Structure of zirconium butoxide complexes in n-butanol solutions

Kanazhevskii, V. V.; Shmachkova, V. P.; Kotsarenko, N. S.; Kolomiichuk, V. N.; Кочубей, Д. И.

doi:10.1007/s10947-006-0322-8

Cited by 12 publications

(39 citation statements)

References 6 publications

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“…The reagent solution mainly contains objects with a radius of 3. 8 A, indicating that the tetramer is the predominant unit, in agreement with Raman results. The associated correlation length was about 20…”

Section: Resultssupporting

confidence: 90%

“…It was found that a tetramer, with R g ¼ 3. 8 A, is the predominant species at low pH for [Zr(IV)] ¼ 0.39 M. After addition of sodium hydroxide, a precipitate appears to be constituted by branched clusters with a mass fractal feature. Upon aging, the precipitate rearranges first giving elongated objects and, finally, primary units with a radius of gyration of about 6 A.…”

Section: Discussionmentioning

confidence: 99%

“…Zr(IV) hydrolyzes even in very acidic aqueous solution to first form a tetramer which then further associates to give larger polymeric networks that can attain colloidal dimensions and, finally, settle out in a nanostructured gel form. The presence in solution of the tetramer, [Zr 4 (OH) 8 (H 2 O) 16 ] 8+ , analogous to that present in ZrOCl 2 $8H 2 O crystals 2 was firstly suggested by Muha and coworkers 3 and then confirmed by several authors using hydrolysis studies, 4 X-ray scattering analysis, 5,6 Raman and NMR spectroscopy, 7 and Extended X-ray Absorption Fine Structure spectroscopy (EXAFS). 8 In the tetramer, the metal atoms are arranged in a distorted square and are held together by double OH bridges along each edge; the coordination sphere of each metal atom is completed by four water molecules, two of which have been suggested to be inert and two labile on the basis of 17 O and 1 H NMR studies.…”

Section: Introductionmentioning

confidence: 90%

“…5 that polynuclear complexes may contain different numbers of chloride ions, and a tetrameric unit with the formula [Zr 4 (OH) 8 (H 2 O) 16 Cl 6 ] 2+ and R g ¼ 3. 8 A was suggested as the predominant species in highly acidic Zr(IV) solutions (pH # 0.3), while an octamer with the formula [Zr 8 (OH) 20 (H 2 O) 24 Cl 12 ] and R g ¼ 5.1…”

Section: Introductionmentioning

confidence: 99%

“…8 A was suggested as the predominant species in highly acidic Zr(IV) solutions (pH # 0.3), while an octamer with the formula [Zr 8 (OH) 20 (H 2 O) 24 Cl 12 ] and R g ¼ 5.1…”

Section: Introductionmentioning

confidence: 99%

See 4 more Smart Citations

Bottom-up/top-down synthesis of stable zirconium hydroxide nanophases

Ambrosi

Fratini

Canton³

et al. 2012

J. Mater. Chem.

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It is well known that the structure of ZrO 2 powder synthesized by low temperature calcination of hydrous zirconia is strongly affected by the nature and properties of precursors. In the present paper, we combined a precipitation/restructuring approach (bottom-up/top-down methodology) to produce zirconium hydroxide nanoparticles that transform into stable nanophasic tetragonal zirconia by low temperature calcination. The dimension and structure of precursors could be modulated by adjusting pH. The synthetic route was investigated by Raman spectroscopy, X-Ray Diffraction, Small-Angle XRay Scattering and High-Resolution Transmission Electron Microscopy. The zirconium hydroxide nanoparticles represent the final product of the overall process, which starts as a bottom-up synthesis of the hydroxide gel, followed by a top-down reorganization stage. During this rearrangement, the evolving structure passes through a mass fractal that arises from the clustering of the primary zirconium hydroxide nano-units.

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Section: Resultssupporting

confidence: 90%

Section: Discussionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 90%

Section: Introductionmentioning

confidence: 99%

“…8 A was suggested as the predominant species in highly acidic Zr(IV) solutions (pH # 0.3), while an octamer with the formula [Zr 8 (OH) 20 (H 2 O) 24 Cl 12 ] and R g ¼ 5.1…”

Section: Introductionmentioning

confidence: 99%

See 3 more Smart Citations

Bottom-up/top-down synthesis of stable zirconium hydroxide nanophases

Ambrosi

Fratini

Canton³

et al. 2012

J. Mater. Chem.

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DFT modeling, UV-Vis and IR spectroscopic study of acetylacetone-modified zirconia sol-gel materials

et al. 2011

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Theoretical and spectroscopic studies of a series of monomeric and dimeric complexes formed through the modification of a zirconium butoxide precursor with acetylacetone and subsequent hydrolysis and/or condensation have been performed by applying DFT/B3LYP/6-31++G(d) and highly accurate RI-ADC(2) methods as well as IR and UV-Vis transmittance and diffuse reflectance spectroscopies. Based on DFT model calculations and simulated and experimental UV-Vis and IR spectra of all the studied structures, the most probable building units of the Zr(IV)-AcAc gel were predicted: the dimeric double hydroxo-bridged complex Zr(2)(AcAc)(2)(OH)(4)(OH)(2br) 9 and the monooxo-bridged complex Zr(2)(AcAc)(2)(OH)(4)O(br)·2H(2)O 12. In both structures, the two AcAc ligands are coordinated to one Zr atom. It was shown that building units 9 and 12 determine the photophysical and vibrational properties of the gel material. The observed UV-Vis and IR spectra of Zr(IV)-AcAc gel were interpreted and a relation between the spectroscopic and structural data was derived. The observed UV-Vis bands at 315 nm and 298/288 nm were assigned to partial ligand-metal transitions and to intra-/inter-AcAc ligand transitions, respectively.

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The molecular composition of non-modified and acac-modified propoxide and butoxide precursors of zirconium and hafnium dioxides

Spijksma

Seisenbaeva²,

Fischer³

et al. 2009

J Sol-Gel Sci Technol

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Long-term storage at 0 °C of a paraffin-sealed flask with commercial 70 wt% solution of zirconium n-propoxide in n-propanol resulted in crystallization of an individual oxoalkoxide complex Zr 4 O(O n Pr) 14 ( n PrOH) 2 in over 20% yield. The structure of this molecule can be described as a triangular Zr 3 (l 3 -O)(OR) 10 (ROH) core of 3 edge-sharing octahedrons with an additional Zr(OR) 4 (ROH) unit attached through a pair of (l-OR) bridges. Mass spectrometric and 1 H NMR investigation of the commercial samples of the most broadly applied zirconium and hafnium n-propoxides and n-butoxides indicate the presence of analogous species in the commercial alkoxide precursors. The content of oxo-alkoxide species in the commercial precursors has been estimated to be *20% for

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Structure of zirconium butoxide complexes in n-butanol solutions

Cited by 12 publications

References 6 publications

Bottom-up/top-down synthesis of stable zirconium hydroxide nanophases

Bottom-up/top-down synthesis of stable zirconium hydroxide nanophases

DFT modeling, UV-Vis and IR spectroscopic study of acetylacetone-modified zirconia sol-gel materials

The molecular composition of non-modified and acac-modified propoxide and butoxide precursors of zirconium and hafnium dioxides

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