4-Hydroxybenzoates

Solution and Solid State Structural Chemistry of Th(IV) and U(IV) 4-Hydroxybenzoates

Preparation of Porous TiO2 from an Iso-Polyoxotitanate Cluster for Rechargeable Sodium-Ion Batteries with High Performance

A New Hepta-Nuclear Ti-Oxo-Cluster-Substituted Tungstoantimonate and Its Catalytic Oxidation of Thioethers

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Preparation of Porous TiO₂ from an Iso-Polyoxotitanate Cluster for Rechargeable Sodium-Ion Batteries with High Performance