Nanospace Decoration with Uranyl-Specific "Hooks" for Selective Uranium Extraction from Seawater with Ultrahigh Enrichment Index

Overview

Journal ACS Cent Sci

Specialty Chemistry

Date 2021 Nov 3

PMID 34729408

Citations 7

Authors

Yanpei Song

Changjia Zhu

Qi Sun

Briana Aguila

Carter W Abney

Lukasz Wojtas

Shengqian Ma

Affiliations

Soon will be listed here.

Abstract

Mining uranium from seawater is highly desirable for sustaining the increasing demand for nuclear fuel; however, access to this unparalleled reserve has been limited by competitive adsorption of a wide variety of concentrated competitors, especially vanadium. Herein, we report the creation of a series of uranyl-specific "hooks" and the decoration of them into the nanospace of porous organic polymers to afford uranium nanotraps for seawater uranium extraction. Manipulating the relative distances and angles of amidoxime moieties in the ligands enabled the creation of uranyl-specific "hooks" that feature ultrahigh affinity and selective sequestration of uranium with a distribution coefficient threefold higher compared to that of vanadium, overcoming the long-term challenge of the competing adsorption of vanadium for uranium extraction from seawater. The optimized uranium nanotrap (2.5 mg) can extract more than one-third of the uranium in seawater (5 gallons), affording an enrichment index of 3836 and thus presenting a new benchmark for uranium adsorbent. Moreover, with improved selectivity, the uranium nanotraps could be regenerated using a mild base treatment. The synergistic combination of experimental and theoretical analyses in this study provides a mechanistic approach for optimizing the selectivity of chelators toward analytes of interest.

Citing Articles

Photoisomerization-mediated tunable pore size in metal organic frameworks for U(VI)/V(V) selective separation.

Zhang P, Zhang Y, Wu F, Xiao W, Hua W, Tang Z Nat Commun. 2025; 16(1):2361.

PMID: 40064899 PMC: 11894057. DOI: 10.1038/s41467-025-57638-4.

An imidazole-based covalent-organic framework enabling a super-efficiency in sunlight-driven uranium extraction from seawater.

Zhong L, Feng X, Zhang Q, Xie X, Luo F Chem Sci. 2024; 15(28):10882-10891.

PMID: 39027273 PMC: 11253174. DOI: 10.1039/d4sc02554g.

Ultra-selective uranium separation by in-situ formation of π-f conjugated 2D uranium-organic framework.

Zhang Q, Zhang L, Zhu J, Gong L, Huang Z, Gao F Nat Commun. 2024; 15(1):453.

PMID: 38212316 PMC: 10784586. DOI: 10.1038/s41467-023-44663-4.

Self-Standing Porous Aromatic Framework Electrodes for Efficient Electrochemical Uranium Extraction.

Chen D, Li Y, Zhao X, Shi M, Shi X, Zhao R ACS Cent Sci. 2024; 9(12):2326-2332.

PMID: 38161362 PMC: 10755849. DOI: 10.1021/acscentsci.3c01291.

Design and Modulation of Selectivity toward Vanadium(V) and Uranium(VI) Ions: Coordination Properties and Affinity of Hydroxylamino-Triazine Siderophores.

Amoiridis A, Papanikolaou M, Vlasiou M, Bandeira N, Miras H, Kabanos T Inorg Chem. 2023; 62(49):19971-19985.

PMID: 38018803 PMC: 10716903. DOI: 10.1021/acs.inorgchem.3c02678.

References

Kou S, Yang Z, Sun F . Protein Hydrogel Microbeads for Selective Uranium Mining from Seawater. ACS Appl Mater Interfaces. 2017; 9(3):2035-2039. DOI: 10.1021/acsami.6b15968. View

Wang X, Chen Y, Song L, Fang Z, Zhang J, Shi F . Cooperative Capture of Uranyl Ions by a Carbonyl-Bearing Hierarchical-Porous Cu-Organic Framework. Angew Chem Int Ed Engl. 2019; 58(52):18808-18812. DOI: 10.1002/anie.201909045. View

Ling L, Zhang W . Enrichment and encapsulation of uranium with iron nanoparticle. J Am Chem Soc. 2015; 137(8):2788-91. DOI: 10.1021/ja510488r. View

Leggett C, Parker B, Teat S, Zhang Z, Dau P, Lukens W . Structural and spectroscopic studies of a rare non-oxido V(v) complex crystallized from aqueous solution. Chem Sci. 2017; 7(4):2775-2786. PMC: 5477013. DOI: 10.1039/c5sc03958d. View

Lu Y . Uranium extraction: Coordination chemistry in the ocean. Nat Chem. 2014; 6(3):175-7. DOI: 10.1038/nchem.1880. View

Cui W, Zhang C, Jiang W, Li F, Liang R, Liu J . Regenerable and stable sp carbon-conjugated covalent organic frameworks for selective detection and extraction of uranium. Nat Commun. 2020; 11(1):436. PMC: 6978342. DOI: 10.1038/s41467-020-14289-x. View

Yuan Y, Yang Y, Ma X, Meng Q, Wang L, Zhao S . Molecularly Imprinted Porous Aromatic Frameworks and Their Composite Components for Selective Extraction of Uranium Ions. Adv Mater. 2018; 30(12):e1706507. DOI: 10.1002/adma.201706507. View

Kelley S, Barber P, Mullins P, Rogers R . Structural clues to UO₂²⁺/VO₂⁺ competition in seawater extraction using amidoxime-based extractants. Chem Commun (Camb). 2014; 50(83):12504-7. DOI: 10.1039/c4cc06370h. View

Yuan Y, Niu B, Yu Q, Guo X, Guo Z, Wen J . Photoinduced Multiple Effects to Enhance Uranium Extraction from Natural Seawater by Black Phosphorus Nanosheets. Angew Chem Int Ed Engl. 2019; 59(3):1220-1227. DOI: 10.1002/anie.201913644. View

10.

Ma S, Huang L, Ma L, Shim Y, Islam S, Wang P . Efficient uranium capture by polysulfide/layered double hydroxide composites. J Am Chem Soc. 2015; 137(10):3670-7. DOI: 10.1021/jacs.5b00762. View

11.

Gilbert A, Bazilian M . Can Distributed Nuclear Power Address Energy Resilience and Energy Poverty?. Joule. 2020; 4(9):1839-1843. PMC: 7437435. DOI: 10.1016/j.joule.2020.08.005. View

12.

Deutch J . Is Net Zero Carbon 2050 Possible?. Joule. 2020; 4(11):2237-2240. PMC: 7485569. DOI: 10.1016/j.joule.2020.09.002. View

13.

Feng L, Wang H, Feng T, Yan B, Yu Q, Zhang J . In Situ Synthesis of Uranyl-Imprinted Nanocage for Selective Uranium Recovery from Seawater. Angew Chem Int Ed Engl. 2021; 61(13):e202101015. DOI: 10.1002/anie.202101015. View

14.

Yuan Y, Feng S, Feng L, Yu Q, Liu T, Wang N . A Bio-inspired Nano-pocket Spatial Structure for Targeting Uranyl Capture. Angew Chem Int Ed Engl. 2020; 59(11):4262-4268. DOI: 10.1002/anie.201916450. View

15.

Chen Z, Chen W, Jia D, Liu Y, Zhang A, Wen T . N, P, and S Codoped Graphene-Like Carbon Nanosheets for Ultrafast Uranium (VI) Capture with High Capacity. Adv Sci (Weinh). 2018; 5(10):1800235. PMC: 6193150. DOI: 10.1002/advs.201800235. View

16.

Sun Q, Dai Z, Meng X, Xiao F . Porous polymer catalysts with hierarchical structures. Chem Soc Rev. 2015; 44(17):6018-34. DOI: 10.1039/c5cs00198f. View

17.

Macerata E, Mossini E, Scaravaggi S, Mariani M, Mele A, Panzeri W . Hydrophilic Clicked 2,6-Bis-triazolyl-pyridines Endowed with High Actinide Selectivity and Radiochemical Stability: Toward a Closed Nuclear Fuel Cycle. J Am Chem Soc. 2016; 138(23):7232-5. DOI: 10.1021/jacs.6b03106. View

18.

Sun Q, Aguila B, Earl L, Abney C, Wojtas L, Thallapally P . Covalent Organic Frameworks as a Decorating Platform for Utilization and Affinity Enhancement of Chelating Sites for Radionuclide Sequestration. Adv Mater. 2018; 30(20):e1705479. DOI: 10.1002/adma.201705479. View

19.

Dresselhaus M, Thomas I . Alternative energy technologies. Nature. 2001; 414(6861):332-7. DOI: 10.1038/35104599. View

20.

Li Z, Meng Q, Yang Y, Zou X, Yuan Y, Zhu G . Constructing amidoxime-modified porous adsorbents with open architecture for cost-effective and efficient uranium extraction. Chem Sci. 2021; 11(18):4747-4752. PMC: 8159166. DOI: 10.1039/d0sc00249f. View