2 research outputs found
Theoretical Study of Oxovanadium(IV) Complexation with Formamidoximate: Implications for the Design of Uranyl-Selective Adsorbents
PolyÂ(acrylamidoxime) fibers are the
current state-of-the-art adsorbent
for mining uranium from seawater. However, the competition between
uranyl (UO<sub>2</sub><sup>2+</sup>) and vanadium ions poses a challenge
to mining on the industrial scale. In this work, we employ density
functional theory and coupled-cluster methods in the restricted formalism
to investigate potential binding motifs of the oxovanadiumÂ(IV) ion
(VO<sup>2+</sup>) with the formamidoximate ligand. Consistent with
experimental extended X-ray absorption fine structure data, the hydrated
six-coordinate complex is predicted to be preferred over the hydrated
five-coordinate complex. Our investigation of formamidoximate–VO<sup>2+</sup> complexes universally identified the most stable binding
motif formed by chelating a tautomerically rearranged imino hydroxylamine
via the imino nitrogen and hydroxylamine oxygen. The alternative binding
motifs for amidoxime chelation via a nonrearranged tautomer and η<sup>2</sup> coordination are found to be ∼11 kcal/mol less stable.
Natural bond orbital analysis was performed to understand the nature
of the interactions in the VO<sup>2+</sup> complexes. The difference
in the most stable VO<sup>2+</sup> and UO<sub>2</sub><sup>2+</sup> binding conformation has important implications for the design of
more selective UO<sub>2</sub><sup>2+</sup> ligands
First-Principles Integrated Adsorption Modeling for Selective Capture of Uranium from Seawater by Polyamidoxime Sorbent Materials
Nuclear power is
a relatively carbon-free energy source that has
the capacity to be utilized today in an effort to stem the tides of
global warming. The growing demand for nuclear energy, however, could
put significant strain on our uranium ore resources, and the mining
activities utilized to extract that ore can leave behind long-term
environmental damage. A potential solution to enhance the supply of
uranium fuel is to recover uranium from seawater using amidoximated
adsorbent fibers. This technology has been studied for decades but
is currently plagued by the material’s relatively poor selectivity
of uranium over its main competitor vanadium. In this work, we investigate
the binding schemes between uranium, vanadium, and the amidoxime functional
groups on the adsorbent surface. Using quantum chemical methods, binding
strengths are approximated for a set of complexation reactions between
uranium and vanadium with amidoxime functionalities. Those approximations
are then coupled with a comprehensive aqueous adsorption model developed
in this work to simulate the adsorption of uranium and vanadium under
laboratory conditions. Experimental adsorption studies with uranium
and vanadium over a wide pH range are performed, and the data collected
are compared against simulation results to validate the model. It
was found that coupling ab initio calculations with process level
adsorption modeling provides accurate predictions of the adsorption
capacity and selectivity of the sorbent materials. Furthermore, this
work demonstrates that this multiscale modeling paradigm could be
utilized to aid in the selection of superior ligands or ligand compositions
for the selective capture of metal ions. Therefore, this first-principles
integrated modeling approach opens the door to the in silico design
of next-generation adsorbents with potentially superior efficiency
and selectivity for uranium over vanadium in seawater