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Solid-State Dynamics of Uranyl Polyoxometalates

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Title Solid-State Dynamics of Uranyl Polyoxometalates
Names Alam, Todd M. (creator)
Liao, Zuolei (creator)
Zakharov, Lev N. (creator)
Nyman, May (creator)
Date Issued 2014-07-01 (iso8601)
Note To the best of our knowledge, one or more authors of this paper were federal employees when contributing to this work. This is the publisher’s final pdf. The published article is copyrighted by John Wiley & Sons Ltd. and can be found at: http://onlinelibrary.wiley.com/journal/10.1002/%28ISSN%291521-3765.
Abstract Understanding fundamental uranyl polyoxometalate
(POM) chemistry in solution and the solid state is
the first step to defining its future role in the development
of new actinide materials and separation processes
that are vital to every step of the nuclear fuel cycle. Many
solid-state geometries of uranyl POMs have been described,
but we are only beginning to understand their
chemical behavior, which thus far includes the role of templates
in their self-assembly, and the dynamics of encapsulated
species in solution. This study provides unprecedented
detail into the exchange dynamics of the encapsulated
species in the solid state through Magic Angle Spinning
Nuclear Magnetic Resonance (MAS NMR) spectroscopy. Although
it was previously recognized that capsule-like molybdate
and uranyl POMs exchange encapsulated species
when dissolved in water, analogous exchange in the solid
state has not been documented, or even considered.
Here, we observe the extremely high rate of transport of
Li⁺ and aqua species across the uranyl shell in the solid
state, a process that is affected by both temperature and
pore blocking by larger species. These results highlight
the untapped potential of emergent f-block element materials
and vesicle-like POMs.
Genre Article
Topic ion-exchange
Identifier Alam, T. M., Liao, Z., Zakharov, L. N. and Nyman, M. (2014). Solid-State Dynamics of Uranyl Polyoxometalates. Chemistry: A European Journal, 20: 8302–8307. doi:10.1002/chem.201402351

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