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Intralanthanide Separation on Layered Titanium(IV) Organophosphate Materials via a Selective Transmetalation Process.

Wenzhong Zhang, Sami Hietala, Leonid Khriachtchev

  • 1Department of Green Chemistry, School of Engineering Science , Lappeenranta University of Technology , Sammonkatu 12 , FI-50130 Mikkeli , Finland.

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|June 13, 2018
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Summary

This study introduces novel titanium(IV) coordination polymers for separating lanthanides (Ln), crucial for renewable energy technologies. The method achieves high purity separation of elements like neodymium and dysprosium through a pH-controlled aqueous process.

Keywords:
ion exchangelanthanide contractionorganophosphate ligandsolid-phase extractiontitanium phosphate

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Area of Science:

  • Materials Science
  • Inorganic Chemistry
  • Separation Science

Background:

  • Lanthanides (Ln) are vital for advanced technologies, with increasing demand driven by renewable energy.
  • The similar chemical properties of lanthanides present significant separation challenges, hindering high-purity applications.
  • Existing separation methods often struggle with efficiency and selectivity for individual lanthanides.

Purpose of the Study:

  • To develop a novel solid-phase extraction method for intralanthanide separation.
  • To utilize titanium(IV) butyl phosphate coordination polymers as selective extractants.
  • To investigate the mechanism and efficiency of lanthanide separation using these coordination polymers.

Main Methods:

  • Characterization of titanium(IV) butyl phosphate coordination polymers with layered structures.
  • Application of coordination polymers as solid-phase extractants for lanthanide separation.
  • Utilizing transmetalation (framework metal cation exchange) for selective Ln uptake.
  • Conducting competitive binary separation models and one-step aqueous separation experiments.

Main Results:

  • Coordination polymers exhibit layered structures driven by hydrophobic interactions.
  • Selective lanthanide uptake occurs via transmetalation, with titanium(IV) acting as sacrificial centers.
  • Observed "tetrad effect" in dilute mixtures; smaller lanthanide ions preferentially extracted in binary separations.
  • Achieved quantitative one-step aqueous separation of neodymium and dysprosium with a separation factor >2000 and 99.1% Dy purity.

Conclusions:

  • Titanium(IV) coordination polymers offer a versatile platform for selective intralanthanide separation.
  • The transmetalation process, influenced by coordination and steric factors, enables reversed lanthanide contraction selectivity.
  • Simple pH control in batch mode allows for efficient separation of specific lanthanide pairs, like Nd and Dy.