Direct Experimental Observations of Ion Distributions during Overcharging at the Muscovite–Water Interface by Adsorption of Rb+ and Halides (Cl–, Br–, I–) at High Salinity

Neumann, Julia; Lee, Sang Soo; Zhao, Eric J.; Fenter, Paul A.

doi:10.1002/cphc.202300545

Direct Experimental Observations of Ion Distributions during Overcharging at the Muscovite–Water Interface by Adsorption of Rb⁺ and Halides (Cl^–, Br^–, I^–) at High Salinity

Journal Article · Sat Aug 26 00:00:00 EDT 2023 · ChemPhysChem

DOI:https://doi.org/10.1002/cphc.202300545· OSTI ID:2368837

^[1]; ^[1]; Zhao, Eric J. ^[2]; ^[1]

Argonne National Laboratory (ANL), Argonne, IL (United States)
Argonne National Laboratory (ANL), Argonne, IL (United States); Univ. of Chicago, IL (United States)

Classical electric double layer (EDL) models have been widely used to describe ion distributions at charged solid-water interfaces in dilute electrolytes. However, the chemistry of EDLs remains poorly constrained at high ionic strength where ion-ion correlations control non-classical behavior such as overcharging, i. e., the accumulation of counter-ions in amounts exceeding the substrate's surface charge. Here, we provide direct experimental observations of correlated cation and anion distributions adsorbed at the muscovite (001)-aqueous electrolyte interface as a function of dissolved RbBr concentration ([RbBr]=0.01–5.8 M) using resonant anomalous X-ray reflectivity. Our results show alternating cation-anion layers in the EDL when [RbBr]≳100 mM, whose spatial extension (i. e., ~20 Å from the surface) far exceeds the dimension of the classical Stern layer. Comparison to RbCl and RbI electrolytes indicates that these behaviors are sensitive to the choice of co-ion. This new in-depth molecular-scale understanding of the EDL structure during transition from classical to non-classical regimes supports the development of realistic EDL models for technologies operating at high salinity such as water purification applications or modern electrochemical storage.

View Accepted Manuscript (DOE)

Research Organization:: Argonne National Laboratory (ANL), Argonne, IL (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division (CSGB); USDOE Office of Science (SC), Basic Energy Sciences (BES). Scientific User Facilities (SUF)

Grant/Contract Number:: AC02-06CH11357

OSTI ID:: 2368837

Journal Information:: ChemPhysChem, Journal Name: ChemPhysChem Journal Issue: 22 Vol. 24; ISSN 1439-4235

Publisher:: ChemPubSoc EuropeCopyright Statement

Country of Publication:: United States

Language:: English

References (56)

Hydration forces between mica surfaces in electrolyte solutions Pashley, R. M. Advances in Colloid and Interface Science, Vol. 16, Issue 1 https://doi.org/10.1016/0001-8686(82)85006-9	journal	July 1982
DLVO and hydration forces between mica surfaces in Li+, Na+, K+, and Cs+ electrolyte solutions: A correlation of double-layer and hydration forces with surface cation exchange properties Pashley, R. M. Journal of Colloid and Interface Science, Vol. 83, Issue 2 https://doi.org/10.1016/0021-9797(81)90348-9	journal	October 1981
Quest for ion–ion correlations in electric double layers and overcharging phenomena Lyklema, J. Advances in Colloid and Interface Science, Vol. 147-148 https://doi.org/10.1016/j.cis.2008.12.002	journal	March 2009
Overcharging, charge reversal: Chemistry or physics? Lyklema, Johannes Colloids and Surfaces A: Physicochemical and Engineering Aspects, Vol. 291, Issue 1-3 https://doi.org/10.1016/j.colsurfa.2006.06.043	journal	December 2006
Cation sorption on the muscovite (001) surface in chloride solutions using high-resolution X-ray reflectivity Schlegel, Michel L.; Nagy, Kathryn. L.; Fenter, Paul Geochimica et Cosmochimica Acta, Vol. 70, Issue 14 https://doi.org/10.1016/j.gca.2006.04.011	journal	July 2006
Distribution of barium and fulvic acid at the mica–solution interface using in-situ X-ray reflectivity Lee, Sang Soo; Nagy, Kathryn L.; Fenter, Paul Geochimica et Cosmochimica Acta, Vol. 71, Issue 23 https://doi.org/10.1016/j.gca.2007.05.031	journal	December 2007
Changes in adsorption free energy and speciation during competitive adsorption between monovalent cations at the muscovite (001)-water interface Lee, Sang Soo; Fenter, Paul; Nagy, Kathryn L. Geochimica et Cosmochimica Acta, Vol. 123 https://doi.org/10.1016/j.gca.2013.07.033	journal	December 2013
Monovalent – divalent cation competition at the muscovite mica surface: Experiment and theory Brugman, Sander J. T.; Werkhoven, Ben L.; Townsend, Eleanor R. Journal of Colloid and Interface Science, Vol. 559 https://doi.org/10.1016/j.jcis.2019.10.009	journal	February 2020
Recent advances in “water in salt” electrolytes for aqueous rechargeable monovalent-ion (Li+, Na+, K+) batteries Gao, Hong; Tang, Kaikai; Xiao, Jun Journal of Energy Chemistry, Vol. 69 https://doi.org/10.1016/j.jechem.2021.12.025	journal	June 2022
Effects of ionic strength on removal of toxic pollutants from aqueous media with multifarious adsorbents: A review Zhang, Yanhong; Zhu, Changqing; Liu, Fuqiang Science of The Total Environment, Vol. 646 https://doi.org/10.1016/j.scitotenv.2018.07.279	journal	January 2019
Resonant anomalous X-ray reflectivity as a probe of ion adsorption at solid–liquid interfaces Fenter, Paul; Park, Changyong; Nagy, Kathryn L. Thin Solid Films, Vol. 515, Issue 14 https://doi.org/10.1016/j.tsf.2006.12.118	journal	May 2007
Electrostatic Correlation Induced Ion Condensation and Charge Inversion in Multivalent Electrolytes Agrawal, Nikhil R.; Wang, Rui Journal of Chemical Theory and Computation, Vol. 18, Issue 10 https://doi.org/10.1021/acs.jctc.2c00607	journal	September 2022
Stern Layer Structure and Energetics at Mica–Water Interfaces Bourg, Ian C.; Lee, Sang Soo; Fenter, Paul The Journal of Physical Chemistry C, Vol. 121, Issue 17 https://doi.org/10.1021/acs.jpcc.7b01828	journal	April 2017
The Electrostatic Screening Length in Concentrated Electrolytes Increases with Concentration Smith, Alexander M.; Lee, Alpha A.; Perkin, Susan The Journal of Physical Chemistry Letters, Vol. 7, Issue 12 https://doi.org/10.1021/acs.jpclett.6b00867	journal	May 2016
Solid–Liquid Interface Structure of Muscovite Mica in CsCl and RbBr Solutions Pintea, Stelian; de Poel, Wester; de Jong, Aryan E. F. Langmuir, Vol. 32, Issue 49 https://doi.org/10.1021/acs.langmuir.6b02121	journal	November 2016
Concentration-Dependent Adsorption of CsI at the Muscovite–Electrolyte Interface Brugman, Sander J. T.; Townsend, Eleanor R.; Smets, Mireille M. H. Langmuir, Vol. 34, Issue 13 https://doi.org/10.1021/acs.langmuir.8b00038	journal	March 2018
Interaction of Monovalent Ions with Hydrophobic and Hydrophilic Colloids: Charge Inversion and Ionic Specificity Calero, Carles; Faraudo, Jordi; Bastos-González, Delfi Journal of the American Chemical Society, Vol. 133, Issue 38 https://doi.org/10.1021/ja204305b	journal	August 2011
Directly Probing the Effects of Ions on Hydration Forces at Interfaces Kilpatrick, Jason I.; Loh, Siu-Hong; Jarvis, Suzanne P. Journal of the American Chemical Society, Vol. 135, Issue 7 https://doi.org/10.1021/ja310255s	journal	February 2013
Ions Tune Interfacial Water Structure and Modulate Hydrophobic Interactions at Silica Surfaces Tuladhar, Aashish; Dewan, Shalaka; Pezzotti, Simone Journal of the American Chemical Society, Vol. 142, Issue 15 https://doi.org/10.1021/jacs.9b13273	journal	April 2020
Monovalent Ion Adsorption at the Muscovite (001)–Solution Interface: Relationships among Ion Coverage and Speciation, Interfacial Water Structure, and Substrate Relaxation Lee, Sang Soo; Fenter, Paul; Nagy, Kathryn L. Langmuir, Vol. 28, Issue 23 https://doi.org/10.1021/la300032h	journal	May 2012
Thermodynamics, Interfacial Structure, and pH Hysteresis of Rb ⁺ and Sr ²⁺ Adsorption at the Muscovite (001)−Solution Interface Park, Changyong; Fenter, Paul A.; Sturchio, Neil C. Langmuir, Vol. 24, Issue 24 https://doi.org/10.1021/la802446m	journal	December 2008
Real-time observation of cation exchange kinetics and dynamics at the muscovite-water interface Lee, Sang Soo; Fenter, Paul; Nagy, Kathryn L. Nature Communications, Vol. 8, Issue 1 https://doi.org/10.1038/ncomms15826	journal	June 2017
A new class of Solvent-in-Salt electrolyte for high-energy rechargeable metallic lithium batteries Suo, Liumin; Hu, Yong-Sheng; Li, Hong Nature Communications, Vol. 4, Issue 1 https://doi.org/10.1038/ncomms2513	journal	February 2013
Water-induced correlation between single ions imaged at the solid–liquid interface Ricci, Maria; Spijker, Peter; Voïtchovsky, Kislon Nature Communications, Vol. 5, Issue 1 https://doi.org/10.1038/ncomms5400	journal	July 2014
Double-slit photoelectron interference in strong-field ionization of the neon dimer Kunitski, Maksim; Eicke, Nicolas; Huber, Pia Nature Communications, Vol. 10, Issue 1 https://doi.org/10.1038/s41467-018-07882-8	journal	January 2019
Resolving the intrinsic short-range ordering of K+ ions on cleaved muscovite mica Franceschi, Giada; Kocán, Pavel; Conti, Andrea Nature Communications, Vol. 14, Issue 1 https://doi.org/10.1038/s41467-023-35872-y	journal	January 2023
Self-assembled nanostructures in ionic liquids facilitate charge storage at electrified interfaces Mao, Xianwen; Brown, Paul; Červinka, Ctirad Nature Materials, Vol. 18, Issue 12 https://doi.org/10.1038/s41563-019-0449-6	journal	August 2019
Electronic screening using a virtual Thomas–Fermi fluid for predicting wetting and phase transitions of ionic liquids at metal surfaces Schlaich, Alexander; Jin, Dongliang; Bocquet, Lyderic Nature Materials, Vol. 21, Issue 2 https://doi.org/10.1038/s41563-021-01121-0	journal	November 2021
Design strategies for nonaqueous multivalent-ion and monovalent-ion battery anodes Li, Matthew; Lu, Jun; Ji, Xiulei Nature Reviews Materials, Vol. 5, Issue 4 https://doi.org/10.1038/s41578-019-0166-4	journal	February 2020
Fast-charging aluminium–chalcogen batteries resistant to dendritic shorting Pang, Quanquan; Meng, Jiashen; Gupta, Saransh Nature, Vol. 608, Issue 7924 https://doi.org/10.1038/s41586-022-04983-9	journal	August 2022
Ultrastructural Characterization of the Lower Motor System in a Mouse Model of Krabbe Disease Cappello, Valentina; Marchetti, Laura; Parlanti, Paola Scientific Reports, Vol. 6, Issue 1 https://doi.org/10.1038/s41598-016-0001-8	journal	December 2016
Resonant anomalous X-ray reflectivity for revealing ion distributions near electrodes Carr, Amanda J. Nature Reviews Physics, Vol. 4, Issue 12 https://doi.org/10.1038/s42254-022-00519-2	journal	October 2022
Direct observation of ionic structure at solid-liquid interfaces: a deep look into the Stern Layer Siretanu, Igor; Ebeling, Daniel; Andersson, Martin P. Scientific Reports, Vol. 4, Issue 1 https://doi.org/10.1038/srep04956	journal	May 2014
Dynamic properties of confined hydration layers Perkin, Susan; Goldberg, Ronit; Chai, Liraz Faraday Discuss., Vol. 141 https://doi.org/10.1039/B805244A	journal	January 2009
Underscreening in concentrated electrolytes Lee, Alpha A.; Perez-Martinez, Carla S.; Smith, Alexander M. Faraday Discussions, Vol. 199 https://doi.org/10.1039/C6FD00250A	journal	January 2017
Breakdown of hydration repulsion between charged surfaces in aqueous Cs+ solutions Goldberg, Ronit; Chai, Liraz; Perkin, Susan Physical Chemistry Chemical Physics, Vol. 10, Issue 32 https://doi.org/10.1039/b807459n	journal	January 2008
Sur la constitution de la charge électrique à la surface d'un électrolyte Gouy, M. Journal de Physique Théorique et Appliquée, Vol. 9, Issue 1 https://doi.org/10.1051/jphystap:019100090045700	journal	January 1910
Focus Article: Oscillatory and long-range monotonic exponential decays of electrostatic interactions in ionic liquids and other electrolytes: The significance of dielectric permittivity and renormalized charges Kjellander, Roland The Journal of Chemical Physics, Vol. 148, Issue 19 https://doi.org/10.1063/1.5010024	journal	May 2018
Long-range electrostatic screening in ionic liquids Gebbie, Matthew A.; Dobbs, Howard A.; Valtiner, Markus Proceedings of the National Academy of Sciences, Vol. 112, Issue 24 https://doi.org/10.1073/pnas.1508366112	journal	May 2015
Ion correlations drive charge overscreening and heterogeneous nucleation at solid–aqueous electrolyte interfaces Lee, Sang Soo; Koishi, Ayumi; Bourg, Ian C. Proceedings of the National Academy of Sciences, Vol. 118, Issue 32 https://doi.org/10.1073/pnas.2105154118	journal	August 2021
LI. A contribution to the theory of electrocapillarity Chapman, David Leonard The London, Edinburgh, and Dublin Philosophical Magazine and Journal of Science, Vol. 25, Issue 148 https://doi.org/10.1080/14786440408634187	journal	April 1913
Surface X-ray diffraction Robinson, I. K.; Tweet, D. J. Reports on Progress in Physics, Vol. 55, Issue 5 https://doi.org/10.1088/0034-4885/55/5/002	journal	May 1992
Beyond standard Poisson–Boltzmann theory: ion-specific interactions in aqueous solutions Ben-Yaakov, Dan; Andelman, David; Harries, Daniel Journal of Physics: Condensed Matter, Vol. 21, Issue 42 https://doi.org/10.1088/0953-8984/21/42/424106	journal	September 2009
Underscreening in ionic liquids: a first principles analysis Rotenberg, Benjamin; Bernard, Olivier; Hansen, Jean-Pierre Journal of Physics: Condensed Matter, Vol. 30, Issue 5 https://doi.org/10.1088/1361-648X/aaa3ac	journal	January 2018
Crystal truncation rods and surface roughness Robinson, I. K. Physical Review B, Vol. 33, Issue 6 https://doi.org/10.1103/PhysRevB.33.3830	journal	March 1986
Morphology transitions during the growth of alkali halides from solution Lamelas, F. J.; Seader, S.; Zunic, M. Physical Review B, Vol. 67, Issue 4 https://doi.org/10.1103/PhysRevB.67.045414	journal	January 2003
Atomic-Scale Distribution of Water Molecules at the Mica-Water Interface Visualized by Three-Dimensional Scanning Force Microscopy Fukuma, Takeshi; Ueda, Yasumasa; Yoshioka, Shunsuke Physical Review Letters, Vol. 104, Issue 1 https://doi.org/10.1103/PhysRevLett.104.016101	journal	January 2010
Double Layer in Ionic Liquids: Overscreening versus Crowding Bazant, Martin Z.; Storey, Brian D.; Kornyshev, Alexei A. Physical Review Letters, Vol. 106, Issue 4 https://doi.org/10.1103/PhysRevLett.106.046102	journal	January 2011
Overcharging in Biological Systems: Reversal of Electrophoretic Mobility of Aqueous Polyaspartate by Multivalent Cations Kubíčková, Anna; Křížek, Tomáš; Coufal, Pavel Physical Review Letters, Vol. 108, Issue 18 https://doi.org/10.1103/PhysRevLett.108.186101	journal	May 2012
Interfacial Layering in the Electric Double Layer of Ionic Liquids de Souza, J. Pedro; Goodwin, Zachary A. H.; McEldrew, Michael Physical Review Letters, Vol. 125, Issue 11 https://doi.org/10.1103/PhysRevLett.125.116001	journal	September 2020
Self-Consistent Description of Vapor-Liquid Interface in Ionic Fluids Agrawal, Nikhil R.; Wang, Rui Physical Review Letters, Vol. 129, Issue 22 https://doi.org/10.1103/PhysRevLett.129.228001	journal	November 2022
Molecular-Scale Density Oscillations in Water Adjacent to a Mica Surface Cheng, L.; Fenter, P.; Nagy, K. L. Physical Review Letters, Vol. 87, Issue 15 https://doi.org/10.1103/PhysRevLett.87.156103	journal	September 2001
Phasing of resonant anomalous X-ray reflectivity spectra and direct Fourier synthesis of element-specific partial structures at buried interfaces Park, Changyong; Fenter, Paul A. Journal of Applied Crystallography, Vol. 40, Issue 2 https://doi.org/10.1107/S0021889806053131	journal	March 2007
Optimizing a flow-through X-ray transmission cell for studies of temporal and spatial variations of ion distributions at mineral–water interfaces Lee, Sang Soo; Fenter, Paul; Park, Changyong Journal of Synchrotron Radiation, Vol. 20, Issue 1 https://doi.org/10.1107/S0909049512041568	journal	November 2012
Cooperativity in Ion Hydration Tielrooij, K. J.; Garcia-Araez, N.; Bonn, M. Science, Vol. 328, Issue 5981 https://doi.org/10.1126/science.1183512	journal	May 2010
X-ray Reflectivity as a Probe of Mineral-Fluid Interfaces: A User Guide Fenter, P. A. Reviews in Mineralogy and Geochemistry, Vol. 49, Issue 1 https://doi.org/10.2138/gsrmg.49.1.149	journal	January 2002

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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
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Direct Experimental Observations of Ion Distributions during Overcharging at the Muscovite–Water Interface by Adsorption of Rb+ and Halides (Cl–, Br–, I–) at High Salinity

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Direct Experimental Observations of Ion Distributions during Overcharging at the Muscovite–Water Interface by Adsorption of Rb⁺ and Halides (Cl^–, Br^–, I^–) at High Salinity