Structure of zirconium complexes in aqueous solutions

Kanazhevskii, V. V.; Новгородов, Б. Н.; Shmachkova, V. P.; Kotsarenko, N. S.; Kriventsov, V. V.; Kochubey, D.I.

doi:10.1070/mc2001v011n06abeh001509

Cited by 23 publications

(23 citation statements)

References 12 publications

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“…Polymerization of Zr in solutions seems to be a fundamental incorporation mechanism of Zr, as evidenced in several studies on Zr in synthetic solutions particularly at high concentrations (e.g. Zielen and Connick, 1956;Kanazhevskii et al, 2001Kanazhevskii et al, , 2006Hagfeldt et al, 2004;Cho et al, 2005). Brendebach et al (2007) identified Ca-Zr-OH complexes with [6] Zr for basic CaCl 2 solutions, which showed high solubility for hydrous zirconium oxide.…”

Section: Origin Of Zircon Solubility Enhancementmentioning

confidence: 99%

Corrigendum to “Zircon solubility and zirconium complexation in H2O+Na2O+SiO2±Al2O3 fluids at high pressure and temperature” [Earth Planet. Sci. Lett. 349–350 (2012) 15–25]

Wilke

Schmidt

Dubrail

et al. 2013

Earth and Planetary Science Letters

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Section: Origin Of Zircon Solubility Enhancementmentioning

confidence: 99%

Corrigendum to “Zircon solubility and zirconium complexation in H2O+Na2O+SiO2±Al2O3 fluids at high pressure and temperature” [Earth Planet. Sci. Lett. 349–350 (2012) 15–25]

Wilke

Schmidt

Dubrail

et al. 2013

Earth and Planetary Science Letters

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“…9,21,22 Defects can therefore be deliberately introduced via the inclusion of these species in the reaction mixture. [23][24][25][26][27][28] In 'modulated' synthesis, a monocarboxlic acid modulator is included in the synthesis, giving a ready source of monocarboxylate groups that compete with the linker to coordinate to the cluster, thereby creating missing-linker defects. 1,14,21,29 While modulated synthesis was originally devised as a method of controlling the morphology of MOF crystals via capping coordination sites on the faces of the MOF crystal, [30][31][32] the linker vacancies introduced by modulated synthesis can be incorporated within the framework, leading to a defective structure.…”

Section: Introductionmentioning

confidence: 99%

Engineering New Defective Phases of UiO Family Metal-Organic Frameworks with Water

Firth

Cliffe²,

Vulpe³

et al. 2018

Preprint

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As defects significantly affect the properties of metal-organic frameworks (MOFs)–from changing their mechanical properties to enhancing their catalytic ability–obtaining synthetic control over defects is essential to tuning the effects on the properties of the MOF. Previous work has shown that synthesis temperature and the identity and concentration of modulating acid are critical factors in determining the nature and distribution of defects in the UiO family of MOFs. In this paper we demonstrate that the amount of water in the reaction mixture in the synthesis of UiO family MOFs is an equally important factor, as it controls the phase which forms for both UiO-67(Hf)<br>and UiO-66(Hf) (F4BDC). We use this new understanding of the importance of water to develop a new route to the stable defect-ordered <b>hcp</b> UiO-66(Hf) phase, demonstrating the effectiveness of this method of defect-engineering in the rational design of MOFs. The insights provided by this<br>investigation open up the possibility of harnessing defects to produce new phases and dimensionalities of other MOFs, including nanosheets, for a variety of applications such as MOF-based membranes.

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“…† Deceased. The structure of inorganic zirconium complexes in oxychloride, oxynitrate, and sulfate aqueous solutions was established earlier (see [1] and references therein). When sulfuric acid is added to inorganic salt solutions, other zirconium complexes are formed.…”

Section: Introductionmentioning

confidence: 99%

Changes in the zirconium local surrounding on ligand substitution in solutions

et al. 2006

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EXAFS and SAXS methods have been used to examine zirconium hydroxide and oxychloride aqueous solutions in the presence of sulfuric acid in a wide range of concentrations, as well as a zirconium sulfate aqueous solution. The structure of the complexes and their transformation regularities were determined. Structures of the given complexes and structures of zirconium hydroxide and zirconium oxychloride and hydroxide complexes in aqueous solutions were compared. Complexes in zirconium hydroxide and oxychloride aqueous solutions have identical structures in the presence of sulfuric acid. When the concentration ratio of sulfuric acid and the initial compound is low (20-30), the complex is an open trimer with zirconium atoms bonded by sulfate groups. Bridge sulfate groups form Zr-O-S-O-Zr bonds. Apart from the bridge sulfate groups, there are three terminal sulfate groups and three terminal hydroxyl groups for each zirconium atom. When the concentration of sulfuric acid is increased (up to a ratio of 40-100), closed trimers are observed in the solution. Keywords: zirconium hydroxide, zirconium oxychloride, zirconium sulfate, aqueous solutions of zirconium salts, sulphate solutions of zirconium salts, zirconium complexes, small-angle X-ray scattering, EXAFS.

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Structure of zirconium complexes in aqueous solutions

Cited by 23 publications

References 12 publications

Corrigendum to “Zircon solubility and zirconium complexation in H2O+Na2O+SiO2±Al2O3 fluids at high pressure and temperature” [Earth Planet. Sci. Lett. 349–350 (2012) 15–25]

Corrigendum to “Zircon solubility and zirconium complexation in H2O+Na2O+SiO2±Al2O3 fluids at high pressure and temperature” [Earth Planet. Sci. Lett. 349–350 (2012) 15–25]

Engineering New Defective Phases of UiO Family Metal-Organic Frameworks with Water

Changes in the zirconium local surrounding on ligand substitution in solutions

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