Structure Activity Relationship Approach toward the Improved Separation of Rare-Earth Elements Using Diglycolamides

Diana Stamberga; Mary R. Healy; Vyacheslav S. Bryantsev; Camille Albisser; Yana Karslyan; Benjamin Reinhart; Alena Paulenova; Mac Foster; Ilja Popovs; Kevin Lyon; Bruce A. Moyer; Santa Jansone-Popova

doi:10.1021/acs.inorgchem.0c02861

Structure Activity Relationship Approach toward the Improved Separation of Rare-Earth Elements Using Diglycolamides

Diana Stamberga, Mary R. Healy, Vyacheslav S. Bryantsev, Camille Albisser, Yana Karslyan, Benjamin Reinhart, Alena Paulenova, Mac Foster, Ilja Popovs, Kevin Lyon, Bruce A. Moyer, Santa Jansone-Popova

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Abstract

The separation of adjacent lanthanides continues to be a challenge worldwide because of the similar physical and chemical properties of these elements and a necessity to advance the use of clean-energy applications. Herein, a systematic structure-performance relationship approach toward understanding the effect of N-alkyl group characteristics in diglycolamides (DGAs) on the separation of lanthanides(III) from a hydrochloric acid medium is presented. In addition to the three most extensively studied DGA complexants [N,N,N′,N′-tetra(n-octyl)diglycolamide, TODGA; N,N,N′,N′-tetra(2-ethylhexyl)diglycolamide, TEHDGA; N,N′-dimethyl-N,N′-di(n-octyl)diglycolamide, DMDODGA], 12 new extracting agents with varying substitution patterns were designed to study the interplay of steric and electronic effects that control rare-earth element extraction. Subtle changes in the structure around diglycolamide carbonyl oxygen atoms result in dramatic shifts in the lanthanide extraction strength and selectivity. The effects of the chain length and branching position of N-alkyl substituents in DGAs are elaborated on with the use of experimental, computational, and solution-structure characterization techniques.

Original language	English
Pages (from-to)	17620-17630
Number of pages	11
Journal	Inorganic Chemistry
Volume	59
Issue number	23
DOIs	https://doi.org/10.1021/acs.inorgchem.0c02861
State	Published - Dec 7 2020

Funding

This research was supported by the Critical Materials Institute, an Energy Innovation Hub funded by the U.S. DOE, Office of Energy Efficiency and Renewable Energy, Advanced Manufacturing Office. We thank The Advanced Photon Source Sector 12BM-B at Argonne National Laboratory, which is supported by the U.S. DOE, Office of Science, Office of Basic Energy Sciences, Scientific User Facilities Division, under Contract DE-AC02-06CH11357. This research used resources of the National Energy Research Scientific Computing Center, a U.S. DOE of Science User Facility operated under Contract DE-AC02-05CH11231. This manuscript has been authored by UT-Battelle, LLC, under Contract DE-AC05-00OR22725 with the U.S. DOE.

Funders	Funder number
Critical Materials Institute
DOE of Science	DE-AC05-00OR22725, DE-AC02-05CH11231
Office of Basic Energy Sciences	DE-AC02-06CH11357
U.S. DOE
Advanced Manufacturing Office
Office of Science
Office of Energy Efficiency and Renewable Energy
Argonne National Laboratory
National Energy Research Scientific Computing Center

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Stamberga, D., Healy, M. R., Bryantsev, V. S., Albisser, C., Karslyan, Y., Reinhart, B., Paulenova, A., Foster, M., Popovs, I., Lyon, K., Moyer, B. A., & Jansone-Popova, S. (2020). Structure Activity Relationship Approach toward the Improved Separation of Rare-Earth Elements Using Diglycolamides. Inorganic Chemistry, 59(23), 17620-17630. https://doi.org/10.1021/acs.inorgchem.0c02861

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abstract = "The separation of adjacent lanthanides continues to be a challenge worldwide because of the similar physical and chemical properties of these elements and a necessity to advance the use of clean-energy applications. Herein, a systematic structure-performance relationship approach toward understanding the effect of N-alkyl group characteristics in diglycolamides (DGAs) on the separation of lanthanides(III) from a hydrochloric acid medium is presented. In addition to the three most extensively studied DGA complexants [N,N,N′,N′-tetra(n-octyl)diglycolamide, TODGA; N,N,N′,N′-tetra(2-ethylhexyl)diglycolamide, TEHDGA; N,N′-dimethyl-N,N′-di(n-octyl)diglycolamide, DMDODGA], 12 new extracting agents with varying substitution patterns were designed to study the interplay of steric and electronic effects that control rare-earth element extraction. Subtle changes in the structure around diglycolamide carbonyl oxygen atoms result in dramatic shifts in the lanthanide extraction strength and selectivity. The effects of the chain length and branching position of N-alkyl substituents in DGAs are elaborated on with the use of experimental, computational, and solution-structure characterization techniques.",

author = "Diana Stamberga and Healy, {Mary R.} and Bryantsev, {Vyacheslav S.} and Camille Albisser and Yana Karslyan and Benjamin Reinhart and Alena Paulenova and Mac Foster and Ilja Popovs and Kevin Lyon and Moyer, {Bruce A.} and Santa Jansone-Popova",

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Stamberga, D, Healy, MR, Bryantsev, VS, Albisser, C, Karslyan, Y, Reinhart, B, Paulenova, A, Foster, M, Popovs, I, Lyon, K, Moyer, BA & Jansone-Popova, S 2020, 'Structure Activity Relationship Approach toward the Improved Separation of Rare-Earth Elements Using Diglycolamides', Inorganic Chemistry, vol. 59, no. 23, pp. 17620-17630. https://doi.org/10.1021/acs.inorgchem.0c02861

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AU - Stamberga, Diana

AU - Healy, Mary R.

AU - Bryantsev, Vyacheslav S.

AU - Albisser, Camille

AU - Karslyan, Yana

AU - Reinhart, Benjamin

AU - Paulenova, Alena

AU - Foster, Mac

AU - Popovs, Ilja

AU - Lyon, Kevin

AU - Moyer, Bruce A.

AU - Jansone-Popova, Santa

PY - 2020/12/7

Y1 - 2020/12/7

N2 - The separation of adjacent lanthanides continues to be a challenge worldwide because of the similar physical and chemical properties of these elements and a necessity to advance the use of clean-energy applications. Herein, a systematic structure-performance relationship approach toward understanding the effect of N-alkyl group characteristics in diglycolamides (DGAs) on the separation of lanthanides(III) from a hydrochloric acid medium is presented. In addition to the three most extensively studied DGA complexants [N,N,N′,N′-tetra(n-octyl)diglycolamide, TODGA; N,N,N′,N′-tetra(2-ethylhexyl)diglycolamide, TEHDGA; N,N′-dimethyl-N,N′-di(n-octyl)diglycolamide, DMDODGA], 12 new extracting agents with varying substitution patterns were designed to study the interplay of steric and electronic effects that control rare-earth element extraction. Subtle changes in the structure around diglycolamide carbonyl oxygen atoms result in dramatic shifts in the lanthanide extraction strength and selectivity. The effects of the chain length and branching position of N-alkyl substituents in DGAs are elaborated on with the use of experimental, computational, and solution-structure characterization techniques.

AB - The separation of adjacent lanthanides continues to be a challenge worldwide because of the similar physical and chemical properties of these elements and a necessity to advance the use of clean-energy applications. Herein, a systematic structure-performance relationship approach toward understanding the effect of N-alkyl group characteristics in diglycolamides (DGAs) on the separation of lanthanides(III) from a hydrochloric acid medium is presented. In addition to the three most extensively studied DGA complexants [N,N,N′,N′-tetra(n-octyl)diglycolamide, TODGA; N,N,N′,N′-tetra(2-ethylhexyl)diglycolamide, TEHDGA; N,N′-dimethyl-N,N′-di(n-octyl)diglycolamide, DMDODGA], 12 new extracting agents with varying substitution patterns were designed to study the interplay of steric and electronic effects that control rare-earth element extraction. Subtle changes in the structure around diglycolamide carbonyl oxygen atoms result in dramatic shifts in the lanthanide extraction strength and selectivity. The effects of the chain length and branching position of N-alkyl substituents in DGAs are elaborated on with the use of experimental, computational, and solution-structure characterization techniques.

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ER -

Structure Activity Relationship Approach toward the Improved Separation of Rare-Earth Elements Using Diglycolamides

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