Shape-Selective Supramolecular Capsules for Actinide Precipitation and Separation

Joseph O’Connell-Danes; Bryne T. Ngwenya; Carole A. Morrison; Gary S. Nichol; Lætitia H. Delmau; Jason B. Love

doi:10.1021/jacsau.3c00793

Shape-Selective Supramolecular Capsules for Actinide Precipitation and Separation

Joseph O’Connell-Danes, Bryne T. Ngwenya, Carole A. Morrison, Gary S. Nichol, Lætitia H. Delmau, Jason B. Love

Process Coordination

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4 Scopus citations

Abstract

Improving actinide separations is key to reducing barriers to medical and industrial actinide isotope production and to addressing the challenges associated with the reprocessing of spent nuclear fuel. Here, we report the first example of a supramolecular anion recognition process that can achieve this goal. We have designed a preorganized triamidoarene receptor that induces quantitative precipitation of the early actinides Th(IV), Np(IV), and Pu(IV) from industrially relevant conditions through the formation of self-assembled hydrogen-bonded capsules. Selectivity over the later An(III) elements is shown through modulation of the nitric acid concentration, and no precipitation of actinyl or transition-metal ions occurs. The Np, Pu, and Am precipitates were characterized structurally by single-crystal X-ray diffraction and reveal shape specificity of the internal hydrogen-bonding array for the encapsulated hexanitratometalates. This work complements ion-exchange resins for 5f-element separations and illustrates the significant potential of supramolecular separation methods that target anionic actinide species.

Original language	English
Pages (from-to)	798-806
Number of pages	9
Journal	JACS Au
Volume	4
Issue number	2
DOIs	https://doi.org/10.1021/jacsau.3c00793
State	Published - Feb 26 2024

Funding

This research was funded by the University of Edinburgh and the Natural Environment Research Council E4: Edinburgh Earth, Ecology and Environment Doctoral Training Partnership, grant number NE/S007407/1 (PhD studentship for J.O’C.-D., received by J.B.L.). The authors are grateful for computational support from the UK Materials and Molecular Modelling Hub, which is partially funded by EPSRC (EP/PO20194 and EP/T022213, C.A.M.), for which access was obtained via the UKCP consortium and funded by EPRSC grant ref EP/P022561/1 (C.A.M.). They thank the Pu-238 Supply Program (NASA) for the use of the Pu-238 and Np-237. They also thank Dr. Luke Sadergaski at ORNL for his assistance with the Raman spectroscopy, Dr. Samantha Schrell, Dr. Connor Parker, and Dr. Frankie White for their assistance with the transuranic crystal preparation and data collection.

Funders	Funder number
Engineering and Physical Sciences Research Council	EP/P022561/1, EP/T022213, EP/PO20194
University of Edinburgh	NE/S007407/1

Keywords

anion recognition
f-elements
nuclear chemistry
radiochemistry
supramolecular

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10.1021/jacsau.3c00793

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abstract = "Improving actinide separations is key to reducing barriers to medical and industrial actinide isotope production and to addressing the challenges associated with the reprocessing of spent nuclear fuel. Here, we report the first example of a supramolecular anion recognition process that can achieve this goal. We have designed a preorganized triamidoarene receptor that induces quantitative precipitation of the early actinides Th(IV), Np(IV), and Pu(IV) from industrially relevant conditions through the formation of self-assembled hydrogen-bonded capsules. Selectivity over the later An(III) elements is shown through modulation of the nitric acid concentration, and no precipitation of actinyl or transition-metal ions occurs. The Np, Pu, and Am precipitates were characterized structurally by single-crystal X-ray diffraction and reveal shape specificity of the internal hydrogen-bonding array for the encapsulated hexanitratometalates. This work complements ion-exchange resins for 5f-element separations and illustrates the significant potential of supramolecular separation methods that target anionic actinide species.",

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AU - Love, Jason B.

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AB - Improving actinide separations is key to reducing barriers to medical and industrial actinide isotope production and to addressing the challenges associated with the reprocessing of spent nuclear fuel. Here, we report the first example of a supramolecular anion recognition process that can achieve this goal. We have designed a preorganized triamidoarene receptor that induces quantitative precipitation of the early actinides Th(IV), Np(IV), and Pu(IV) from industrially relevant conditions through the formation of self-assembled hydrogen-bonded capsules. Selectivity over the later An(III) elements is shown through modulation of the nitric acid concentration, and no precipitation of actinyl or transition-metal ions occurs. The Np, Pu, and Am precipitates were characterized structurally by single-crystal X-ray diffraction and reveal shape specificity of the internal hydrogen-bonding array for the encapsulated hexanitratometalates. This work complements ion-exchange resins for 5f-element separations and illustrates the significant potential of supramolecular separation methods that target anionic actinide species.

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Shape-Selective Supramolecular Capsules for Actinide Precipitation and Separation

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