A Telescoping View of Solute Architectures in a Complex Fluid System
Abstract
Short- and long-range correlations between solutes in solvents can influence the macroscopic chemistry and physical properties of solutions in ways that are not fully understood. The class of liquids known as complex (structured) fluids—containing multiscale aggregates resulting from weak self-assembly—are especially important in energy-relevant systems employed for a variety of chemical- and biological-based purification, separation, and catalytic processes. In these, solute (mass) transfer across liquid–liquid (water, oil) phase boundaries is the core function. Oftentimes the operational success of phase transfer chemistry is dependent upon the bulk fluid structures for which a common functional motif and an archetype aggregate is the micelle. In particular, there is an emerging consensus that mass transfer and bulk organic phase behaviors—notably the critical phenomenon of phase splitting—are impacted by the effects of micellar-like aggregates in water-in-oil microemulsions. In this study, we elucidate the microscopic structures and mesoscopic architectures of metal-, water-, and acid-loaded organic phases using a combination of X-ray and neutron experimentation as well as density functional theory and molecular dynamics simulations. The key conclusion is that the transfer of metal ions between an aqueous phase and an organic one involves the formation of small mononuclear clusters typical of metal–ligand coordination chemistry, at onemore »
- Authors:
-
- Materials Sciences Research Center, Japan Atomic Energy Agency, Tokai, Ibaraki 319-1195, Japan
- Materials Sciences Research Center, Japan Atomic Energy Agency, Tokai, Ibaraki 319-1195, Japan, Neutron Science Division, Institute of Materials Structure Science, and Materials and Life Science Division, J-PARC Center, High Energy Accelerator Research Organization, 203-1 Shirakata, Tokai, Ibaraki 319-1106, Japan, Department of Materials Structure Science, The Graduate University for Advanced Studies (SOKENDAI), 203-1 Shirakata, Tokai, Ibaraki 319-1106, Japan
- School of Chemical Engineering and Analytical Science, The University of Manchester, Oxford Road, Manchester M13 9PL, United Kingdom
- Chemical Sciences &, Engineering Division, Argonne National Laboratory, Lemont, Illinois 60439, United States
- Neutron Scattering Division, Oak Ridge National Laboratory, Oak Ridge, Tennessee 37831, United States
- NIST Center for Neutron Research, National Institute of Standards and Technology, Gaithersburg, Maryland 20899-6102, United States, Center for Exploration of Energy and Matter, Department of Physics, Indiana University, Bloomington, Indiana 47408, United States
- Publication Date:
- Research Org.:
- Argonne National Lab. (ANL), Argonne, IL (United States); Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences, and Biosciences Division; Ministry of Education, Culture, Sports, Science and Technology (MEXT) of Japan
- OSTI Identifier:
- 1489165
- Alternate Identifier(s):
- OSTI ID: 1494559; OSTI ID: 1508830; OSTI ID: 1607238
- Grant/Contract Number:
- AC02-06CH11357; AC05-00OR22725
- Resource Type:
- Published Article
- Journal Name:
- ACS Central Science
- Additional Journal Information:
- Journal Name: ACS Central Science Journal Volume: 5 Journal Issue: 1; Journal ID: ISSN 2374-7943
- Publisher:
- American Chemical Society (ACS)
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; DFT; density functional theory; EXAFS; extended X-ray absorption fine structure; PUREX; Plutonium uranium reduction extraction; SANS; small-angle neutron scattering; Solvent extraction; Zirconium
Citation Formats
Motokawa, Ryuhei, Kobayashi, Tohru, Endo, Hitoshi, Mu, Junju, Williams, Christopher D., Masters, Andrew J., Antonio, Mark R., Heller, William T., and Nagao, Michihiro. A Telescoping View of Solute Architectures in a Complex Fluid System. United States: N. p., 2018.
Web. doi:10.1021/acscentsci.8b00669.
Motokawa, Ryuhei, Kobayashi, Tohru, Endo, Hitoshi, Mu, Junju, Williams, Christopher D., Masters, Andrew J., Antonio, Mark R., Heller, William T., & Nagao, Michihiro. A Telescoping View of Solute Architectures in a Complex Fluid System. United States. https://doi.org/10.1021/acscentsci.8b00669
Motokawa, Ryuhei, Kobayashi, Tohru, Endo, Hitoshi, Mu, Junju, Williams, Christopher D., Masters, Andrew J., Antonio, Mark R., Heller, William T., and Nagao, Michihiro. Mon .
"A Telescoping View of Solute Architectures in a Complex Fluid System". United States. https://doi.org/10.1021/acscentsci.8b00669.
@article{osti_1489165,
title = {A Telescoping View of Solute Architectures in a Complex Fluid System},
author = {Motokawa, Ryuhei and Kobayashi, Tohru and Endo, Hitoshi and Mu, Junju and Williams, Christopher D. and Masters, Andrew J. and Antonio, Mark R. and Heller, William T. and Nagao, Michihiro},
abstractNote = {Short- and long-range correlations between solutes in solvents can influence the macroscopic chemistry and physical properties of solutions in ways that are not fully understood. The class of liquids known as complex (structured) fluids—containing multiscale aggregates resulting from weak self-assembly—are especially important in energy-relevant systems employed for a variety of chemical- and biological-based purification, separation, and catalytic processes. In these, solute (mass) transfer across liquid–liquid (water, oil) phase boundaries is the core function. Oftentimes the operational success of phase transfer chemistry is dependent upon the bulk fluid structures for which a common functional motif and an archetype aggregate is the micelle. In particular, there is an emerging consensus that mass transfer and bulk organic phase behaviors—notably the critical phenomenon of phase splitting—are impacted by the effects of micellar-like aggregates in water-in-oil microemulsions. In this study, we elucidate the microscopic structures and mesoscopic architectures of metal-, water-, and acid-loaded organic phases using a combination of X-ray and neutron experimentation as well as density functional theory and molecular dynamics simulations. The key conclusion is that the transfer of metal ions between an aqueous phase and an organic one involves the formation of small mononuclear clusters typical of metal–ligand coordination chemistry, at one extreme, in the organic phase, and their aggregation to multinuclear primary clusters that self-assemble to form even larger superclusters typical of supramolecular chemistry, at the other. Our metrical results add an orthogonal perspective to the energetics-based view of phase splitting in chemical separations known as the micellar model—founded upon the interpretation of small-angle neutron scattering data—with respect to a more general phase-space (gas–liquid) model of soft matter self-assembly and particle growth. The structure hierarchy observed in the aggregation of our quinary (zirconium nitrate–nitric acid–water–tri-n-butyl phosphate–n-octane) system is relevant to understanding solution phase transitions, in general, and the function of engineered fluids with metalloamphiphiles, in particular, for mass transfer applications, such as demixing in separation and synthesis in catalysis science.},
doi = {10.1021/acscentsci.8b00669},
journal = {ACS Central Science},
number = 1,
volume = 5,
place = {United States},
year = {2018},
month = {12}
}
https://doi.org/10.1021/acscentsci.8b00669
Web of Science
Works referenced in this record:
A predictive model of reverse micelles solubilizing water for solvent extraction
journal, October 2016
- Bley, Michael; Siboulet, Bertrand; Karmakar, Anwesa
- Journal of Colloid and Interface Science, Vol. 479
How Hydrogen Bonds Affect the Growth of Reverse Micelles around Coordinating Metal Ions
journal, March 2014
- Qiao, Baofu; Demars, Thomas; Olvera de la Cruz, Monica
- The Journal of Physical Chemistry Letters, Vol. 5, Issue 8
Reversed micelle solvents as tools of enzyme purification and enzyme-catalyzed conversion
journal, November 2008
- Tonova, Konstantza; Lazarova, Zdravka
- Biotechnology Advances, Vol. 26, Issue 6
Colloidal quasicrystals with 12-fold and 18-fold diffraction symmetry
journal, January 2011
- Fischer, Steffen; Exner, Alexander; Zielske, Kathrin
- Proceedings of the National Academy of Sciences, Vol. 108, Issue 5
Recycling metals by controlled transfer of ionic species between complex fluids: en route to “ienaics”
journal, November 2014
- Zemb, Thomas; Bauer, Caroline; Bauduin, Pierre
- Colloid and Polymer Science, Vol. 293, Issue 1
Depletion of water-in-oil aggregates from poor solvents: Transition from weak aggregates towards reverse micelles
journal, February 2015
- Guilbaud, Philippe; Zemb, Thomas
- Current Opinion in Colloid & Interface Science, Vol. 20, Issue 1
A Novel Microemulsion Phase Transition: Toward the Elucidation of Third-Phase Formation in Spent Nuclear Fuel Reprocessing
journal, January 2018
- Mu, Junju; Motokawa, Ryuhei; Akutsu, Kazuhiro
- The Journal of Physical Chemistry B, Vol. 122, Issue 4
Sans Study of Reverse Micelles Formed upon the Extraction of Inorganic Acids by TBP in n ‐Octane
journal, July 2008
- Chiarizia, R.; Briand, A.; Jensen, M. P.
- Solvent Extraction and Ion Exchange, Vol. 26, Issue 4
CRYSOL – a Program to Evaluate X-ray Solution Scattering of Biological Macromolecules from Atomic Coordinates
journal, December 1995
- Svergun, D.; Barberato, C.; Koch, M. H. J.
- Journal of Applied Crystallography, Vol. 28, Issue 6
Zerstreuung von Röntgenstrahlen
journal, January 1915
- Debye, P.
- Annalen der Physik, Vol. 351, Issue 6
EFFECT OF NITRIC ACID EXTRACTION ON PHASE BEHAVIOR, MICROSTRUCTURE AND INTERACTIONS BETWEEN PRIMARY AGGREGATES IN THE SYSTEM DIMETHYLDIBUTYLTETRADECYLMALONAMIDE (DMDBTDMA) / n-DODECANE / WATER: A PHASE ANALYSIS AND SMALL ANGLE X-RAY SCATTERING (SAXS) CHARACTERISATION STUDY
journal, May 1998
- Erlinger, C.; Gazeau, D.; Zemb, T.
- Solvent Extraction and Ion Exchange, Vol. 16, Issue 3
Reversed micelle formation in a model liquid–liquid extraction system
journal, June 2008
- Guo, Fuqiang; Li, Hongfei; Zhang, Zhifeng
- Journal of Colloid and Interface Science, Vol. 322, Issue 2
Reverse-Micelle Formation in the Partitioning of Trivalent f-Element Cations by Biphasic Systems Containing a Tetraalkyldiglycolamide
journal, April 2007
- Jensen, Mark P.; Yaita, Tsuyoshi; Chiarizia, Renato
- Langmuir, Vol. 23, Issue 9
Metal Recognition Driven by Weak Interactions: A Case Study in Solvent Extraction
journal, May 2016
- Poirot, Rémi; Le Goff, Xavier; Diat, Olivier
- ChemPhysChem, Vol. 17, Issue 14
Aggregation, reversed micelles, and microemulsions in liquid-liquid extraction: the tri-n-butyl phosphatediluent-water-electrolyte system
journal, November 1991
- Osseo-Asare, K.
- Advances in Colloid and Interface Science, Vol. 37, Issue 1-2
Stability of reverse micelles in rare-earth separation: a chemical model based on a molecular approach
journal, January 2017
- Chen, Yushu; Duvail, Magali; Guilbaud, Philippe
- Physical Chemistry Chemical Physics, Vol. 19, Issue 10
Sans Study Of Third Phase Formation In The Th(iv)-hno 3 /tbp- n -octane System
journal, January 2003
- Borkowski, M.; Chiarizia, R.; Jensen, M. P.
- Separation Science and Technology, Vol. 38, Issue 12-13
Free energy approach to micellization and aggregation: Equilibrium, metastability, and kinetics
journal, April 2016
- Diamant, Haim; Andelman, David
- Current Opinion in Colloid & Interface Science, Vol. 22
Characterization of reversed micelles formed in solvent extraction of thorium(IV) by bis(2-ethylhexyl) phosphoric acid. Transforming from rodlike to wormlike morphology
journal, January 2016
- Gao, Song; Sun, Taoxiang; Chen, Qingde
- Radiochimica Acta, Vol. 104, Issue 7
Applications of Diglycolamide Based Solvent Extraction Processes in Spent Nuclear Fuel Reprocessing, Part 1: TODGA
journal, April 2018
- Whittaker, Daniel; Geist, Andreas; Modolo, Giuseppe
- Solvent Extraction and Ion Exchange, Vol. 36, Issue 3
Periodic Behavior of Lanthanide Coordination within Reverse Micelles
journal, January 2013
- Ellis, Ross J.; Meridiano, Yannick; Chiarizia, Renato
- Chemistry - A European Journal, Vol. 19, Issue 8
Theoretical Modeling of Associated Structures in Aqueous Solutions of Hydrophobically Modified Telechelic PNIPAM Based on a Neutron Scattering Study
journal, December 2008
- Koga, Tsuyoshi; Tanaka, Fumihiko; Motokawa, Ryuhei
- Macromolecules, Vol. 41, Issue 23
Network analysis and percolation transition in hydrogen bonded clusters: nitric acid and water extracted by tributyl phosphate
journal, January 2017
- Servis, Michael J.; Wu, David T.; Braley, Jenifer C.
- Physical Chemistry Chemical Physics, Vol. 19, Issue 18
TODGA based w/o microemulsion in dodecane: An insight into the micellar aggregation characteristics by dynamic light scattering and viscometry
journal, March 2011
- Ganguly, Rajib; Sharma, Joti N.; Choudhury, Niharendu
- Journal of Colloid and Interface Science, Vol. 355, Issue 2
Third Phase Formation Revisited: The U(VI), HNO 3 –TBP, n ‐Dodecane System
journal, January 2003
- Chiarizia, R.; Jensen, M. P.; Borkowski, M.
- Solvent Extraction and Ion Exchange, Vol. 21, Issue 1
Extraction of Zirconium Nitrate by TBP in n -Octane: Influence of Cation Type on Third Phase Formation According to the “Sticky Spheres” Model
journal, December 2004
- Chiarizia, Renato; Jensen, Mark P.; Rickert, Paul G.
- Langmuir, Vol. 20, Issue 25
Structural insights into the multinuclear speciation of tetravalent cerium in the tri-n-butyl phosphate–n-dodecane solvent extraction system
journal, January 2017
- Antonio, Mark R.; Ellis, Ross J.; Estes, Shanna L.
- Physical Chemistry Chemical Physics, Vol. 19, Issue 32
Gelation of particles with short-range attraction
journal, May 2008
- Lu, Peter J.; Zaccarelli, Emanuela; Ciulla, Fabio
- Nature, Vol. 453, Issue 7194
Solvent Penetration and Sterical Stabilization of Reverse Aggregates based on the DIAMEX Process Extracting Molecules: Consequences for the Third Phase Formation
journal, August 2007
- Berthon, L.; Martinet, L.; Testard, F.
- Solvent Extraction and Ion Exchange, Vol. 25, Issue 5
Pattern formation and self-assembly driven by competing interactions
journal, January 2017
- Pini, Davide; Parola, Alberto
- Soft Matter, Vol. 13, Issue 48
Editorial overview
journal, April 2016
- Zemb, Thomas; Holmberg, Krister; Kunz, Werner
- Current Opinion in Colloid & Interface Science, Vol. 22
Weak aggregation: State of the art, expectations and open questions
journal, April 2016
- Zemb, Thomas; Kunz, Werner
- Current Opinion in Colloid & Interface Science, Vol. 22
Percus–Yevick Equation for Hard Spheres with Surface Adhesion
journal, September 1968
- Baxter, R. J.
- The Journal of Chemical Physics, Vol. 49, Issue 6
The structure of tributyl phosphate solutions: Nitric acid, uranium (VI), and zirconium (IV)
journal, November 2017
- Baldwin, Anna G.; Servis, Michael J.; Yang, Yuan
- Journal of Molecular Liquids, Vol. 246
Mesoscopic structure formation in colloidal aggregation and gelation
journal, October 1997
- Poon, W. C. K.; Haw, M. D.
- Advances in Colloid and Interface Science, Vol. 73
Real-space multiple-scattering calculation and interpretation of x-ray-absorption near-edge structure
journal, September 1998
- Ankudinov, A. L.; Ravel, B.; Rehr, J. J.
- Physical Review B, Vol. 58, Issue 12
Self-assembly, phase behaviour and structural behaviour as observed by scattering for classical and non-classical microemulsions
journal, September 2017
- Prévost, Sylvain; Gradzielski, Michael; Zemb, Thomas
- Advances in Colloid and Interface Science, Vol. 247
Neutron Polarization Analysis for Biphasic Solvent Extraction Systems
journal, June 2016
- Motokawa, Ryuhei; Endo, Hitoshi; Nagao, Michihiro
- Solvent Extraction and Ion Exchange, Vol. 34, Issue 5
Third phase inversion, red oil formation, and multinuclear speciation of tetravalent cerium in the tri- n -butyl phosphate– n -dodecane solvent extraction system
journal, February 2017
- Antonio, Mark R.; Demars, Thomas J.; Audras, Matthieu
- Separation Science and Technology, Vol. 53, Issue 12
Liquid/liquid metal extraction: Phase diagram topology resulting from molecular interactions between extractant, ion, oil and water
journal, November 2012
- Bauer, C.; Bauduin, P.; Dufrêche, J. F.
- The European Physical Journal Special Topics, Vol. 213, Issue 1
Molecular Origins of Mesoscale Ordering in a Metalloamphiphile Phase
journal, December 2015
- Qiao, Baofu; Ferru, Geoffroy; Olvera de la Cruz, Monica
- ACS Central Science, Vol. 1, Issue 9
Complexation-Induced Supramolecular Assembly Drives Metal-Ion Extraction
journal, August 2014
- Ellis, Ross J.; Meridiano, Yannick; Muller, Julie
- Chemistry - A European Journal, Vol. 20, Issue 40
Critical Exponents for Solvent Extraction Resolved Using SAXS
journal, December 2013
- Ellis, Ross J.
- The Journal of Physical Chemistry B, Vol. 118, Issue 1
Lanthanide cationextraction by malonamideligands: from liquid–liquid interfaces to microemulsions. A molecular dynamics study
journal, January 2005
- Diss, Romain; Wipff, Georges
- Phys. Chem. Chem. Phys., Vol. 7, Issue 2
Small‐Angle Neutron Scattering Study of Plutonium Third Phase Formation in 30% TBP/HNO 3 /Alkane Diluent Systems
journal, July 2006
- Plaue, J.; Gelis, A.; Czerwinski, K.
- Solvent Extraction and Ion Exchange, Vol. 24, Issue 3
Square supramolecular assemblies of uranyl complexes in organic solvents
journal, January 2018
- Servis, Michael J.; Wu, David T.; Shafer, Jenifer C.
- Chemical Communications, Vol. 54, Issue 72
Organic and Third Phase in HNO 3 /TBP/ n -Dodecane System: No Reverse Micelles
journal, June 2017
- Ivanov, P.; Mu, J.; Leay, L.
- Solvent Extraction and Ion Exchange, Vol. 35, Issue 4
Scaling of Dynamics with the Range of Interaction in Short-Range Attractive Colloids
journal, February 2005
- Foffi, G.; Michele, C. De; Sciortino, F.
- Physical Review Letters, Vol. 94, Issue 7
Monte Carlo calculations of cluster statistics in continuum models of composite morphology
journal, January 1988
- Sevick, E. M.; Monson, P. A.; Ottino, J. M.
- The Journal of Chemical Physics, Vol. 88, Issue 2
Flexibility, persistence length and bicontinuous microstructures in microemulsions
journal, January 2009
- Zemb, Thomas
- Comptes Rendus Chimie, Vol. 12, Issue 1-2
Microemulsions in Technical Processes
journal, June 1995
- Schwuger, Milan-Johann; Stickdorn, Katrin; Schomaecker, Reinhard
- Chemical Reviews, Vol. 95, Issue 4
Effect of n -Octanol on the Structure at the Supramolecular Scale of Concentrated Dimethyldioctylhexylethoxymalonamide Extractant Solutions
journal, August 2003
- Abécassis, B.; Testard, F.; Zemb, Th.
- Langmuir, Vol. 19, Issue 17
Aggregation of Heteropolyanions in Aqueous Solutions Exhibiting Short-Range Attractions and Long-Range Repulsions
journal, December 2015
- Bera, Mrinal K.; Qiao, Baofu; Seifert, Soenke
- The Journal of Physical Chemistry C, Vol. 120, Issue 2
Supramolecular solvents in the extraction of organic compounds. A review
journal, September 2010
- Ballesteros-Gómez, Ana; Sicilia, María Dolores; Rubio, Soledad
- Analytica Chimica Acta, Vol. 677, Issue 2
Colloidal gels: equilibrium and non-equilibrium routes
journal, July 2007
- Zaccarelli, Emanuela
- Journal of Physics: Condensed Matter, Vol. 19, Issue 32
A neutron scattering study of the structure of a bimodal colloidal crystal
journal, February 1992
- Bartlett, P.; Ottewill, R. H.
- The Journal of Chemical Physics, Vol. 96, Issue 4
Low-symmetry sphere packings of simple surfactant micelles induced by ionic sphericity
journal, April 2017
- Kim, Sung A.; Jeong, Kyeong-Jun; Yethiraj, Arun
- Proceedings of the National Academy of Sciences, Vol. 114, Issue 16