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Embedding hexanuclear tantalum bromide cluster {Ta6Br12} into SiO2 nanoparticles by reverse microemulsion method.

Wanghui Chen1,2, Maxence Wilmet1,3, Thai Giang Truong3

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Heliyon
|July 17, 2018
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Summary

Hexanuclear tantalum bromide clusters were successfully embedded into silica nanoparticles using a reverse microemulsion method. This technique preserves the cluster integrity and allows for optical property analysis of the tantalum bromide materials.

Keywords:
Materials chemistryMaterials scienceNanotechnology

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Area of Science:

  • Materials Science
  • Nanotechnology
  • Inorganic Chemistry

Background:

  • Hexanuclear tantalum bromide clusters, [{Ta₆Brⁱ¹²}Lᵃ₆], are unique inorganic building blocks.
  • Embedding these clusters into matrices like SiO₂ is challenging but offers potential for novel material properties.
  • Previous methods for synthesizing such composite materials have limitations in preserving cluster integrity.

Purpose of the Study:

  • To develop a robust method for embedding hexanuclear tantalum bromide clusters into SiO₂ nanoparticles.
  • To characterize the size, morphology, and elemental composition of the resulting {Ta₆Br₁₂}@SiO₂ nanoparticles.
  • To investigate the integrity and optical properties of the embedded tantalum bromide clusters.

Main Methods:

  • A reverse microemulsion (RM) method was employed using n-heptane, Brij L4 surfactant, ethanol, tetraethyl orthosilicate (TEOS), ammonia solution, and an aqueous sol of [{Ta₆Brⁱ¹²}Brᵃ₂(H₂O)ᵃ₄]·nH₂O (TBH).
  • High-angle annular dark-field scanning transmission electron microscopy (HAADF-STEM) and energy-dispersive X-ray (EDS) mappings were used for morphological and compositional analysis.
  • Inductively coupled plasma optical emission spectrometry/ion chromatography (ICP-OES/IC) and X-ray photoelectron spectroscopy (XPS) confirmed the presence and integrity of the tantalum bromide clusters.

Main Results:

  • Successfully synthesized {Ta₆Br₁₂}@SiO₂ nanoparticles with well-dispersed tantalum bromide clusters.
  • EDS mapping, ICP-OES/IC, and XPS analyses confirmed the successful embedding and integrity of the [{Ta₆Brⁱ¹²}] units within the SiO₂ matrix.
  • Diffuse reflectance UV-vis spectroscopy revealed the optical properties, indicating the presence of both Ta₆Br₁₂²⁺ and the more stable Ta₆Br₁₂³⁺ oxidation states.

Conclusions:

  • The reverse microemulsion method is effective for synthesizing SiO₂ nanoparticles embedding hexanuclear tantalum bromide clusters.
  • The integrity of the [{Ta₆Brⁱ¹²}] clusters is maintained during the encapsulation process.
  • The embedded tantalum bromide clusters exhibit distinct optical properties, with Ta₆Br₁₂³⁺ being the predominant and more stable species.