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Title: Accomplishing simple, solubility-based separations of rare earth elements with complexes bearing size-sensitive molecular apertures

Abstract

Rare earth (RE) metals are critical components of electronic materials and permanent magnets. Recycling of consumer materials is a promising new source of rare REs. To incentivize recycling, there is a clear need for the development of simple methods for targeted separations of mixtures of RE metal salts. Metal complexes of a tripodal hydroxylaminato ligand, TriNOx 3– , featured a size-sensitive aperture formed of its three η 2 -( N , O ) ligand arms. Exposure of cations in the aperture induced a self-associative equilibrium comprising RE(TriNOx)THF and [RE(TriNOx)] 2 species. Differences in the equilibrium constants K dimer for early and late metals enabled simple separations through leaching. Separations were performed on RE1/RE2 mixtures, where RE1 = La–Sm and RE2 = Gd–Lu, with emphasis on Eu/Y separations for potential applications in the recycling of phosphor waste from compact fluorescent light bulbs. Using the leaching method, separations factors approaching 2,000 were obtained for early–late RE combinations. Following solvent optimization, >95% pure samples of Eu were obtained with a 67% recovery for the technologically relevant Eu/Y separation.

Authors:
; ; ; ; ; ;
Publication Date:
Research Org.:
Univ. of Pennsylvania, Philadelphia, PA (United States)
Sponsoring Org.:
USDOE Office of Science (SC)
OSTI Identifier:
1335528
Alternate Identifier(s):
OSTI ID: 1465110
Grant/Contract Number:  
SC0006518
Resource Type:
Published Article
Journal Name:
Proceedings of the National Academy of Sciences of the United States of America
Additional Journal Information:
Journal Name: Proceedings of the National Academy of Sciences of the United States of America Journal Volume: 113 Journal Issue: 52; Journal ID: ISSN 0027-8424
Publisher:
Proceedings of the National Academy of Sciences
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE; 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Bogart, Justin A., Cole, Bren E., Boreen, Michael A., Lippincott, Connor A., Manor, Brian C., Carroll, Patrick J., and Schelter, Eric J. Accomplishing simple, solubility-based separations of rare earth elements with complexes bearing size-sensitive molecular apertures. United States: N. p., 2016. Web. doi:10.1073/pnas.1612628113.
Bogart, Justin A., Cole, Bren E., Boreen, Michael A., Lippincott, Connor A., Manor, Brian C., Carroll, Patrick J., & Schelter, Eric J. Accomplishing simple, solubility-based separations of rare earth elements with complexes bearing size-sensitive molecular apertures. United States. doi:10.1073/pnas.1612628113.
Bogart, Justin A., Cole, Bren E., Boreen, Michael A., Lippincott, Connor A., Manor, Brian C., Carroll, Patrick J., and Schelter, Eric J. Mon . "Accomplishing simple, solubility-based separations of rare earth elements with complexes bearing size-sensitive molecular apertures". United States. doi:10.1073/pnas.1612628113.
@article{osti_1335528,
title = {Accomplishing simple, solubility-based separations of rare earth elements with complexes bearing size-sensitive molecular apertures},
author = {Bogart, Justin A. and Cole, Bren E. and Boreen, Michael A. and Lippincott, Connor A. and Manor, Brian C. and Carroll, Patrick J. and Schelter, Eric J.},
abstractNote = {Rare earth (RE) metals are critical components of electronic materials and permanent magnets. Recycling of consumer materials is a promising new source of rare REs. To incentivize recycling, there is a clear need for the development of simple methods for targeted separations of mixtures of RE metal salts. Metal complexes of a tripodal hydroxylaminato ligand, TriNOx 3– , featured a size-sensitive aperture formed of its three η 2 -( N , O ) ligand arms. Exposure of cations in the aperture induced a self-associative equilibrium comprising RE(TriNOx)THF and [RE(TriNOx)] 2 species. Differences in the equilibrium constants K dimer for early and late metals enabled simple separations through leaching. Separations were performed on RE1/RE2 mixtures, where RE1 = La–Sm and RE2 = Gd–Lu, with emphasis on Eu/Y separations for potential applications in the recycling of phosphor waste from compact fluorescent light bulbs. Using the leaching method, separations factors approaching 2,000 were obtained for early–late RE combinations. Following solvent optimization, >95% pure samples of Eu were obtained with a 67% recovery for the technologically relevant Eu/Y separation.},
doi = {10.1073/pnas.1612628113},
journal = {Proceedings of the National Academy of Sciences of the United States of America},
number = 52,
volume = 113,
place = {United States},
year = {2016},
month = {12}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record
DOI: 10.1073/pnas.1612628113

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Cited by: 1 work
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Figures / Tables:

Fig. 1 Fig. 1: Thermal ellipsoid plots of (Top) 1-La and (Bottom) 2-La shown at 30% probability. Interstitial solvent molecules and hydrogen atoms have been omitted for clarity. tert-butyl groups are depicted using a wireframe model.

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