Bridging the Transuranics with Uranium(IV) Sulfate Aqueous Species and Solid Phases

Colliard, Ian; Falaise, Clement; Nyman, May

doi:10.1021/acs.inorgchem.0c02267

Title: Bridging the Transuranics with Uranium(IV) Sulfate Aqueous Species and Solid Phases

Journal Article · Thu Nov 19 00:00:00 EST 2020 · Inorganic Chemistry

DOI:https://doi.org/10.1021/acs.inorgchem.0c02267· OSTI ID:1725817

Colliard, Ian ^[1];

^[1];

^[1]

Oregon State Univ., Corvallis, OR (United States)

Isolating isomorphic compounds of tetravalent actinides (i.e., Th^IV, U^IV, Np^IV, and Pu^IV) improve our understanding of the bonding behavior across the series, in addition to their relationship with tetravalent transition metals (Zr and Hf) and lanthanides (Ce). Similarities between these tetravalent metals are particularly illuminated in their hydrolysis and condensation behavior in aqueous systems, leading to polynuclear clusters typified by the hexamer [M^IV ₆O₄(OH)₄]¹²⁺ building block. Prior studies have shown the predominance and coexistence of smaller species for Th^IV (monomers, dimers, and hexamers) and larger species for U^IV, Np^IV, and Pu^IV (including 38-mers and 70-mers). We show here that aqueous uranium(IV) sulfate also displays behavior similar to that of Th^IV (and Zr^IV) in its isolated solidphase and solution speciation. Two single-crystal X-ray structures are described: a dihydroxide-bridged dimer (U₂) formulated as U₂(OH)₂(SO₄)₃(H₂O)₄ and a monomer-linked hexamer framework (U-U₆) as (U(H₂O)_3.5)₂U₆O₄(OH)₄(SO₄)₁₀(H₂O)₉. These structures are similar to those previously described for ThIV. Moreover, cocrystallization of monomer and dimer and of dimer and monomer–hexamer phases for both Th^IV (prior) and U^IV (current) indicates the coexistence of these species in solution. Because it was not possible to effectively study the sulfate-rich solutions via X-ray scattering from which U₂ and U-U₆ crystallized, we provide a parallel solution speciation study in low sulfate conditions, as a function of the pH. Raman spectroscopy, UV–vis spectroscopy, and small-angle X-ray scattering of these show decreasing sulfate binding, increased hydrolysis, increased species size, and increased complexity, with increasing pH. Furthermore, this study describes a bridge across the first half the actinide series, highlighting U^IV similarities to Th^IV, in addition to the previously known similarities to the transuranic elements.

View Accepted Manuscript (DOE)

Cite

Export

Save

Research Organization:: University of Notre Dame, IN (United States)

Sponsoring Organization:: USDOE National Nuclear Security Administration (NNSA)

Grant/Contract Number:: NA0003763

OSTI ID:: 1725817

Journal Information:: Inorganic Chemistry, Vol. 59, Issue 23; ISSN 0020-1669

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

References (59)

Unexpected Roles of Alkali-Metal Cations in the Assembly of Low-Valent Uranium Sulfate Molecular Complexes Yue, Zenghui; Guo, Xiaofeng; Feng, Mei-Ling Inorganic Chemistry, Vol. 59, Issue 4 https://doi.org/10.1021/acs.inorgchem.9b03182	journal	February 2020
Solution and Solid-State Structural Chemistry of Actinide Hydrates and Their Hydrolysis and Condensation Products Knope, Karah E.; Soderholm, L. Chemical Reviews, Vol. 113, Issue 2 https://doi.org/10.1021/cr300212f	journal	October 2012
Extension of the Plutonium Oxide Nanocluster Family to Include {Pu ₁₆ } and {Pu ₂₂ } Sigmon, Ginger E.; Hixon, Amy E. Chemistry - A European Journal, Vol. 25, Issue 10 https://doi.org/10.1002/chem.201805605	journal	January 2019
X-ray diffraction "fingerprinting" of DNA structure in solution for quantitative evaluation of molecular dynamics simulation Zuo, X.; Cui, G.; Merz, K. M. Proceedings of the National Academy of Sciences, Vol. 103, Issue 10 https://doi.org/10.1073/pnas.0600022103	journal	February 2006
Advancement of Actinide Metal–Organic Framework Chemistry via Synthesis of Pu-UiO-66 Hastings, Ashley M.; Ray, Debmalya; Jeong, WooSeok Journal of the American Chemical Society, Vol. 142, Issue 20 https://doi.org/10.1021/jacs.0c01895	journal	April 2020
Uranium(IV) Sulfates: Investigating Structural Periodicity in the Tetravalent Actinides Schnaars, David D.; Wilson, Richard E. Inorganic Chemistry, Vol. 51, Issue 17 https://doi.org/10.1021/ic301291w	journal	August 2012
Synthesis and structural characterization of the first neptunium based metal–organic frameworks incorporating {Np ₆ O ₈ } hexanuclear clusters Martin, N. P.; März, J.; Feuchter, H. Chemical Communications, Vol. 54, Issue 51 https://doi.org/10.1039/C8CC03121E	journal	January 2018
Experimental and Quantum Mechanical Characterization of an Oxygen‐Bridged Plutonium(IV) Dimer Ray, Debmalya; Xie, Jing; White, Jacob Chemistry – A European Journal, Vol. 26, Issue 36 https://doi.org/10.1002/chem.202000638	journal	June 2020
Aqueous chemistry of metal cations: Hydrolysis, condensation and complexation Henry, Marc; Jolivet, Jean Pierre; Livage, Jacques Chemistry, Spectroscopy and Applications of Sol-Gel Glasses, p. 153-206 https://doi.org/10.1007/BFb0036968	book	December 2005
A novel nonanuclear hafnium oxide–hydroxide–sulphate cluster crystallised from aqueous solution Kalaji, A.; Soderholm, L. Chem. Commun., Vol. 50, Issue 8 https://doi.org/10.1039/C3CC48167K	journal	January 2014
Isolation of the Large {Actinide} ₃₈ Poly-oxo Cluster with Uranium Falaise, Clément; Volkringer, Christophe; Vigier, Jean-François Journal of the American Chemical Society, Vol. 135, Issue 42 https://doi.org/10.1021/ja4067207	journal	October 2013
Peroxide-Promoted Disassembly Reassembly of Zr-Polyoxocations Sommers, James A.; Hutchison, Danielle C.; Martin, Nicolas P. Journal of the American Chemical Society, Vol. 141, Issue 42 https://doi.org/10.1021/jacs.9b08627	journal	September 2019
The Crystal Structure of Hf(OH)2SO4. Hansson, Margareta; Brattås, Leif; Kjekshus, Arne Acta Chemica Scandinavica, Vol. 27 https://doi.org/10.3891/acta.chem.scand.27-2455	journal	January 1973
Understanding the Role of Aqueous Solution Speciation and Its Application to the Directed Syntheses of Complex Oxidic Zr Chlorides and Sulfates Hu, Yung-Jin; Knope, Karah E.; Skanthakumar, S. Journal of the American Chemical Society, Vol. 135, Issue 38 https://doi.org/10.1021/ja405555h	journal	September 2013
Building [U ^IV ₇₀ (OH) ₃₆ (O) ₆₄ ] ⁴⁻ Oxocluster Frameworks with Sulfate, Transition Metals, and U ^V Colliard, Ian; Nyman, May Chemistry – A European Journal, Vol. 26, Issue 54 https://doi.org/10.1002/chem.202002403	journal	September 2020
Exploring the Actinide−Actinide Bond: Theoretical Studies of the Chemical Bond in Ac ₂ , Th ₂ , Pa ₂ , and U ₂ Roos, Björn O.; Malmqvist, Per-Åke; Gagliardi, Laura Journal of the American Chemical Society, Vol. 128, Issue 51 https://doi.org/10.1021/ja066615z	journal	December 2006
The structures of oxide and hydroxide salts of some tetrapositive ions Lundgren, Georg Recueil des Travaux Chimiques des Pays-Bas, Vol. 75, Issue 5 https://doi.org/10.1002/recl.19560750514	journal	January 1956
Changing Hafnium Speciation in Aqueous Sulfate Solutions: A High-Energy X-ray Scattering Study Kalaji, Ali; Skanthakumar, S.; Kanatzidis, Mercouri G. Inorganic Chemistry, Vol. 53, Issue 12 https://doi.org/10.1021/ic500938k	journal	May 2014
Hafnium Sulfate Prenucleation Clusters and the Hf ₁₈ Polyoxometalate Red Herring Ruther, Rose E.; Baker, Brenna M.; Son, Jung-Ho Inorganic Chemistry, Vol. 53, Issue 8 https://doi.org/10.1021/ic500375v	journal	March 2014
U(IV) Aqueous Speciation from the Monomer to UO ₂ Nanoparticles: Two Levels of Control from Zwitterionic Glycine Ligands Falaise, Clément; Neal, Harrison A.; Nyman, May Inorganic Chemistry, Vol. 56, Issue 11 https://doi.org/10.1021/acs.inorgchem.7b00616	journal	May 2017
OLEX2 : a complete structure solution, refinement and analysis program Dolomanov, Oleg V.; Bourhis, Luc J.; Gildea, Richard J. Journal of Applied Crystallography, Vol. 42, Issue 2 https://doi.org/10.1107/S0021889808042726	journal	January 2009
Stable Metal–Organic Frameworks with Group 4 Metals: Current Status and Trends Yuan, Shuai; Qin, Jun-Sheng; Lollar, Christina T. ACS Central Science, Vol. 4, Issue 4 https://doi.org/10.1021/acscentsci.8b00073	journal	February 2018
Irena : tool suite for modeling and analysis of small-angle scattering Ilavsky, Jan; Jemian, Peter R. Journal of Applied Crystallography, Vol. 42, Issue 2 https://doi.org/10.1107/S0021889809002222	journal	February 2009
The first water-based synthesis of Ce( iv )-MOFs with saturated chiral and achiral C ₄ -dicarboxylate linkers Jacobsen, Jannick; Achenbach, Bastian; Reinsch, Helge Dalton Transactions, Vol. 48, Issue 23 https://doi.org/10.1039/C9DT01542F	journal	January 2019
Plutonium(IV) Cluster with a Hexanuclear [Pu ₆ (OH) ₄ O ₄ ] ¹²⁺ Core Knope, Karah E.; Soderholm, L. Inorganic Chemistry, Vol. 52, Issue 12 https://doi.org/10.1021/ic4007185	journal	May 2013
{Np ₃₈ } clusters: the missing link in the largest poly-oxo cluster series of tetravalent actinides Martin, Nicolas P.; Volkringer, Christophe; Roussel, Pascal Chemical Communications, Vol. 54, Issue 72 https://doi.org/10.1039/C8CC03744B	journal	January 2018
SHELXT – Integrated space-group and crystal-structure determination Sheldrick, George M. Acta Crystallographica Section A Foundations and Advances, Vol. 71, Issue 1, p. 3-8 https://doi.org/10.1107/S2053273314026370	journal	January 2015
Preparation, infrared and visible spectra of Sulfate Complexes of Uranium(IV) Perez, F. Mata; Gil, J. Martin; Gil, F. J. Martin Zeitschrift f�r anorganische und allgemeine Chemie, Vol. 462, Issue 1 https://doi.org/10.1002/zaac.19804620127	journal	March 1980
Structural Snapshots of Cluster Growth from {U ₆ } to {U ₃₈ } During the Hydrolysis of UCl ₄ Chatelain, Lucile; Faizova, Radmila; Fadaei-Tirani, Farzaneh Angewandte Chemie International Edition, Vol. 58, Issue 10 https://doi.org/10.1002/anie.201812509	journal	January 2019
Th ₃ [Th ₆ (OH) ₄ O ₄ (H ₂ O) ₆ ](SO ₄ ) ₁₂ (H ₂ O) ₁₃ : A Self-Assembled Microporous Open-Framework Thorium Sulfate Lin, Jian; Jin, Geng Bang; Soderholm, L. Inorganic Chemistry, Vol. 55, Issue 20 https://doi.org/10.1021/acs.inorgchem.6b01762	journal	September 2016
An X-Ray Investigation of the Coordination and the Hydrolysis of the Uranium(IV) Ion in Aqueous Perchlorate Solutions. Pocev, Stevan; Johansson, Georg; Grønvold, Fredrik Acta Chemica Scandinavica, Vol. 27 https://doi.org/10.3891/acta.chem.scand.27-2146	journal	January 1973
Synthesis and Characterization of Thorium(IV) Sulfates Knope, Karah E.; Wilson, Richard E.; Skanthakumar, S. Inorganic Chemistry, Vol. 50, Issue 17 https://doi.org/10.1021/ic201175u	journal	September 2011
Mononuclear to Polynuclear U ^IV Structural Units: Effects of Reaction Conditions on U‐Furoate Phase Formation Vanagas, Nicole A.; Higgins, Robert F.; Wacker, Jennifer N. Chemistry – A European Journal, Vol. 26, Issue 26 https://doi.org/10.1002/chem.201905759	journal	April 2020
Formation of a new type of uranium( iv ) poly-oxo cluster {U ₃₈ } based on a controlled release of water via esterification reaction Martin, Nicolas P.; Volkringer, Christophe; Henry, Natacha Chemical Science, Vol. 9, Issue 22 https://doi.org/10.1039/C8SC00752G	journal	January 2018
A short history of SHELX Sheldrick, George M. Acta Crystallographica Section A Foundations of Crystallography, Vol. 64, Issue 1, p. 112-122 https://doi.org/10.1107/S0108767307043930	journal	December 2007
Coordination of Tetravalent Actinides (An=Th ^IV , U ^IV , Np ^IV , Pu ^IV ) with DOTA: From Dimers to Hexamers Tamain, Christelle; Dumas, Thomas; Hennig, Christoph Chemistry - A European Journal, Vol. 23, Issue 28 https://doi.org/10.1002/chem.201700493	journal	April 2017
Nanometre-size products of uranium bioreduction Suzuki, Yohey; Kelly, Shelly D.; Kemner, Kenneth M. Nature, Vol. 419, Issue 6903 https://doi.org/10.1038/419134a	journal	September 2002
The Crystal Structure of U(SO4)2-4H2O. Kierkegaard, Peder; Parck, Curt; Ulfvarson, Ulf Acta Chemica Scandinavica, Vol. 10 https://doi.org/10.3891/acta.chem.scand.10-0599	journal	January 1956
Actinide-based MOFs: a middle ground in solution and solid-state structural motifs Dolgopolova, Ekaterina A.; Rice, Allison M.; Shustova, Natalia B. Chemical Communications, Vol. 54, Issue 50 https://doi.org/10.1039/C7CC09780H	journal	January 2018
The Structure of the Plutonium Oxide Nanocluster [Pu38O56Cl54(H2O)8]14− Soderholm, L.; Almond, Philip M.; Skanthakumar, S. Angewandte Chemie International Edition, Vol. 47, Issue 2 https://doi.org/10.1002/anie.200704420	journal	January 2008
Unraveling 5f-6d hybridization in uranium compounds via spin-resolved L-edge spectroscopy dos Reis, R. D.; Veiga, L. S. I.; Escanhoela, C. A. Nature Communications, Vol. 8, Issue 1 https://doi.org/10.1038/s41467-017-01524-1	journal	October 2017
Solution and Solid State Structural Chemistry of Th(IV) and U(IV) 4-Hydroxybenzoates Vanagas, Nicole A.; Wacker, Jennifer N.; Rom, Christopher L. Inorganic Chemistry, Vol. 57, Issue 12 https://doi.org/10.1021/acs.inorgchem.8b00919	journal	June 2018
Understanding the Ligand-Directed Assembly of a Hexanuclear Th ^IV Molecular Cluster in Aqueous Solution Hu, Yung-Jin; Knope, Karah E.; Skanthakumar, S. European Journal of Inorganic Chemistry, Vol. 2013, Issue 24 https://doi.org/10.1002/ejic.201300805	journal	July 2013
Protactinium and the intersection of actinide and transition metal chemistry Wilson, Richard E.; De Sio, Stephanie; Vallet, Valérie Nature Communications, Vol. 9, Issue 1 https://doi.org/10.1038/s41467-018-02972-z	journal	February 2018
The Crystal Structure of Zr ₂ (OH) ₂ (SO ₄ ) ₃ (H ₂ O) ₄ McWhan, D. B.; Lundgren, Georg Inorganic Chemistry, Vol. 5, Issue 2 https://doi.org/10.1021/ic50036a027	journal	February 1966
ABSORPTION SPECTRA OF URANIUM(III) AND URANIUM(IV) IN DClO ₄ SOLUTION ¹ Cohen, Donald; Carnall, W. T. The Journal of Physical Chemistry, Vol. 64, Issue 12 https://doi.org/10.1021/j100841a031	journal	December 1960
First Hexanuclear U ^IV and Th ^IV Formate Complexes - Structure and Stability Range in Aqueous Solution : First Hexanuclear U Takao, Shinobu; Takao, Koichiro; Kraus, Werner European Journal of Inorganic Chemistry, Vol. 2009, Issue 32 https://doi.org/10.1002/ejic.200900899	journal	October 2009
Supramolecular Assembly of U(IV) Clusters and Superatoms with Unconventional Countercations Colliard, Ian; Morrison, Gregory; Loye, Hans-Conrad zur Journal of the American Chemical Society, Vol. 142, Issue 19 https://doi.org/10.1021/jacs.0c03041	journal	April 2020
Cerium(IV) Hexanuclear Clusters from Cerium(III) Precursors: Molecular Models for Oxidative Growth of Ceria Nanoparticles Mathey, Laurent; Paul, Mitali; Copéret, Christophe Chemistry - A European Journal, Vol. 21, Issue 38 https://doi.org/10.1002/chem.201501731	journal	July 2015
Monomeric and Trimeric Thorium Chlorides Isolated from Acidic Aqueous Solution Wacker, Jennifer N.; Vasiliu, Monica; Colliard, Ian Inorganic Chemistry, Vol. 58, Issue 16 https://doi.org/10.1021/acs.inorgchem.9b01238	journal	June 2019
Two Dihydroxo-Bridged Plutonium(IV) Nitrate Dimers and Their Relevance to Trends in Tetravalent Ion Hydrolysis and Condensation Knope, Karah E.; Skanthakumar, S.; Soderholm, L. Inorganic Chemistry, Vol. 54, Issue 21 https://doi.org/10.1021/acs.inorgchem.5b01242	journal	October 2015
Thorium Oxo‐Clusters as Building Blocks for Open Frameworks Falaise, Clément; Kozma, Karoly; Nyman, May Chemistry – A European Journal, Vol. 24, Issue 53 https://doi.org/10.1002/chem.201802671	journal	August 2018
Avogadro: an advanced semantic chemical editor, visualization, and analysis platform Hanwell, Marcus D.; Curtis, Donald E.; Lonie, David C. Journal of Cheminformatics, Vol. 4, Issue 1 https://doi.org/10.1186/1758-2946-4-17	journal	August 2012
Nature of hydrous zirconia and sulfated hydrous zirconia Clearfield, A.; Serrette, G. P. D.; Khazi-Syed, A. H. Catalysis Today, Vol. 20, Issue 2 https://doi.org/10.1016/0920-5861(94)80008-1	journal	June 1994
Aqueous Isolation of 17-Nuclear Zr/Hf Oxide Clusters during the Hydrothermal Synthesis of ZrO ₂ /HfO ₂ Sun, Qing; Liu, Caiyun; Zhang, Guanyun Chemistry - A European Journal, Vol. 24, Issue 55 https://doi.org/10.1002/chem.201801267	journal	September 2018
Solution Species and Crystal Structure of Zr(IV) Acetate Hennig, Christoph; Weiss, Stephan; Kraus, Werner Inorganic Chemistry, Vol. 56, Issue 5 https://doi.org/10.1021/acs.inorgchem.6b01624	journal	February 2017
In situ immobilization of heavy metals associated with uranium leach mines by bacterial sulfate reduction Uhrie, John L.; Drever, James I.; Colberg, Patricia J. S. Hydrometallurgy, Vol. 43, Issue 1-3 https://doi.org/10.1016/0304-386X(95)00087-W	journal	November 1996
The crystal chemistry of four thorium sulfates Albrecht, Amanda J.; Sigmon, Ginger E.; Moore-Shay, Laura Journal of Solid State Chemistry, Vol. 184, Issue 7 https://doi.org/10.1016/j.jssc.2011.04.024	journal	July 2011
The Structure of the Plutonium Oxide Nanocluster [Pu38O56Cl54(H2O)8]14− Soderholm, L.; Almond, Philip M.; Skanthakumar, S. Angewandte Chemie, Vol. 120, Issue 2 https://doi.org/10.1002/ange.200704420	journal	January 2008

Similar Records

Metal–Oxo Cluster Formation Using Ammonium and Sulfate to Differentiate M^IV (Th, U, Ce) Chemistries

Journal Article · Mon Jul 04 00:00:00 EDT 2022 · Inorganic Chemistry · OSTI ID:1725817

Colliard, Ian; Brown, Jessica C.; Nyman, May

Thorium Oxo‐Clusters as Building Blocks for Open Frameworks

Journal Article · Thu Aug 23 00:00:00 EDT 2018 · Chemistry - A European Journal · OSTI ID:1725817

Falaise, Clément; Kozma, Karoly; Nyman, May

Solution and Solid State Structural Chemistry of Th(IV) and U(IV) 4-Hydroxybenzoates

Journal Article · Thu Jun 07 00:00:00 EDT 2018 · Inorganic Chemistry · OSTI ID:1725817

Vanagas, Nicole A.; Wacker, Jennifer N.; Rom, Christopher L.; +8 more

Related Subjects

77 NANOSCIENCE AND NANOTECHNOLOGY
38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEAR CHEMISTRY
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Anions
Uranium
Monomers
Oligomers
Scattering

CSD 2015781: Experimental Crystal Structure Determination Ian, Colliard,; Clement, Falaise,; May, Nyman, https://doi.org/10.25505/fiz.icsd.cc25nl6n The current record is supplemented by this dataset	dataset	January 2020
CSD 2015780: Experimental Crystal Structure Determination Ian, Colliard,; Clement, Falaise,; May, Nyman, https://doi.org/10.25505/fiz.icsd.cc25nl5m The current record is supplemented by this dataset	dataset	January 2020

Title: Bridging the Transuranics with Uranium(IV) Sulfate Aqueous Species and Solid Phases

Citation Formats

References (59)

Linked Research (2)

Similar Records

Related Subjects