A report on emergent uranyl binding phenomena by an amidoxime phosphonic acid co-polymer

C. W. Abney; S. Das; R. T. Mayes; L. J. Kuo; J. Wood; G. Gill; M. Piechowicz; Z. Lin; W. Lin; S. Dai

doi:10.1039/c6cp04772f

A report on emergent uranyl binding phenomena by an amidoxime phosphonic acid co-polymer

C. W. Abney, S. Das, R. T. Mayes, L. J. Kuo, J. Wood, G. Gill, M. Piechowicz, Z. Lin, W. Lin, S. Dai

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Abstract

The development of technology to harvest the uranium dissolved in seawater would enable access to vast quantities of this critical metal for nuclear power generation. Amidoxime polymers are the most promising platforms for achieving this separation, yet the design of advanced adsorbents is hindered by uncertainty regarding the uranium binding mode. In this work we use XAFS to investigate the uranium coordination environment in an amidoxime-phosphonic acid copolymer adsorbent. In contrast to the binding mode predicted computationally and from small molecule studies, a cooperative chelating model is favoured, attributable to emergent behavior resulting from inclusion of amidoxime in the polymer. Samples exposed to seawater also display a feature consistent with a μ²-oxo-bridged transition metal, suggesting the formation of an in situ specific binding site. These findings challenge long held assumptions and provide new opportunities for the design of advanced adsorbent materials.

Original language	English
Pages (from-to)	23462-23468
Number of pages	7
Journal	Physical Chemistry Chemical Physics
Volume	18
Issue number	34
DOIs	https://doi.org/10.1039/c6cp04772f
State	Published - 2016

Funding

This research was conducted at Oak Ridge National Laboratory (ORNL), the Marine Sciences Laboratory of Pacific Northwest National Laboratory (PNNL), and the University of Chicago. Work at ORNL and PNNL was sponsored by the U.S. Department of Energy (DOE), Office of Nuclear Energy. Work at the University of Chicago was supported by the U.S DOE Office of Nuclear Energy's Nuclear Energy University Program (Sub-Contract - 20 #120427, Project #3151). XAFS data were collected at the Advanced Photon Source at Argonne National Laboratory on a Beamline 10BM-B, supported by the Materials Research Collaborative Access Team (MRCAT). MRCAT operations are supported by the DOE and the MRCAT member institutions. The Advanced Photon Source is a U.S. DOE Office of Science User Facility operated for the DOE Office of Science by Argonne National Laboratory under Contract No. DE-AC02-06CH11357. The United States Government retains, and by accepting the article for publication the publisher acknowledges that the United States Government retains, a non-exclusive, paid-up, irrevocable, world-wide license to publish or reproduce the published form of this manuscript, or allow others to do so, for the United States Government purposes. The Department of Energy will provide public access to these results of federally sponsored research in accordance with the DOE Public Access Plan (url="http://energy.gov/downloads/doe-public-access-plan http://energy.gov/downloads/doe-public-access-plan).

Funders	Funder number
DOE Public Access Plan
Marine Sciences Laboratory of Pacific Northwest National Laboratory
Materials Research Collaborative Access Team
United States Government
U.S. Department of Energy
Office of Science	DE-AC02-06CH11357
Office of Nuclear Energy	3151, 120427
Argonne National Laboratory
Oak Ridge National Laboratory
University of Chicago
Pacific Northwest National Laboratory

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abstract = "The development of technology to harvest the uranium dissolved in seawater would enable access to vast quantities of this critical metal for nuclear power generation. Amidoxime polymers are the most promising platforms for achieving this separation, yet the design of advanced adsorbents is hindered by uncertainty regarding the uranium binding mode. In this work we use XAFS to investigate the uranium coordination environment in an amidoxime-phosphonic acid copolymer adsorbent. In contrast to the binding mode predicted computationally and from small molecule studies, a cooperative chelating model is favoured, attributable to emergent behavior resulting from inclusion of amidoxime in the polymer. Samples exposed to seawater also display a feature consistent with a μ2-oxo-bridged transition metal, suggesting the formation of an in situ specific binding site. These findings challenge long held assumptions and provide new opportunities for the design of advanced adsorbent materials.",

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AU - Piechowicz, M.

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A report on emergent uranyl binding phenomena by an amidoxime phosphonic acid co-polymer

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