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Outer-Sphere Water Clusters Tune the Lanthanide Selectivity of Diglycolamides
journal contribution
posted on 2018-06-13, 21:29 authored by Anna G. Baldwin, Alexander S. Ivanov, Neil J. Williams, Ross J. Ellis, Bruce A. Moyer, Vyacheslav S. Bryantsev, Jenifer C. ShaferFundamental
understanding of the selective recognition and separation of f-block metal ions by chelating agents is of crucial importance
for advancing sustainable energy systems. Current investigations in
this area are mostly focused on the study of inner-sphere interactions
between metal ions and donor groups of ligands, while the effects
on the selectivity resulting from molecular interactions in the outer-sphere
region have been largely overlooked. Herein, we explore the fundamental
origins of the selectivity of the solvating extractant N,N,N′,N′-tetraoctyl diglycolamide (TODGA) for adjacent lanthanides
in a liquid–liquid extraction system, which is of relevance
to nuclear fuel reprocessing and rare-earth refining technologies.
Complementary investigations integrating distribution studies, quantum
mechanical calculations, and classical molecular dynamics simulations
establish a relationship between coextracted water and lanthanide
extraction by TODGA across the series, pointing to the importance
of the hydrogen-bonding interactions between outer-sphere nitrate
ions and water clusters in a nonpolar environment. Our findings have
significant implications for the design of novel efficient separation
systems and processes, emphasizing the importance of tuning both inner-
and outer-sphere interactions to obtain total control over selectivity
in the biphasic extraction of lanthanides.
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distribution studiesmetal ionsLanthanide Selectivityinner-sphere interactionsOuter-Sphere Water Clusters Tuneselectivityextractant Nouter-sphere interactionsTODGAComplementary investigationsimportancefuel reprocessingseparation systemsouter-sphere nitrate ionswater clustersbiphasic extractionrare-earth refining technologiesnonpolar environmentlanthanide extractioncoextracted waterCurrent investigationsblock metal ionshydrogen-bonding interactionsenergy systemsouter-sphere regionchelating agentsdonor groupsdynamics simulations
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