Highly Preorganized Ligand 1,10-Phenanthroline-2,9-dicarboxylic Acid for the Selective Recovery of Uranium from Seawater in the Presence of Competing Vanadium Species

Lashley, Mark A.; Ivanov, Alexander S.; Bryantsev, Vyacheslav S.; Dai, Sheng; Hancock, Robert D.

doi:10.1021/acs.inorgchem.6b02234

Highly Preorganized Ligand 1,10-Phenanthroline-2,9-dicarboxylic Acid for the Selective Recovery of Uranium from Seawater in the Presence of Competing Vanadium Species

Journal Article · Fri Sep 30 00:00:00 EDT 2016 · Inorganic Chemistry

DOI:https://doi.org/10.1021/acs.inorgchem.6b02234· OSTI ID:1329747

Lashley, Mark A. ^[1]; Ivanov, Alexander S. ^[2]; Bryantsev, Vyacheslav S. ^[2]; Dai, Sheng ^[2]; Hancock, Robert D. ^[1]

Univ. of North Carolina Wilmington, NC (United States). Dept. of Chemistry and Biochemistry
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Chemical Sciences Division

Studies of the complexation of new promising ligands with uranyl (UO₂²⁺) and other seawater cations can aid the development of more efficient, selective, and robust sorbents for the recovery of uranium from seawater. Here, we propose that the ligand design principles based on structural preorganization can be successfully applied to obtain a dramatic enhancement in UO₂²⁺ ion binding affinity and selectivity. This concept is exemplified through the investigation of the com-plexes of UO₂²⁺, VO²⁺, and VO²⁺ with the highly preorganized ligand PDA (1,10-phenanthroline-2,9-dicarboxylic acid) using a combination of fluores-cence and absorbance techniques, along with den-sity functional theory (DFT) calculations. Moreover, the measured stability constant value, log K1, of 16.5 for the UO₂²⁺/PDA complex is very high compared to uranyl complexes with other dicarboxylic ligands. Moreover, PDA exhibits strong selectivity for uranyl over vanadium ions, since the determined sta-bility constant values of the PDA complexes of the vanadium ions are quite low (V(IV) log K1 = 7.4, V(V) = 7.3). Finally, the structures of the corresponding UO₂²⁺, VO²⁺, and VO²⁺ complexes with PDA were identified by systematic DFT calculations, and helped to interpret the stronger binding affinity for uranium over the vanadium ions. Due to its high chemical stability, selectivity, and structural preor-ganization for UO₂²⁺ complexation, PDA is a very promising candidate that can be potentially used in the development of novel adsorbent materials for the selective extraction of uranium from sea-water.

View Accepted Manuscript (DOE)

Research Organization:: Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)

Sponsoring Organization:: USDOE Office of Nuclear Energy (NE)

Grant/Contract Number:: AC02-05CH11231; AC05-00OR22725

OSTI ID:: 1329747

Journal Information:: Inorganic Chemistry, Journal Name: Inorganic Chemistry Journal Issue: 20 Vol. 55; ISSN 0020-1669

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

References (64)

Topological analysis of electron density distribution taken from a pseudopotential calculation Vyboishchikov, Sergei F.; Sierraalta, Anibal; Frenking, Gernot Journal of Computational Chemistry, Vol. 18, Issue 3 https://doi.org/10.1002/(SICI)1096-987X(199702)18:3<416::AID-JCC11>3.0.CO;2-G	journal	February 1997
Synthesis of some 2,9-disubstituted-1,10-phenanthrolines Chandler, Christopher J.; Deady, Leslie W.; Reiss, James A. Journal of Heterocyclic Chemistry, Vol. 18, Issue 3 https://doi.org/10.1002/jhet.5570180332	journal	May 1981
Principles of Fluorescence Spectroscopy Lakowicz, Joseph R. Springer New York, NY https://doi.org/10.1007/978-0-387-46312-4	book	January 2006
The M06 suite of density functionals for main group thermochemistry, thermochemical kinetics, noncovalent interactions, excited states, and transition elements: two new functionals and systematic testing of four M06-class functionals and 12 other functionals Zhao, Yan; Truhlar, Donald G. Theoretical Chemistry Accounts, Vol. 120, Issue 1-3 https://doi.org/10.1007/s00214-007-0310-x	journal	July 2007
Vanadyl in natural waters: Adsorption and hydrolysis promote oxygenation Wehrli, Bernhard; Stumm, Werner Geochimica et Cosmochimica Acta, Vol. 53, Issue 1 https://doi.org/10.1016/0016-7037(89)90273-1	journal	January 1989
Vanadium behaviour in the global ocean and in the Mediterranean sea Jeandel, C.; Caisso, M.; Minster, J. F. Marine Chemistry, Vol. 21, Issue 1 https://doi.org/10.1016/0304-4203(87)90029-6	journal	May 1987
Hyperquad simulation and speciation (HySS): a utility program for the investigation of equilibria involving soluble and partially soluble species Alderighi, Lucia; Gans, Peter; Ienco, Andrea Coordination Chemistry Reviews, Vol. 184, Issue 1 https://doi.org/10.1016/S0010-8545(98)00260-4	journal	April 1999
Preparation of hydrophilic amidoxime fibers by cografting acrylonitrile and methacrylic acid from an optimized monomer composition Kawai, Tomomi; Saito, Kyoichi; Sugita, Kazuyuki Radiation Physics and Chemistry, Vol. 59, Issue 4, p. 405-411 https://doi.org/10.1016/S0969-806X(00)00298-X	journal	October 2000
Adsorption of UO2+2 by polyethylene adsorbents with amidoxime, carboxyl, and amidoxime/carboxyl group Choi, Seong-Ho; Nho, Young Chang Radiation Physics and Chemistry, Vol. 57, Issue 2 https://doi.org/10.1016/S0969-806X(99)00348-5	journal	February 2000
Complexes of the highly preorganized ligand PDALC (2,9-bis(hydroxymethyl)-1,10-phenanthroline) with trivalent lanthanides. A thermodynamic and crystallographic study Williams, Neil J.; Ballance, Daniel G.; Reibenspies, Joseph H. Inorganica Chimica Acta, Vol. 363, Issue 14 https://doi.org/10.1016/j.ica.2010.05.023	journal	November 2010
Vanadium speciation and cycling in coastal waters Wang, Deli; Sañudo Wilhelmy, Sergio A. Marine Chemistry, Vol. 117, Issue 1-4 https://doi.org/10.1016/j.marchem.2009.06.001	journal	December 2009
Current status of adsorbent for metal ions with radiation grafting and crosslinking techniques Seko, Noriaki; Tamada, Masao; Yoshii, Fumio Nuclear Instruments and Methods in Physics Research Section B: Beam Interactions with Materials and Atoms, Vol. 236, Issue 1-4 https://doi.org/10.1016/j.nimb.2005.03.244	journal	July 2005
Amidoximes as ligand functionalities for braided polymeric materials for the recovery of uranium from seawater Lashley, Mark A.; Mehio, Nada; Nugent, Joseph W. Polyhedron, Vol. 109 https://doi.org/10.1016/j.poly.2016.01.026	journal	April 2016
Alternative Alkaline Conditioning of Amidoxime Based Adsorbent for Uranium Extraction from Seawater Das, S.; Liao, W. -P.; Flicker Byers, M. Industrial & Engineering Chemistry Research, Vol. 55, Issue 15 https://doi.org/10.1021/acs.iecr.5b03210	journal	October 2015
Theoretical Study of Oxovanadium(IV) Complexation with Formamidoximate: Implications for the Design of Uranyl-Selective Adsorbents Mehio, Nada; Ivanov, Alexander S.; Ladshaw, Austin P. Industrial & Engineering Chemistry Research, Vol. 55, Issue 15 https://doi.org/10.1021/acs.iecr.5b03398	journal	December 2015
Scientific Basis for Efficient Extraction of Uranium from Seawater. I: Understanding the Chemical Speciation of Uranium under Seawater Conditions Endrizzi, Francesco; Leggett, Christina J.; Rao, Linfeng Industrial & Engineering Chemistry Research, Vol. 55, Issue 15 https://doi.org/10.1021/acs.iecr.5b03679	journal	December 2015
Predicting Stability Constants for Uranyl Complexes Using Density Functional Theory Vukovic, Sinisa; Hay, Benjamin P.; Bryantsev, Vyacheslav S. Inorganic Chemistry, Vol. 54, Issue 8 https://doi.org/10.1021/acs.inorgchem.5b00264	journal	March 2015
Design of complexes between synthetic hosts and organic guests Cram, Donald J.; Cram, Jane M. Accounts of Chemical Research, Vol. 11, Issue 1 https://doi.org/10.1021/ar50121a002	journal	January 1978
Ligand design for selective complexation of metal ions in aqueous solution Hancock, Robert D.; Martell, Arthur E. Chemical Reviews, Vol. 89, Issue 8 https://doi.org/10.1021/cr00098a011	journal	December 1989
All-Electron Scalar Relativistic Basis Sets for Third-Row Transition Metal Atoms Pantazis, Dimitrios A.; Chen, Xian-Yang; Landis, Clark R. Journal of Chemical Theory and Computation, Vol. 4, Issue 6 https://doi.org/10.1021/ct800047t	journal	May 2008
Chelate ring size and metal ion selection. The basis of selectivity for metal ions in open-chain ligands and macrocycles Hancock, Robert D. Journal of Chemical Education, Vol. 69, Issue 8 https://doi.org/10.1021/ed069p615	journal	August 1992
Complexes of Greatly Enhanced Thermodynamic Stability and Metal Ion Size-Based Selectivity, Formed by the Highly Preorganized Non-Macrocyclic Ligand 1,10-Phenanthroline-2,9-dicarboxylic Acid. A Thermodynamic and Crystallographic Study Melton, Darren L.; VanDerveer, Donald G.; Hancock, Robert D. Inorganic Chemistry, Vol. 45, Issue 23 https://doi.org/10.1021/ic061010p	journal	October 2006
Unusual Metal Ion Selectivities of the Highly Preorganized Tetradentrate Ligand 1,10-Phenanthroline-2,9-dicarboxamide: A Thermodynamic and Fluorescence Study Merrill, Danielle; Harrington, James M.; Lee, Hee-Seung Inorganic Chemistry, Vol. 50, Issue 17 https://doi.org/10.1021/ic200905f	journal	September 2011
Selectivity of the Highly Preorganized Tetradentate Ligand 2,9-Di(pyrid-2-yl)-1,10-phenanthroline for Metal Ions in Aqueous Solution, Including Lanthanide(III) Ions and the Uranyl(VI) Cation Carolan, Ashley N.; Cockrell, Gregory M.; Williams, Neil J. Inorganic Chemistry, Vol. 52, Issue 1 https://doi.org/10.1021/ic3002509	journal	December 2012
Theoretical Insights on the Interaction of Uranium with Amidoxime and Carboxyl Groups Wang, Cong-Zhi; Lan, Jian-Hui; Wu, Qun-Yan Inorganic Chemistry, Vol. 53, Issue 18 https://doi.org/10.1021/ic500202g	journal	August 2014
Affinity of the Highly Preorganized Ligand PDA (1,10-Phenanthroline-2,9-dicarboxylic acid) for Large Metal Ions of Higher Charge. A Crystallographic and Thermodynamic Study of PDA Complexes of Thorium(IV) and the Uranyl(VI) ion Dean, Nolan E.; Hancock, Robert D.; Cahill, Christopher L. Inorganic Chemistry, Vol. 47, Issue 6 https://doi.org/10.1021/ic701574j	journal	March 2008
Metal Ion Complexing Properties of the Highly Preorganized Ligand 2,9-bis(Hydroxymethyl)-1,10-phenanthroline: A Crystallographic and Thermodynamic Study Gephart, Raymond T.; Williams, Neil J.; Reibenspies, Joseph H. Inorganic Chemistry, Vol. 47, Issue 22 https://doi.org/10.1021/ic8008656	journal	November 2008
Complexation of Metal Ions of Higher Charge by the Highly Preorganized Tetradentate Ligand 2,9-Bis(hydroxymethyl)-1,10-Phenanthroline. A Crystallographic and Thermodynamic Study Gephart, Raymond T.; Williams, Neil J.; Reibenspies, Joseph H. Inorganic Chemistry, Vol. 48, Issue 17 https://doi.org/10.1021/ic900650d	journal	September 2009
Strong Metal Ion Size Based Selectivity of the Highly Preorganized Ligand PDA (1,10-Phenanthroline-2,9-dicarboxylic Acid) with Trivalent Metal Ions. A Crystallographic, Fluorometric, and Thermodynamic Study Williams, Neil J.; Dean, Nolan E.; VanDerveer, Donald G. Inorganic Chemistry, Vol. 48, Issue 16 https://doi.org/10.1021/ic900737q	journal	July 2009
Uptake of Uranium from Seawater by Amidoxime-Based Polymeric Adsorbent: Field Experiments, Modeling, and Updated Economic Assessment Kim, Jungseung; Tsouris, Costas; Oyola, Yatsandra Industrial & Engineering Chemistry Research, Vol. 53, Issue 14 https://doi.org/10.1021/ie4039828	journal	March 2014
Relativistic and correlation effects for element 105 (hahnium, Ha): a comparative study of M and MO (M = Nb, Ta, Ha) using energy-adjusted ab initio pseudopotentials Dolg, Michael; Stoll, Hermann; Preuss, Heinzwerner The Journal of Physical Chemistry, Vol. 97, Issue 22 https://doi.org/10.1021/j100124a012	journal	June 1993
Molecular design of calixarene-based uranophiles which exhibit remarkably high stability and selectivity Shinkai, Seiji; Koreishi, Hiroshi; Ueda, Kaori Journal of the American Chemical Society, Vol. 109, Issue 21 https://doi.org/10.1021/ja00255a023	journal	October 1987
Natural hybrid orbitals Foster, J. P.; Weinhold, F. Journal of the American Chemical Society, Vol. 102, Issue 24 https://doi.org/10.1021/ja00544a007	journal	September 1980
Enhanced Metal Ion Selectivity of 2,9-Di-(pyrid-2-yl)-1,10-phenanthroline and Its Use as a Fluorescent Sensor for Cadmium(II) Cockrell, Gregory M.; Zhang, Gang; VanDerveer, Donald G. Journal of the American Chemical Society, Vol. 130, Issue 4 https://doi.org/10.1021/ja077141m	journal	January 2008
Universal Solvation Model Based on Solute Electron Density and on a Continuum Model of the Solvent Defined by the Bulk Dielectric Constant and Atomic Surface Tensions Marenich, Aleksandr V.; Cramer, Christopher J.; Truhlar, Donald G. The Journal of Physical Chemistry B, Vol. 113, Issue 18, p. 6378-6396 https://doi.org/10.1021/jp810292n	journal	May 2009
Crystal Structure of a Uranyl/p-tert-Butylcalix[5]arene Complex Thuéry, Pierre; Nierlich, Martine Journal of Inclusion Phenomena and Molecular Recognition in Chemistry, Vol. 27, Issue 1, p. 13-20 https://doi.org/10.1023/A:1007938218723	journal	January 1997
Extraction of uranium from seawater by polymer-bound macrocyclic hexaketone Tabushi, Iwao; Kobuke, Yoshiaki; Nishiya, Takako Nature, Vol. 280, Issue 5724 https://doi.org/10.1038/280665a0	journal	August 1979
Seven chemical separations to change the world Sholl, David S.; Lively, Ryan P. Nature, Vol. 532, Issue 7600 https://doi.org/10.1038/532435a	journal	April 2016
A protein engineered to bind uranyl selectively and with femtomolar affinity Zhou, Lu; Bosscher, Mike; Zhang, Changsheng Nature Chemistry, Vol. 6, Issue 3 https://doi.org/10.1038/nchem.1856	journal	January 2014
Structure, equilibrium and ligand exchange dynamics in the binary and ternary dioxouranium( vi )-ethylenediamine-N,N′-diacetic acid-fluoride system: a potentiometric, NMR and X-ray crystallographic study Palladino, Giuseppe; Szabó, Zoltán; Fischer, Andreas Dalton Trans., Issue 43 https://doi.org/10.1039/B608814G	journal	January 2006
Solvent extraction: the coordination chemistry behind extractive metallurgy Wilson, A. Matthew; Bailey, Phillip J.; Tasker, Peter A. Chem. Soc. Rev., Vol. 43, Issue 1 https://doi.org/10.1039/C3CS60275C	journal	January 2014
Quantifying the binding strength of U( vi ) with phthalimidedioxime in comparison with glutarimidedioxime Sun, Xiaoqi; Tian, Guoxin; Xu, Chao Dalton Trans., Vol. 43, Issue 2 https://doi.org/10.1039/C3DT52206G	journal	January 2014
Theoretical study of the coordination behavior of formate and formamidoximate with dioxovanadium( v ) cation: implications for selectivity towards uranyl Mehio, Nada; Johnson, J. Casey; Dai, Sheng Physical Chemistry Chemical Physics, Vol. 17, Issue 47 https://doi.org/10.1039/C5CP06165B	journal	January 2015
Structural and spectroscopic studies of a rare non-oxido V( v ) complex crystallized from aqueous solution Leggett, C. J.; Parker, B. F.; Teat, S. J. Chemical Science, Vol. 7, Issue 4 https://doi.org/10.1039/C5SC03958D	journal	January 2016
Quantifying the binding strength of salicylaldoxime–uranyl complexes relative to competing salicylaldoxime–transition metal ion complexes in aqueous solution: a combined experimental and computational study Mehio, Nada; Ivanov, Alexander S.; Williams, Neil J. Dalton Transactions, Vol. 45, Issue 22 https://doi.org/10.1039/C6DT00116E	journal	January 2016
Assessing ligand selectivity for uranium over vanadium ions to aid in the discovery of superior adsorbents for extraction of UO ₂ ²⁺ from seawater Ivanov, Alexander S.; Bryantsev, Vyacheslav S. Dalton Transactions, Vol. 45, Issue 26 https://doi.org/10.1039/C6DT01752E	journal	January 2016
Encapsulation of the uranyl dication Beer, Stephan; Berryman, Orion B.; Ajami, Dariush Chemical Science, Vol. 1, Issue 1 https://doi.org/10.1039/c0sc00116c	journal	January 2010
Sequestering uranium from seawater: binding strength and modes of uranyl complexes with glutarimidedioxime Tian, Guoxin; Teat, Simon J.; Zhang, Zhiyong Dalton Transactions, Vol. 41, Issue 38 https://doi.org/10.1039/c2dt30978e	journal	January 2012
Challenges to achievement of metal sustainability in our high-tech society Izatt, Reed M.; Izatt, Steven R.; Bruening, Ronald L. Chem. Soc. Rev., Vol. 43, Issue 8 https://doi.org/10.1039/c3cs60440c	journal	January 2014
Thermodynamic studies of U(vi) complexation with glutardiamidoxime for sequestration of uranium from seawater Tian, Guoxin; Teat, Simon J.; Rao, Linfeng Dalton Transactions, Vol. 42, Issue 16 https://doi.org/10.1039/c3dt32940b	journal	January 2013
Complexation of glutarimidedioxime with Fe(iii), Cu(ii), Pb(ii), and Ni(ii), the competing ions for the sequestration of U(vi) from seawater Sun, Xiaoqi; Xu, Chao; Tian, Guoxin Dalton Transactions, Vol. 42, Issue 40 https://doi.org/10.1039/c3dt51767e	journal	January 2013
Energy Levels and Thermodynamic Functions for Molecules with Internal Rotation I. Rigid Frame with Attached Tops Pitzer, Kenneth S.; Gwinn, William D. The Journal of Chemical Physics, Vol. 10, Issue 7 https://doi.org/10.1063/1.1723744	journal	July 1942
Density‐functional thermochemistry. III. The role of exact exchange Becke, Axel D. The Journal of Chemical Physics, Vol. 98, Issue 7, p. 5648-5652 https://doi.org/10.1063/1.464913	journal	April 1993
Identification and treatment of internal rotation in normal mode vibrational analysis Ayala, Philippe Y.; Schlegel, H. Bernhard The Journal of Chemical Physics, Vol. 108, Issue 6 https://doi.org/10.1063/1.475616	journal	February 1998
Recovery of Uranium from Seawater: A Review of Current Status and Future Research Needs Kim, Jungseung; Tsouris, Costas; Mayes, Richard T. Separation Science and Technology, Vol. 48, Issue 3 https://doi.org/10.1080/01496395.2012.712599	journal	January 2013
Present Status of Study on Extraction of Uranium from Sea Water Kanno, Masayoshi Journal of Nuclear Science and Technology, Vol. 21, Issue 1 https://doi.org/10.1080/18811248.1984.9731004	journal	January 1984
Development of the Colle-Salvetti correlation-energy formula into a functional of the electron density Lee, Chengteh; Yang, Weitao; Parr, Robert G. Physical Review B, Vol. 37, Issue 2 https://doi.org/10.1103/PhysRevB.37.785	journal	January 1988
Revised effective ionic radii and systematic studies of interatomic distances in halides and chalcogenides Shannon, R. D. Acta Crystallographica Section A, Vol. 32, Issue 5, p. 751-767 https://doi.org/10.1107/S0567739476001551	journal	September 1976
Stability Constants of Some Uranyl Complexes Ramamoorthy, S.; Santappa, M. Bulletin of the Chemical Society of Japan, Vol. 41, Issue 6 https://doi.org/10.1246/bcsj.41.1330	journal	June 1968
Aquaculture of Uranium in Seawater by a Fabric-Adsorbent Submerged System Seko, Noriaki; Katakai, Akio; Hasegawa, Shin Nuclear Technology, Vol. 144, Issue 2 https://doi.org/10.13182/NT03-2	journal	November 2003
Metal ion selectivities of the highly preorganized tetradentate ligand 1,10-phenanthroline-2,9-dicarboxamide with lanthanide(III) ions and some actinide ions Merrill, Danielle; Hancock, Robert D. Radiochimica Acta, Vol. 99, Issue 3 https://doi.org/10.1524/ract.2011.1805	journal	March 2011
Fractional Elution and Determination of Uranium and Vanadium Adsorbed on Amidoxime Fiber from Seawater. Suzuki, Toshihiro; Saito, Kyoichi; Sugo, Takanobu Analytical Sciences, Vol. 16, Issue 4 https://doi.org/10.2116/analsci.16.429	journal	January 2000
Recent International R&D Activities in the Extraction of Uranium from Seawater Rao, Linfeng https://doi.org/10.2172/1000969	report	March 2010
Cost Estimation of Uranium Recovery from Seawater with System of Braid Type Adsorbent [モール状捕集システムによる海水ウラン捕集のコスト試算] Tamada, Masao; Seko, Noriaki; Kasai, Noboru Transactions of the Atomic Energy Society of Japan, Vol. 5, Issue 4 https://doi.org/10.3327/taesj2002.5.358	journal	January 2006

Cited By (4)

Predicting Stability Constants for Terbium(III) Complexes with Dipicolinic Acid and 4-Substituted Dipicolinic Acid Analogues using Density Functional Theory Chen, Hsieh; Shi, Rena; Ow, Hooisweng ACS Omega, Vol. 4, Issue 24 https://doi.org/10.1021/acsomega.9b02851	journal	November 2019
Strategic Design and Utilization of Molecular Flexibility for Straddling the Application of Organic Superbases: A DFT Study Singh, Ajeet; Ojha, Animesh K.; Jang, Hyun Myung ChemistrySelect, Vol. 3, Issue 2 https://doi.org/10.1002/slct.201702912	journal	January 2018
A highly efficient uranium grabber derived from acrylic fiber for extracting uranium from seawater Pan, Horng-Bin; Wai, Chien M.; Kuo, Li-Jung Dalton Transactions, Vol. 49, Issue 9 https://doi.org/10.1039/c9dt04562g	journal	January 2020
The impact of alicyclic substituents on the extraction ability of new family of 1,10-phenanthroline-2,9-diamides Lemport, Pavel S.; Matveev, Petr I.; Yatsenko, Alexander V. RSC Advances, Vol. 10, Issue 44 https://doi.org/10.1039/d0ra05182a	journal	January 2020