Probing the interaction of U(VI) with phosphonate-functionalized mesoporous silica using solid-state NMR spectroscopy

Uribe, Eva C.; Mason, Harris E.; Shusterman, Jennifer A.; Bruchet, Anthony; Nitsche, Heino

doi:10.1039/C6DT01200K

Title: Probing the interaction of U_(VI) with phosphonate-functionalized mesoporous silica using solid-state NMR spectroscopy

Journal Article · Mon May 30 00:00:00 EDT 2016 · Dalton Transactions

DOI:https://doi.org/10.1039/C6DT01200K· OSTI ID:1281682

Uribe, Eva C. ^[1]; Mason, Harris E. ^[2]; Shusterman, Jennifer A. ^[3]; Bruchet, Anthony ^[1]; Nitsche, Heino ^[1]

Univ. of California, Berkeley, CA (United States)
Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States)
Univ. of California, Berkeley, CA (United States); Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States)

The fundamental interaction of U_(VI) with diethylphosphatoethyl triethoxysilane functionalized SBA-15 mesoporous silica is studied by macroscopic batch experiments and solid-state NMR spectroscopy. DPTS-functionalized silica has been shown to extract U_(VI) from nitric acid solutions at or above pH 3. Extraction is dependent on pH and ionic strength. Single-pulse ³¹P NMR on U_(VI) contacted samples revealed that U_(VI)only interacts with a fraction of the ligands present on the surface. At pH 4 the U_(VI) extraction capacity of the material is limited to 27–37% of the theoretical capacity, based on ligand loading. We combined single pulse ³¹P NMR on U_(VI)-contacted samples with batch studies to measure a ligand-to-metal ratio of approximately 2 : 1 at pH 3 and 4. Batch studies and cross-polarization NMR measurements reveal that U_(VI) binds to deprotonated phosphonate and/or silanol sites. We use ³¹P–³¹P DQ-DRENAR NMR studies to compare the average dipolar coupling between phosphorus spins for both U_(VI)-complexed and non-complexed ligand environments. Furthermore, these measurements reveal that U_(VI) extraction is not limited by inadequate surface distribution of ligands, but rather by low stability of the surface phosphonate complex.

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Research Organization:: Lawrence Livermore National Lab., Livermore, CA (United States)

Sponsoring Organization:: USDOE

Grant/Contract Number:: AC52-07NA27344

OSTI ID:: 1281682

Report Number(s):: LLNL-JRNL-689079; ICHBD9

Journal Information:: Dalton Transactions, Vol. 45, Issue 25; ISSN 1477-9226

Publisher:: Royal Society of ChemistryCopyright Statement

Country of Publication:: United States

Language:: English

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Cited by: 7 works

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References (62)

Triblock Copolymer Syntheses of Mesoporous Silica with Periodic 50 to 300 Angstrom Pores Zhao, Dongyuan; Feng, Jianglin; Huo, Qisheng Science, Vol. 279, Issue 5350, p. 548-552 https://doi.org/10.1126/science.279.5350.548	journal	January 1998
Nonionic Triblock and Star Diblock Copolymer and Oligomeric Surfactant Syntheses of Highly Ordered, Hydrothermally Stable, Mesoporous Silica Structures Zhao, Dongyuan; Huo, Qisheng; Feng, Jianglin Journal of the American Chemical Society, Vol. 120, Issue 24 https://doi.org/10.1021/ja974025i	journal	June 1998
Morphological Control of Highly Ordered Mesoporous Silica SBA-15 Zhao, Dongyuan; Sun, Jinyu; Li, Quanzhi Chemistry of Materials, Vol. 12, Issue 2 https://doi.org/10.1021/cm9911363	journal	February 2000
Morphology-selective synthesis of mesoporous SBA-15 particles over micrometer, submicrometer and nanometer scales Lee, Hyung Ik; Kim, Jin Hoe; Stucky, Galen D. Journal of Materials Chemistry, Vol. 20, Issue 39 https://doi.org/10.1039/c0jm00820f	journal	January 2010
Removal of Heavy Metals from Aqueous Solution Using Novel Nanoengineered Sorbents: Self‐Assembled Carbamoylphosphonic Acids on Mesoporous Silica Yantasee, Wassana; Lin, Yuehe; Fryxell, Glen E. Separation Science and Technology, Vol. 38, Issue 15 https://doi.org/10.1081/SS-120024232	journal	January 2003
Direct Syntheses of Ordered SBA-15 Mesoporous Silica Containing Sulfonic Acid Groups Margolese, D.; Melero, J. A.; Christiansen, S. C. Chemistry of Materials, Vol. 12, Issue 8 https://doi.org/10.1021/cm0010304	journal	August 2000
Fischer–Tropsch synthesis of hydrocarbons over mesoporous Co/SBA-15 catalysts: the influence of metal loading, cobalt precursor, and promoters Martı́nez, Agustı́n; López, Carlos; Márquez, Francisco Journal of Catalysis, Vol. 220, Issue 2 https://doi.org/10.1016/S0021-9517(03)00289-6	journal	December 2003
Ordered mesoporous materials for drug delivery Wang, Shaobin Microporous and Mesoporous Materials, Vol. 117, Issue 1-2 https://doi.org/10.1016/j.micromeso.2008.07.002	journal	January 2009
The role of SBA-15 in drug delivery Fathi Vavsari, Vaezeh; Mohammadi Ziarani, Ghodsi; Badiei, Alireza RSC Advances, Vol. 5, Issue 111 https://doi.org/10.1039/C5RA17780D	journal	January 2015
Functionalized SBA-15 Materials as Carriers for Controlled Drug Delivery: Influence of Surface Properties on Matrix−Drug Interactions Song, S. -W.; Hidajat, K.; Kawi, S. Langmuir, Vol. 21, Issue 21 https://doi.org/10.1021/la051167e	journal	October 2005
Synthesis of large pore-diameter SBA-15 mesostructured spherical silica and its application in ultra-high-performance liquid chromatography Liu, Xianbin; Li, Laisheng; Du, Yu Journal of Chromatography A, Vol. 1216, Issue 45 https://doi.org/10.1016/j.chroma.2009.09.013	journal	November 2009
Large-pore mesoporous silica spheres: synthesis and application in HPLC Ma, Yurong; Qi, Limin; Ma, Jiming Colloids and Surfaces A: Physicochemical and Engineering Aspects, Vol. 229, Issue 1-3 https://doi.org/10.1016/j.colsurfa.2003.08.010	journal	November 2003
Functionalized Monolayers on Ordered Mesoporous Supports Feng, X.; Fryxell, G. E.; Wang, L. -Q. Science, Vol. 276, Issue 5314 https://doi.org/10.1126/science.276.5314.923	journal	May 1997
Lanthanide selective sorbents: self-assembled monolayers on mesoporous supports (SAMMS) Fryxell, Glen E.; Wu, Hong; Lin, Yuehe Journal of Materials Chemistry, Vol. 14, Issue 22 https://doi.org/10.1039/b408181a	journal	January 2004
Improved deposition and deprotection of silane tethered 3,4 hydroxypyridinone (HOPO) ligands on functionalized nanoporous silica Davidson, Joseph D.; Wiacek, Robert J.; Burton, Sarah Inorganic Chemistry Communications, Vol. 18 https://doi.org/10.1016/j.inoche.2012.01.025	journal	April 2012
Actinide Sequestration Using Self-Assembled Monolayers on Mesoporous Supports Fryxell, Glen E.; Lin, Yuehe; Fiskum, Sandy Environmental Science & Technology, Vol. 39, Issue 5 https://doi.org/10.1021/es049201j	journal	March 2005
Templated synthesis of mesoporous titanium phosphates for the sequestration of radionuclides Li, X. Shari; Courtney, Andrea R.; Yantasee, Wassana Inorganic Chemistry Communications, Vol. 9, Issue 3 https://doi.org/10.1016/j.inoche.2005.11.014	journal	March 2006
Preconcentration and assay of radionuclides with self assembled monolayers on mesoporous supports Addleman, R. S.; Egorov, O. B.; O'Hara, M. J. Journal of Radioanalytical and Nuclear Chemistry, Vol. 263, Issue 1 https://doi.org/10.1007/s10967-005-0012-6	journal	January 2005
Mesoporous materials in the field of nuclear industry: applications and perspectives Makowski, Philippe; Deschanels, Xavier; Grandjean, Agnès New J. Chem., Vol. 36, Issue 3 https://doi.org/10.1039/C1NJ20703B	journal	January 2012
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
Ordered SBA-15 mesoporous silica containing phosphonic acid groups prepared by a direct synthetic approach Corriu, Robert J. P.; Guari, Yannick; Mehdi, Ahmad Chemical Communications, Issue 8 https://doi.org/10.1039/b100515o	journal	January 2001
Phosphonate-functionalized large pore 3-D cubic mesoporous (KIT-6) hybrid as highly efficient actinide extracting agent Lebed, Pablo J.; de Souza, Kellen; Bilodeau, François Chemical Communications, Vol. 47, Issue 41 https://doi.org/10.1039/c1cc14053a	journal	January 2011
Large Pore Mesostructured Organosilica-Phosphonate Hybrids as Highly Efficient and Regenerable Sorbents for Uranium Sequestration Lebed, Pablo J.; Savoie, Jean-Daniel; Florek, Justyna Chemistry of Materials, Vol. 24, Issue 21 https://doi.org/10.1021/cm3023709	journal	October 2012
Mesoporous silica SBA-15 functionalized with phosphonate derivatives for uranium uptake Wang, Yu-Long; Zhu, Lu; Guo, Bo-Long New J. Chem., Vol. 38, Issue 8 https://doi.org/10.1039/C3NJ01494K	journal	January 2014
Organo-functionalized mesoporous silicas for efficient uranium extraction Vivero-Escoto, Juan L.; Carboni, Michaël; Abney, Carter W. Microporous and Mesoporous Materials, Vol. 180 https://doi.org/10.1016/j.micromeso.2013.05.030	journal	November 2013
High performance of phosphonate-functionalized mesoporous silica for U(vi) sorption from aqueous solution Yuan, Li-Yong; Liu, Ya-Lan; Shi, Wei-Qun Dalton Transactions, Vol. 40, Issue 28 https://doi.org/10.1039/c1dt10085h	journal	January 2011
Mesoporous silica SBA-15 functionalized with phosphonate and amino groups for uranium uptake Wang, XiaoLiang; Yuan, LiYong; Wang, YanFei Science China Chemistry, Vol. 55, Issue 9 https://doi.org/10.1007/s11426-012-4625-7	journal	June 2012
The reaction between aqueous uranyl ion and the surface of silica gel Stanton, Jimmy; Maatman, Russell W. Journal of Colloid Science, Vol. 18, Issue 2 https://doi.org/10.1016/0095-8522(63)90003-5	journal	February 1963
Sorption and desorption of uranyl ions by silica gel: pH, particle size and porosity effects Michard, P.; Guibal, E.; Vincent, T. Microporous Materials, Vol. 5, Issue 5 https://doi.org/10.1016/0927-6513(95)00067-4	journal	January 1996
Removal of uranium (VI) ion from aqueous solution by SBA-15 Wang, Xinghui; Zhu, Guiru; Guo, Feng Annals of Nuclear Energy, Vol. 56 https://doi.org/10.1016/j.anucene.2013.01.041	journal	June 2013
Characterization of Hydrous Uranyl Silicate by EXAFS Reich, T.; Moll, H.; Denecke, M. A. Radiochimica Acta, Vol. 74, Issue s1 https://doi.org/10.1524/ract.1996.74.special-issue.219	journal	January 1996
An EXAFS study of uranium(VI) sorption onto silica gel and ferrihydrite Reich, T.; Moll, H.; Arnold, T. Journal of Electron Spectroscopy and Related Phenomena, Vol. 96, Issue 1-3 https://doi.org/10.1016/S0368-2048(98)00242-4	journal	November 1998
The structure of uranium (VI) sorption complexes on silica, alumina, and montmorillonite Sylwester, E. R.; Hudson, E. A.; Allen, P. G. Geochimica et Cosmochimica Acta, Vol. 64, Issue 14 https://doi.org/10.1016/S0016-7037(00)00376-8	journal	July 2000
Analysis of trivalent cation complexation to functionalized mesoporous silica using solid-state NMR spectroscopy Shusterman, Jennifer; Mason, Harris; Bruchet, Anthony Dalton Trans., Vol. 43, Issue 44 https://doi.org/10.1039/C4DT02380C	journal	January 2014
Development and Testing of Diglycolamide Functionalized Mesoporous Silica for Sorption of Trivalent Actinides and Lanthanides Shusterman, Jennifer A.; Mason, Harris E.; Bowers, Jon ACS Applied Materials & Interfaces, Vol. 7, Issue 37 https://doi.org/10.1021/acsami.5b04481	journal	September 2015
Solid-State NMR Spectroscopic Studies of Propylphosphonic Acid Functionalized SBA-15 Mesoporous Silica: Characterization of Hydrogen-Bonding Interactions Bibent, Nicolas; Charpentier, Thibault; Devautour-Vinot, Sabine European Journal of Inorganic Chemistry, Vol. 2013, Issue 13 https://doi.org/10.1002/ejic.201201404	journal	March 2013
Probing the Nature and Local Structure of Phosphonic Acid Groups Functionalized in Mesoporous Silica SBA-15 Pan, Yu-Chi; Gavin Tsai, Hui-Hsu; Jiang, Jyh-Chiang The Journal of Physical Chemistry C, Vol. 116, Issue 2 https://doi.org/10.1021/jp206017j	journal	January 2012
Description of partition equilibria for uranyl nitrate, nitric acid and water extracted by tributyl phosphate in dodecane Hlushak, S. P.; Simonin, J. P.; Caniffi, B. Hydrometallurgy, Vol. 109, Issue 1-2 https://doi.org/10.1016/j.hydromet.2011.05.014	journal	September 2011
Synthesis of ordered large pore SBA-15 spherical particles for adsorption of biomolecules Katiyar, Amit; Yadav, Santosh; Smirniotis, Panagiotis G. Journal of Chromatography A, Vol. 1122, Issue 1-2 https://doi.org/10.1016/j.chroma.2006.04.055	journal	July 2006
Influence of Stationary Phase Chemistry on Shape Recognition in Liquid Chromatography Sander, Lane C.; Wise, Stephen A. Analytical Chemistry, Vol. 67, Issue 18 https://doi.org/10.1021/ac00114a027	journal	September 1995
Adsorption of Gases in Multimolecular Layers Brunauer, Stephen; Emmett, P. H.; Teller, Edward Journal of the American Chemical Society, Vol. 60, Issue 2, p. 309-319 https://doi.org/10.1021/ja01269a023	journal	February 1938
The Determination of Pore Volume and Area Distributions in Porous Substances. I. Computations from Nitrogen Isotherms Barrett, Elliott P.; Joyner, Leslie G.; Halenda, Paul P. Journal of the American Chemical Society, Vol. 73, Issue 1 https://doi.org/10.1021/ja01145a126	journal	January 1951
Solid-state high-resolution silicon-29 chemical shifts in silicates Magi, M.; Lippmaa, E.; Samoson, A. The Journal of Physical Chemistry, Vol. 88, Issue 8 https://doi.org/10.1021/j150652a015	journal	April 1984
Formation of hydroxylapatite from co-sorption of phosphate and calcium by boehmite Li, Wei; Xu, Wenqian; Parise, John B. Geochimica et Cosmochimica Acta, Vol. 85 https://doi.org/10.1016/j.gca.2012.02.021	journal	May 2012
A Homonuclear Rotational Echo Double-Resonance Method for Measuring Site-Resolved Distance Distributions in I = 1/2 Spin Pairs, Clusters, and Multispin Systems Ren, Jinjun; Eckert, Hellmut Angewandte Chemie International Edition, Vol. 51, Issue 51 https://doi.org/10.1002/anie.201207094	journal	November 2012
A Review: Fundamental Aspects of Silicate Mesoporous Materials ALOthman, Zeid Materials, Vol. 5, Issue 12 https://doi.org/10.3390/ma5122874	journal	December 2012
Tailoring Surface and Structural Properties of MCM-41 Silicas by Bonding Organosilanes Jaroniec, C. P.; Kruk, M.; Jaroniec, M. The Journal of Physical Chemistry B, Vol. 102, Issue 28 https://doi.org/10.1021/jp981304z	journal	June 1998
The Fumed Silica Surface: A Study by NMR Liu, Changhua C.; Maciel, Gary E. Journal of the American Chemical Society, Vol. 118, Issue 21 https://doi.org/10.1021/ja954120w	journal	January 1996
Kinetics of Cross-Polarization in Solid-State NMR: A Guide for Chemists Kolodziejski, Waclaw; Klinowski, Jacek Chemical Reviews, Vol. 102, Issue 3 https://doi.org/10.1021/cr000060n	journal	March 2002
Dynamic NMR Study of Ligand Exchange Reactions in U(VI)−Phosphonic Acid Systems Muntean, J. V.; Nash, K. L.; Rickert, P. G. The Journal of Physical Chemistry A, Vol. 103, Issue 18 https://doi.org/10.1021/jp9848041	journal	April 1999
Synthesis and crystal and molecular structure of bis(nitrato)[diisopropyl (N,N-diethylcarbamyl)methylenephosphonate]dioxouranium(VI) Bowen, Scott M.; Duesler, Eileen N.; Paine, Robert T. Inorganic Chemistry, Vol. 22, Issue 2 https://doi.org/10.1021/ic00144a018	journal	January 1983
Proton‐enhanced NMR of dilute spins in solids Pines, A.; Gibby, M. G.; Waugh, J. S. The Journal of Chemical Physics, Vol. 59, Issue 2 https://doi.org/10.1063/1.1680061	journal	July 1973
Nuclear Double Resonance in the Rotating Frame Hartmann, S. R.; Hahn, E. L. Physical Review, Vol. 128, Issue 5 https://doi.org/10.1103/PhysRev.128.2042	journal	December 1962
DQ-DRENAR: A new NMR technique to measure site-resolved magnetic dipole-dipole interactions in multispin-1/2 systems: Theory and validation on crystalline phosphates Ren, Jinjun; Eckert, Hellmut The Journal of Chemical Physics, Vol. 138, Issue 16 https://doi.org/10.1063/1.4801634	journal	April 2013
On the Nature of the Brønsted Acidic Groups on Native and Functionalized Mesoporous Siliceous SBA-15 as Studied by Benzylamine Adsorption from Solution Rosenholm, Jessica M.; Czuryszkiewicz, Teresa; Kleitz, Freddy Langmuir, Vol. 23, Issue 8 https://doi.org/10.1021/la062450w	journal	April 2007
Adsorption of Crystal Violet to the Silica−Water Interface Monitored by Evanescent Wave Cavity Ring-Down Spectroscopy Shaw, Andrew M.; Hannon, Theresa E.; Li, Fuping The Journal of Physical Chemistry B, Vol. 107, Issue 29 https://doi.org/10.1021/jp027636s	journal	July 2003
Modeling Cadmium Adsorption by Activated Carbon Using the Langmuir and Freundlich Isotherm Expressions Reed, Brian E.; Matsumoto, Mark R. Separation Science and Technology, Vol. 28, Issue 13-14 https://doi.org/10.1080/01496399308016742	journal	October 1993
Probing the Surface Structure of Divalent Transition Metals Using Surface Specific Solid-State NMR Spectroscopy Mason, Harris E.; Harley, Stephen J.; Maxwell, Robert S. Environmental Science & Technology, Vol. 46, Issue 5 https://doi.org/10.1021/es203733c	journal	February 2012
Kinetics of 1H→31P cross-polarization in human trabecular bone Kaflak, Agnieszka; Chmielewski, Dariusz; Górecki, Andrzej Solid State Nuclear Magnetic Resonance, Vol. 10, Issue 4 https://doi.org/10.1016/S0926-2040(97)00085-4	journal	February 1998
Crystal structure of low cristobalite at 10, 293, and 473 K: Variation of framework geometry with temperature Pluth, J. J.; Smith, J. V.; Faber, J. Journal of Applied Physics, Vol. 57, Issue 4 https://doi.org/10.1063/1.334545	journal	February 1985
A Detailed Model of Local Structure and Silanol Hydrogen Bonding of Silica Gel Surfaces Chuang, I-Ssuer; Maciel, Gary E. The Journal of Physical Chemistry B, Vol. 101, Issue 16 https://doi.org/10.1021/jp9629046	journal	April 1997
Structure of dinitratodioxobis(triisobutyl phosphate)uranium(VI) at 139 K Burns, J. H.; Brown, G. M.; Ryan, R. R. Acta Crystallographica Section C Crystal Structure Communications, Vol. 41, Issue 10 https://doi.org/10.1107/S0108270185008125	journal	October 1985

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Title: Probing the interaction of U_(VI) with phosphonate-functionalized mesoporous silica using solid-state NMR spectroscopy