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Nanoconfinement Inside Molecular Metal Oxide Clusters: Dynamics and Modified Encapsulation Behavior.

Zhe Wang1,2, Luke L Daemen3, Yongqiang Cheng3

  • 1Shull Wollan Center, Neutron Sciences Directorate Oak Ridge National Laboratory, Oak Ridge, Tennessee, 37831, USA.

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|July 28, 2016
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Summary

The {Mo132} metal oxide cluster acts as a nanoreactor. Its rigid internal ligands enable size-selective encapsulation and separation of molecules based on size.

Keywords:
confinementdynamicsencapsulationneutron scatteringpolyoxometaltes

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Area of Science:

  • Materials Science
  • Nanotechnology
  • Supramolecular Chemistry

Background:

  • The 3 nm hollow spherical metal oxide cluster {Mo132} exhibits encapsulation behavior and possesses internal catalytically active sites.
  • Its well-defined structure and tunable properties make it a suitable model for studying materials under nanoconfinement.
  • The internal void space is comparable to the volume of small molecules, offering unique opportunities for confinement studies.

Purpose of the Study:

  • To investigate the dynamics of materials within the {Mo132} cluster under nanoconfinement.
  • To explore the encapsulation behavior and size-selective properties of the {Mo132} cluster.
  • To understand the role of internal ligands in controlling guest molecule access.

Main Methods:

  • Neutron scattering studies were employed to probe the dynamics of internal ligands.
  • Nuclear Magnetic Resonance (NMR) spectroscopy was used to analyze molecular interactions and confinement effects.
  • The {Mo132} cluster's structure and guest molecule interactions were characterized.

Main Results:

  • Neutron scattering revealed slower and limited dynamics of bulky internal ligands compared to bulk states, indicating a rigid ligand skeleton.
  • NMR studies showed that rigid internal ligands partially block interfacial pores on the molybdenum oxide shells.
  • This blocking effect was demonstrated to prevent larger guest molecules from entering the cluster.

Conclusions:

  • The {Mo132} cluster serves as an effective encapsulation host and nanoreactor.
  • The rigid internal ligands are crucial for achieving size-selective encapsulation and separation.
  • This study provides a robust protocol for size-selective encapsulation and separation using the {Mo132} cluster.