%0 Journal Article
%A Baldwin, Anna G.
%A Ivanov, Alexander S.
%A Williams, Neil J.
%A Ellis, Ross J.
%A Moyer, Bruce A.
%A Bryantsev, Vyacheslav S.
%A Shafer, Jenifer C.
%D 2018
%T Outer-Sphere Water Clusters Tune the Lanthanide Selectivity
of Diglycolamides
%U https://acs.figshare.com/articles/journal_contribution/Outer-Sphere_Water_Clusters_Tune_the_Lanthanide_Selectivity_of_Diglycolamides/6515942
%R 10.1021/acscentsci.8b00223.s001
%2 https://acs.figshare.com/ndownloader/files/11984150
%K distribution studies
%K metal ions
%K Lanthanide Selectivity
%K inner-sphere interactions
%K Outer-Sphere Water Clusters Tune
%K selectivity
%K extractant N
%K outer-sphere interactions
%K TODGA
%K Complementary investigations
%K importance
%K fuel reprocessing
%K separation systems
%K outer-sphere nitrate ions
%K water clusters
%K biphasic extraction
%K rare-earth refining technologies
%K nonpolar environment
%K lanthanide extraction
%K coextracted water
%K Current investigations
%K block metal ions
%K hydrogen-bonding interactions
%K energy systems
%K outer-sphere region
%K chelating agents
%K donor groups
%K dynamics simulations
%X Fundamental
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.
%I ACS Publications