Title: 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 » 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.« less

Authors:

Motokawa, Ryuhei  ^[1];

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Kobayashi, Tohru ^[1]; Endo, Hitoshi ^[2]; Mu, Junju  ^[3];

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Williams, Christopher D.  ^[3];

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Masters, Andrew J.  ^[3];

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Antonio, Mark R.  ^[4];

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Heller, William T.  ^[5];

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Nagao, Michihiro  ^[6]

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+ Show Author Affiliations

1. Materials Sciences Research Center, Japan Atomic Energy Agency, Tokai, Ibaraki 319-1195, Japan
2. 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
3. School of Chemical Engineering and Analytical Science, The University of Manchester, Oxford Road, Manchester M13 9PL, United Kingdom
4. Chemical Sciences &, Engineering Division, Argonne National Laboratory, Lemont, Illinois 60439, United States
5. Neutron Scattering Division, Oak Ridge National Laboratory, Oak Ridge, Tennessee 37831, United States
6. 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:

2018-12-31

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