Sequestration of trivalent americium and lanthanide nitrates with bis-lactam-1,10-phenanthroline ligand in a hydrocarbon solvent

Karslyan, Yana; Sloop, Frederick V.; Delmau, Laetitia H.; Moyer, Bruce A.; Popovs, Ilja; Paulenova, Alena; Jansone-Popova, Santa

doi:10.1039/C9RA06115K

Title: Sequestration of trivalent americium and lanthanide nitrates with bis-lactam-1,10-phenanthroline ligand in a hydrocarbon solvent

Abstract

Efficient separation of minor actinides and lanthanides from used nuclear fuel could potentially lead to the development of sustainable nuclear fuel cycles. In this work, we report an in-depth study on selectivity and speciation in the extraction of the trivalent minor actinide Am and rare earth metal ions with a pre-organized phenanthroline-based ligand in a hydrocarbon solvent system relevant to nuclear fuel reprocessing. The 1:1 and 2:1 ligand-to-metal complexes determine the speciation in the organic solvent over a range of ligand-to-metal concentrations, as evidenced by experimental data and supported by modeling.

Authors:

^[1];

^[2];

^[3];

^[2];

^[1];

^[2]

Laboratory of Transuranic Elements; Department of Chemistry; Oregon State University; Corvallis; USA
Chemical Sciences Division; Oak Ridge National Laboratory; Oak Ridge; USA
Isotope and Fuel Cycle Technology Division; Oak Ridge National Laboratory; Oak Ridge; USA

Publication Date:: 2019-01-01

Research Org.:: Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)

Sponsoring Org.:: USDOE Office of Nuclear Energy (NE), Fuel Cycle Technologies (NE-5)

OSTI Identifier:: 1558683

Alternate Identifier(s):: OSTI ID: 1558526

Grant/Contract Number:: AC05-00OR22725

Resource Type:: Published Article

Journal Name:: RSC Advances

Additional Journal Information:: Journal Name: RSC Advances Journal Volume: 9 Journal Issue: 46; Journal ID: ISSN 2046-2069

Publisher:: Royal Society of Chemistry

Country of Publication:: United Kingdom

Language:: English

Subject:: 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats


                    Karslyan, Yana, Sloop, Frederick V., Delmau, Laetitia H., Moyer, Bruce A., Popovs, Ilja, Paulenova, Alena, and Jansone-Popova, Santa. Sequestration of trivalent americium and lanthanide nitrates with bis-lactam-1,10-phenanthroline ligand in a hydrocarbon solvent.  United Kingdom: N. p., 2019. 
        Web.  doi:10.1039/C9RA06115K.

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                    Karslyan, Yana, Sloop, Frederick V., Delmau, Laetitia H., Moyer, Bruce A., Popovs, Ilja, Paulenova, Alena, & Jansone-Popova, Santa. Sequestration of trivalent americium and lanthanide nitrates with bis-lactam-1,10-phenanthroline ligand in a hydrocarbon solvent.  United Kingdom.  doi:https://doi.org/10.1039/C9RA06115K

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                    Karslyan, Yana, Sloop, Frederick V., Delmau, Laetitia H., Moyer, Bruce A., Popovs, Ilja, Paulenova, Alena, and Jansone-Popova, Santa. Tue .  
        "Sequestration of trivalent americium and lanthanide nitrates with bis-lactam-1,10-phenanthroline ligand in a hydrocarbon solvent".  United Kingdom.  doi:https://doi.org/10.1039/C9RA06115K.

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@article{osti_1558683,

  title        = {Sequestration of trivalent americium and lanthanide nitrates with bis-lactam-1,10-phenanthroline ligand in a hydrocarbon solvent},

  author       = {Karslyan, Yana and Sloop, Frederick V. and Delmau, Laetitia H. and Moyer, Bruce A. and Popovs, Ilja and Paulenova, Alena and Jansone-Popova, Santa},

  abstractNote = {Efficient separation of minor actinides and lanthanides from used nuclear fuel could potentially lead to the development of sustainable nuclear fuel cycles. In this work, we report an in-depth study on selectivity and speciation in the extraction of the trivalent minor actinide Am and rare earth metal ions with a pre-organized phenanthroline-based ligand in a hydrocarbon solvent system relevant to nuclear fuel reprocessing. The 1:1 and 2:1 ligand-to-metal complexes determine the speciation in the organic solvent over a range of ligand-to-metal concentrations, as evidenced by experimental data and supported by modeling.},

  doi          = {10.1039/C9RA06115K},

  journal      = {RSC Advances},

  number       = 46,

  volume       = 9,

  place        = {United Kingdom},

  year         = {2019},

  month        = {1}

}

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DOI: https://doi.org/10.1039/C9RA06115K

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Works referenced in this record:

A REVIEW OF THE BASIC CHEMISTRY AND RECENT DEVELOPMENTS IN TRIVALENT f-ELEMENTS SEPARATIONS
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Nash, Kenneth L.
Solvent Extraction and Ion Exchange, Vol. 11, Issue 4
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Deliberate Design of Ligand Architecture Yields Dramatic Enhancement of Metal Ion Affinity
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Selective Separation and Complexation of Trivalent Actinide and Lanthanide by a Tetradentate Soft–Hard Donor Ligand: Solvent Extraction, Spectroscopy, and DFT Calculations
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Xu, Lei; Pu, Ning; Li, Youzhen
Inorganic Chemistry, Vol. 58, Issue 7
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Gelis, Artem V.; Lumetta, Gregg J.
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Highly Efficient Trivalent Americium/Europium Separation by Phenanthroline-Derived Bis(pyrazole) Ligands
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Liu, Ying; Yang, Xiuying; Ding, Songdong
Inorganic Chemistry, Vol. 57, Issue 10
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Excellent Selectivity for Actinides with a Tetradentate 2,9-Diamide-1,10-Phenanthroline Ligand in Highly Acidic Solution: A Hard–Soft Donor Combined Strategy
journal, January 2014

Xiao, Cheng-Liang; Wang, Cong-Zhi; Yuan, Li-Yong
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A novel highly selective ligand for separation of actinides and lanthanides in the nuclear fuel cycle. Experimental verification of the theoretical prediction
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Solvent Extraction and Ion Exchange, Vol. 34, Issue 2
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Efficient Separation of Light Lanthanides(III) by Using Bis‐Lactam Phenanthroline Ligands
journal, March 2019

Healy, Mary R.; Ivanov, Alexander S.; Karslyan, Yana
Chemistry – A European Journal, Vol. 25, Issue 25
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Bis-lactam-1,10-phenanthroline (BLPhen), a New Type of Preorganized Mixed N,O-Donor Ligand That Separates Am(III) over Eu(III) with Exceptionally High Efficiency
journal, April 2017

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journal, January 2017

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Works referencing / citing this record:

Lanthanide Intra-series Separation by a 1,10-Phenanthroline Derivative: Counterion Effect
journal, March 2020

Simonnet, Marie; Suzuki, Shinichi; Miyazaki, Yuji
Solvent Extraction and Ion Exchange, Vol. 38, Issue 4
DOI: 10.1080/07366299.2020.1744806

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Efficient Separation of Light Lanthanides(III) by Using Bis-Lactam Phenanthroline Ligands

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Due to the ever-increasing demand for high-purity individual rare-earth elements, novel and highly selective separation processes are increasingly sought after. Herein, we report a separation protocol that employs shape-persistent 2,9-bis-lactam-1,10-phenanthroline (BLPhen) ligands exhibiting unparalleled selectivity for light trivalent lanthanides. The highly preorganised binding pockets of the ligands allowed for the separation of lanthanides with high fidelity, even in the presence of competing transition metals, in a biphasic separation system. Furthermore, the selectivity trends of the BLPhen ligands towards metal ions across the lanthanide series can be chemically modulated by altering the molecular rigidity of the extractant.
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The hydrophobic organic molecules CyMe{sub 4}-BTPhen (1) and CyMe{sub 4}-BTBP (2) have been developed and tuned over many years to be able to separate the trivalent actinides from the trivalent lanthanides (Ln) selectively in bi-phasic solvent extraction processes for the separation of the long-lived radio-toxic minor actinides from spent nuclear fuel. The ability of these N-donor ligands to perform this separation is poorly understood, as is their speciation with the metal ions when extracted into the organic phase. Our previous work has shown Ln{sup 3+} speciation to be largely 1:2 Ln:L in nature with another small molecule, either water ormore »« less
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Similar Records

Title: Sequestration of trivalent americium and lanthanide nitrates with bis-lactam-1,10-phenanthroline ligand in a hydrocarbon solvent

Abstract

Citation Formats

A REVIEW OF THE BASIC CHEMISTRY AND RECENT DEVELOPMENTS IN TRIVALENT f-ELEMENTS SEPARATIONS journal, May 1993

Deliberate Design of Ligand Architecture Yields Dramatic Enhancement of Metal Ion Affinity journal, May 2002

Selective Separation and Complexation of Trivalent Actinide and Lanthanide by a Tetradentate Soft–Hard Donor Ligand: Solvent Extraction, Spectroscopy, and DFT Calculations journal, March 2019

Actinide Lanthanide Separation Process—ALSEP journal, January 2014

Multicoordinate ligands for actinide/lanthanide separations journal, January 2007

The Actinide-Lanthanide Separation Concept journal, May 2014

Highly Efficient Trivalent Americium/Europium Separation by Phenanthroline-Derived Bis(pyrazole) Ligands journal, May 2018

Highly Efficient Separation of Actinides from Lanthanides by a Phenanthroline-Derived Bis-triazine Ligand journal, August 2011

Uncovering Heavy Actinide Covalency: Implications for Minor Actinide Partitioning journal, February 2019

Extraction of Trivalent Lanthanides and Actinides by “Cmpo-Like” Calixarenes journal, January 1999

Separation of actinides from spent nuclear fuel: A review journal, November 2016

Nuclear fuel cycle strategies including Partitioning and Transmutation journal, March 2005

Excellent Selectivity for Actinides with a Tetradentate 2,9-Diamide-1,10-Phenanthroline Ligand in Highly Acidic Solution: A Hard–Soft Donor Combined Strategy journal, January 2014

The Chemistry of TALSPEAK: A Review of the Science journal, December 2014

A novel highly selective ligand for separation of actinides and lanthanides in the nuclear fuel cycle. Experimental verification of the theoretical prediction journal, January 2017

Synthesis of Novel BTPhen-Functionalized Silica-Coated Magnetic Nanoparticles for Separating Trivalent Actinides and Lanthanides journal, August 2017

“Straining” to Separate the Rare Earths: How the Lanthanide Contraction Impacts Chelation by Diglycolamide Ligands journal, November 2016

Thermodynamic Considerations of Covalency in Trivalent Actinide-(poly)aminopolycarboxylate Interactions journal, January 2016

Efficient Separation of Light Lanthanides(III) by Using Bis‐Lactam Phenanthroline Ligands journal, March 2019

Bis-lactam-1,10-phenanthroline (BLPhen), a New Type of Preorganized Mixed N,O-Donor Ligand That Separates Am(III) over Eu(III) with Exceptionally High Efficiency journal, April 2017

Thermodynamic, Spectroscopic, and Computational Studies of f -Element Complexation by N -Hydroxyethyl-diethylenetriamine- N,N ′, N ″, N ″-tetraacetic Acid journal, January 2017

Comparison of Covalency in the Complexes of Trivalent Actinide and Lanthanide Cations journal, August 2002

Lanthanide Intra-series Separation by a 1,10-Phenanthroline Derivative: Counterion Effect journal, March 2020

A REVIEW OF THE BASIC CHEMISTRY AND RECENT DEVELOPMENTS IN TRIVALENT f-ELEMENTS SEPARATIONS
journal, May 1993

Deliberate Design of Ligand Architecture Yields Dramatic Enhancement of Metal Ion Affinity
journal, May 2002

Selective Separation and Complexation of Trivalent Actinide and Lanthanide by a Tetradentate Soft–Hard Donor Ligand: Solvent Extraction, Spectroscopy, and DFT Calculations
journal, March 2019

Actinide Lanthanide Separation Process—ALSEP
journal, January 2014

Multicoordinate ligands for actinide/lanthanide separations
journal, January 2007

The Actinide-Lanthanide Separation Concept
journal, May 2014

Highly Efficient Trivalent Americium/Europium Separation by Phenanthroline-Derived Bis(pyrazole) Ligands
journal, May 2018

Highly Efficient Separation of Actinides from Lanthanides by a Phenanthroline-Derived Bis-triazine Ligand
journal, August 2011

Uncovering Heavy Actinide Covalency: Implications for Minor Actinide Partitioning
journal, February 2019

Extraction of Trivalent Lanthanides and Actinides by “Cmpo-Like” Calixarenes
journal, January 1999

Separation of actinides from spent nuclear fuel: A review
journal, November 2016

Nuclear fuel cycle strategies including Partitioning and Transmutation
journal, March 2005

Excellent Selectivity for Actinides with a Tetradentate 2,9-Diamide-1,10-Phenanthroline Ligand in Highly Acidic Solution: A Hard–Soft Donor Combined Strategy
journal, January 2014

The Chemistry of TALSPEAK: A Review of the Science
journal, December 2014

A novel highly selective ligand for separation of actinides and lanthanides in the nuclear fuel cycle. Experimental verification of the theoretical prediction
journal, January 2017

Synthesis of Novel BTPhen-Functionalized Silica-Coated Magnetic Nanoparticles for Separating Trivalent Actinides and Lanthanides
journal, August 2017

“Straining” to Separate the Rare Earths: How the Lanthanide Contraction Impacts Chelation by Diglycolamide Ligands
journal, November 2016

Thermodynamic Considerations of Covalency in Trivalent Actinide-(poly)aminopolycarboxylate Interactions
journal, January 2016

Efficient Separation of Light Lanthanides(III) by Using Bis‐Lactam Phenanthroline Ligands
journal, March 2019

Bis-lactam-1,10-phenanthroline (BLPhen), a New Type of Preorganized Mixed N,O-Donor Ligand That Separates Am(III) over Eu(III) with Exceptionally High Efficiency
journal, April 2017

Thermodynamic, Spectroscopic, and Computational Studies of f -Element Complexation by N -Hydroxyethyl-diethylenetriamine- N,N ′, N ″, N ″-tetraacetic Acid
journal, January 2017

Comparison of Covalency in the Complexes of Trivalent Actinide and Lanthanide Cations
journal, August 2002

Lanthanide Intra-series Separation by a 1,10-Phenanthroline Derivative: Counterion Effect
journal, March 2020