The Interplay of Solvation and Polarization Effects on Ion Pairing in Nanoconfined Electrolytes

Fong, Kara D.; Sumić, Barbara; O’Neill, Niamh; Schran, Christoph; Grey, Clare P.; Michaelides, Angelos

doi:10.1021/acs.nanolett.4c00890

Title: The Interplay of Solvation and Polarization Effects on Ion Pairing in Nanoconfined Electrolytes

Journal Article · 09 April 2024 · Nano Letters

DOI: https://doi.org/10.1021/acs.nanolett.4c00890 · OSTI ID:2469559

^[1]; Sumić, Barbara ^[1];

^[1];

^[1]

University of Cambridge (United Kingdom)

The nature of ion–ion interactions in electrolytes confined to nanoscale pores has important implications for energy storage and separation technologies. However, the physical effects dictating the structure of nanoconfined electrolytes remain debated. Here we employ machine-learning-based molecular dynamics simulations to investigate ion–ion interactions with density functional theory level accuracy in a prototypical confined electrolyte, aqueous NaCl within graphene slit pores. We find that the free energy of ion pairing in highly confined electrolytes deviates substantially from that in bulk solutions, observing a decrease in contact ion pairing but an increase in solvent-separated ion pairing. These changes arise from an interplay of ion solvation effects and graphene’s electronic structure. Notably, the behavior observed from our first-principles-level simulations is not reproduced even qualitatively with the classical force fields conventionally used to model these systems. The insight provided in this work opens new avenues for predicting and controlling the structure of nanoconfined electrolytes.

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Research Organization:: Brookhaven National Laboratory (BNL), Upton, NY (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES). Scientific User Facilities (SUF); European Research Council; Engineering and Physical Sciences Research Council

Grant/Contract Number:: SC0012704

OSTI ID:: 2469559

Journal Information:: Nano Letters, Journal Name: Nano Letters Journal Issue: 16 Vol. 24; ISSN 1530-6984

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

References (56)

Nanofluidics: A New Arena for Materials Science Xu, Yan Advanced Materials, Vol. 30, Issue 3 https://doi.org/10.1002/adma.201702419	journal	November 2017
Porous Electrode Materials for Lithium-Ion Batteries - How to Prepare Them and What Makes Them Special Vu, Anh; Qian, Yuqiang; Stein, Andreas Advanced Energy Materials, Vol. 2, Issue 9 https://doi.org/10.1002/aenm.201200320	journal	August 2012
Multiscale Simulation of the Interaction and Adsorption of Ions on a Hydrophobic Graphene Surface Chen, Luohao; Guo, Yanan; Xu, Zhijun ChemPhysChem, Vol. 19, Issue 21 https://doi.org/10.1002/cphc.201800428	journal	August 2018
Improved grid-based algorithm for Bader charge allocation Sanville, Edward; Kenny, Steven D.; Smith, Roger Journal of Computational Chemistry, Vol. 28, Issue 5 https://doi.org/10.1002/jcc.20575	journal	January 2007
Nanofluidics: what is it and what can we expect from it? Eijkel, Jan C. T.; Berg, Albert van den Microfluidics and Nanofluidics, Vol. 1, Issue 3 https://doi.org/10.1007/s10404-004-0012-9	journal	April 2005
A fast and robust algorithm for Bader decomposition of charge density Henkelman, Graeme; Arnaldsson, Andri; Jónsson, Hannes Computational Materials Science, Vol. 36, Issue 3 https://doi.org/10.1016/j.commatsci.2005.04.010	journal	June 2006
Carbon nanotube membranes for water purification: A bright future in water desalination Das, Rasel; Ali, Md. Eaqub; Hamid, Sharifah Bee Abd Desalination, Vol. 336 https://doi.org/10.1016/j.desal.2013.12.026	journal	March 2014
Mechanisms of lithium selection from mixed LiCl-NaCl solution by nanopores: The synergistic effects of nanoconfinement and electric fields Liao, Gang; Yue, Xing-Yi; Zheng, Shi-Qi Desalination, Vol. 553 https://doi.org/10.1016/j.desal.2023.116455	journal	May 2023
Machine Learning Force Fields Unke, Oliver T.; Chmiela, Stefan; Sauceda, Huziel E. Chemical Reviews https://doi.org/10.1021/acs.chemrev.0c01111	journal	March 2021
Ab Initio Molecular Dynamics Investigation of the Solvation States of Hydrated Ions in Confined Water Qian, Chen; Zhou, Ke Inorganic Chemistry, Vol. 62, Issue 43 https://doi.org/10.1021/acs.inorgchem.3c02443	journal	October 2023
Free Energy Profile of NaCl in Water: First-Principles Molecular Dynamics with SCAN and ωB97X-V Exchange–Correlation Functionals Yao, Yi; Kanai, Yosuke Journal of Chemical Theory and Computation, Vol. 14, Issue 2 https://doi.org/10.1021/acs.jctc.7b00846	journal	January 2018
PhysNet: A Neural Network for Predicting Energies, Forces, Dipole Moments, and Partial Charges Unke, Oliver T.; Meuwly, Markus Journal of Chemical Theory and Computation, Vol. 15, Issue 6 https://doi.org/10.1021/acs.jctc.9b00181	journal	April 2019
A Deep Neural Network Potential for Water Confined in Graphene Nanocapillaries Zhao, Wen; Qiu, Hu; Guo, Wanlin The Journal of Physical Chemistry C, Vol. 126, Issue 25 https://doi.org/10.1021/acs.jpcc.2c02423	journal	June 2022
Machine Learning Force Fields: Construction, Validation, and Outlook Botu, V.; Batra, R.; Chapman, J. The Journal of Physical Chemistry C, Vol. 121, Issue 1 https://doi.org/10.1021/acs.jpcc.6b10908	journal	December 2016
Molecular Dynamics of Graphene–Electrolyte Interface: Interfacial Solution Structure and Molecular Diffusion Dočkal, Jan; Moučka, Filip; Lísal, Martin The Journal of Physical Chemistry C, Vol. 123, Issue 43 https://doi.org/10.1021/acs.jpcc.9b07487	journal	October 2019
Insights into Water Permeation through hBN Nanocapillaries by Ab Initio Machine Learning Molecular Dynamics Simulations Ghorbanfekr, Hossein; Behler, Jörg; Peeters, François M. The Journal of Physical Chemistry Letters, Vol. 11, Issue 17 https://doi.org/10.1021/acs.jpclett.0c01739	journal	August 2020
Effective Polarization in Pairwise Potentials at the Graphene–Electrolyte Interface Williams, Christopher D.; Dix, James; Troisi, Alessandro The Journal of Physical Chemistry Letters, Vol. 8, Issue 3 https://doi.org/10.1021/acs.jpclett.6b02783	journal	January 2017
Onsager Transport Coefficients and Transference Numbers in Polyelectrolyte Solutions and Polymerized Ionic Liquids Fong, Kara D.; Self, Julian; McCloskey, Bryan D. Macromolecules, Vol. 53, Issue 21 https://doi.org/10.1021/acs.macromol.0c02001	journal	October 2020
Nanoscale Confinement Effects on Ionic Conductivity of Solid Polymer Electrolytes: The Interplay between Diffusion and Dissociation Chen, Xiupeng; Kong, Xian Nano Letters, Vol. 23, Issue 11 https://doi.org/10.1021/acs.nanolett.3c01171	journal	May 2023
Dehydration as a Universal Mechanism for Ion Selectivity in Graphene and Other Atomically Thin Pores Sahu, Subin; Di Ventra, Massimiliano; Zwolak, Michael Nano Letters, Vol. 17, Issue 8 https://doi.org/10.1021/acs.nanolett.7b01399	journal	July 2017
Ion Structure Transition Enhances Charging Dynamics in Subnanometer Pores Mo, Tangming; Bi, Sheng; Zhang, Yuan ACS Nano, Vol. 14, Issue 2 https://doi.org/10.1021/acsnano.9b09648	journal	January 2020
Molecular Dynamics Study of Interfacial Confinement Effects of Aqueous NaCl Brines in Nanoporous Carbon Wander, Matthew C. F.; Shuford, Kevin L. The Journal of Physical Chemistry C, Vol. 114, Issue 48 https://doi.org/10.1021/jp104972e	journal	August 2010
Kinetic Pathways of Ion Pair Dissociation in Water Geissler, Phillip L.; Dellago, Christoph; Chandler, David The Journal of Physical Chemistry B, Vol. 103, Issue 18 https://doi.org/10.1021/jp984837g	journal	May 1999
Ion Adsorption at the Graphene/Electrolyte Interface Cole, Daniel J.; Ang, Priscilla K.; Loh, Kian Ping The Journal of Physical Chemistry Letters, Vol. 2, Issue 14 https://doi.org/10.1021/jz200765z	journal	June 2011
Probing the Structure of Salt Water under Confinement with First-Principles Molecular Dynamics and Theoretical X-ray Absorption Spectroscopy Kulik, Heather J.; Schwegler, Eric; Galli, Giulia The Journal of Physical Chemistry Letters, Vol. 3, Issue 18 https://doi.org/10.1021/jz300932p	journal	September 2012
Graphene-Based Supercapacitor with an Ultrahigh Energy Density Liu, Chenguang; Yu, Zhenning; Neff, David Nano Letters, Vol. 10, Issue 12 https://doi.org/10.1021/nl102661q	journal	December 2010
Water Desalination across Nanoporous Graphene Cohen-Tanugi, David; Grossman, Jeffrey C. Nano Letters, Vol. 12, Issue 7, p. 3602-3608 https://doi.org/10.1021/nl3012853	journal	June 2012
Selective Ionic Transport through Tunable Subnanometer Pores in Single-Layer Graphene Membranes O’Hern, Sean C.; Boutilier, Michael S. H.; Idrobo, Juan-Carlos Nano Letters, Vol. 14, Issue 3 https://doi.org/10.1021/nl404118f	journal	February 2014
Molecular transport through capillaries made with atomic-scale precision Radha, B.; Esfandiar, A.; Wang, F. C. Nature, Vol. 538, Issue 7624 https://doi.org/10.1038/nature19363	journal	September 2016
Direct observation of ion dynamics in supercapacitor electrodes using in situ diffusion NMR spectroscopy Forse, Alexander C.; Griffin, John M.; Merlet, Céline Nature Energy, Vol. 2, Issue 3 https://doi.org/10.1038/nenergy.2016.216	journal	February 2017
Efficient storage mechanisms for building better supercapacitors Salanne, M.; Rotenberg, B.; Naoi, K. Nature Energy, Vol. 1, Issue 6 https://doi.org/10.1038/nenergy.2016.70	journal	May 2016
Two-dimensional monolayer salt nanostructures can spontaneously aggregate rather than dissolve in dilute aqueous solutions Zhao, Wenhui; Sun, Yunxiang; Zhu, Weiduo Nature Communications, Vol. 12, Issue 1 https://doi.org/10.1038/s41467-021-25938-0	journal	September 2021
Rich proton dynamics and phase behaviours of nanoconfined ices Jiang, Jian; Gao, Yurui; Li, Lei Nature Physics, Vol. 20, Issue 3 https://doi.org/10.1038/s41567-023-02341-8	journal	January 2024
The first-principles phase diagram of monolayer nanoconfined water Kapil, Venkat; Schran, Christoph; Zen, Andrea Nature, Vol. 609, Issue 7927 https://doi.org/10.1038/s41586-022-05036-x	journal	September 2022
Nanofluidics, from bulk to interfaces Bocquet, Lydéric; Charlaix, Elisabeth Chem. Soc. Rev., Vol. 39, Issue 3 https://doi.org/10.1039/B909366B	journal	January 2010
Temperature dependence of ion diffusion coefficients in NaCl electrolyte confined within graphene nanochannels Kong, Jing; Bo, Zheng; Yang, Huachao Physical Chemistry Chemical Physics, Vol. 19, Issue 11 https://doi.org/10.1039/C6CP08752C	journal	January 2017
Confinement-enhanced Li⁺ ion dynamics in an ionic liquid-based electrolyte in porous material Hessling, Janis; Lange, Martin; Schönhoff, Monika Physical Chemistry Chemical Physics, Vol. 25, Issue 35 https://doi.org/10.1039/D3CP02901H	journal	January 2023
A consistent and accurate ab initio parametrization of density functional dispersion correction (DFT-D) for the 94 elements H-Pu Grimme, Stefan; Antony, Jens; Ehrlich, Stephan The Journal of Chemical Physics, Vol. 132, Issue 15 https://doi.org/10.1063/1.3382344	journal	April 2010
Accurate and efficient algorithm for Bader charge integration Yu, Min; Trinkle, Dallas R. The Journal of Chemical Physics, Vol. 134, Issue 6 https://doi.org/10.1063/1.3553716	journal	February 2011
Perspective: Machine learning potentials for atomistic simulations Behler, Jörg The Journal of Chemical Physics, Vol. 145, Issue 17 https://doi.org/10.1063/1.4966192	journal	November 2016
When do short-range atomistic machine-learning models fall short? Yue, Shuwen; Muniz, Maria Carolina; Calegari Andrade, Marcos F. The Journal of Chemical Physics, Vol. 154, Issue 3 https://doi.org/10.1063/5.0031215	journal	January 2021
Interaction confinement and electronic screening in two-dimensional nanofluidic channels Kavokine, Nikita; Robin, Paul; Bocquet, Lydéric The Journal of Chemical Physics, Vol. 157, Issue 11 https://doi.org/10.1063/5.0102002	journal	September 2022
Machine learning potentials for complex aqueous systems made simple Schran, Christoph; Thiemann, Fabian L.; Rowe, Patrick Proceedings of the National Academy of Sciences, Vol. 118, Issue 38 https://doi.org/10.1073/pnas.2110077118	journal	September 2021
Ion Pairing in Confined Electrolytes Nicholson, D.; Quirke, N. Molecular Simulation, Vol. 29, Issue 4 https://doi.org/10.1080/0892702031000078427	journal	January 2003
A grid-based Bader analysis algorithm without lattice bias Tang, W.; Sanville, E.; Henkelman, G. Journal of Physics: Condensed Matter, Vol. 21, Issue 8 https://doi.org/10.1088/0953-8984/21/8/084204	journal	January 2009
Charge storage mechanism in nanoporous carbons and its consequence for electrical double layer capacitors Simon, P.; Gogotsi, Y. Philosophical Transactions of the Royal Society A: Mathematical, Physical and Engineering Sciences, Vol. 368, Issue 1923, p. 3457-3467 https://doi.org/10.1098/rsta.2010.0109	journal	June 2010
High-dimensional neural-network potentials for multicomponent systems: Applications to zinc oxide Artrith, Nongnuch; Morawietz, Tobias; Behler, Jörg Physical Review B, Vol. 83, Issue 15 https://doi.org/10.1103/PhysRevB.83.153101	journal	April 2011
Comment on “Generalized Gradient Approximation Made Simple” Zhang, Yingkai; Yang, Weitao Physical Review Letters, Vol. 80, Issue 4 https://doi.org/10.1103/PhysRevLett.80.890	journal	January 1998
Enhanced water permeability and tunable ion selectivity in subnanometer carbon nanotube porins Tunuguntla, Ramya H.; Henley, Robert Y.; Yao, Yun-Chiao Science, Vol. 357, Issue 6353 https://doi.org/10.1126/science.aan2438	journal	August 2017
Ion-capture electrodialysis using multifunctional adsorptive membranes Uliana, Adam A.; Bui, Ngoc T.; Kamcev, Jovan Science, Vol. 372, Issue 6539 https://doi.org/10.1126/science.abf5991	journal	April 2021
Modeling of emergent memory and voltage spiking in ionic transport through angstrom-scale slits Robin, Paul; Kavokine, Nikita; Bocquet, Lydéric Science, Vol. 373, Issue 6555 https://doi.org/10.1126/science.abf7923	journal	August 2021
Machine learning potentials for extended systems: a perspective Behler, Jörg; Csányi, Gábor The European Physical Journal B, Vol. 94, Issue 7 https://doi.org/10.1140/epjb/s10051-021-00156-1	journal	July 2021
Water Treatment: Are Membranes the Panacea? Landsman, Matthew R.; Sujanani, Rahul; Brodfuehrer, Samuel H. Annual Review of Chemical and Biomolecular Engineering, Vol. 11, Issue 1 https://doi.org/10.1146/annurev-chembioeng-111919-091940	journal	June 2020
Neural Network Potentials: A Concise Overview of Methods Kocer, Emir; Ko, Tsz Wai; Behler, Jörg Annual Review of Physical Chemistry, Vol. 73, Issue 1 https://doi.org/10.1146/annurev-physchem-082720-034254	journal	April 2022
Crumbling Crystals: On the Dissolution Mechanism of NaCl in Water O'Neill, Niamh; Schran, Christoph; Cox, Stephen J. arXiv https://doi.org/10.48550/arXiv.2211.04345	preprint	January 2022
To Pair or not to Pair? Machine-Learned Explicitly-Correlated Electronic Structure for NaCl in Water O'Neill, Niamh; Shi, Benjamin X.; Fong, Kara arXiv https://doi.org/10.48550/arXiv.2311.01527	preprint	January 2023

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Title: The Interplay of Solvation and Polarization Effects on Ion Pairing in Nanoconfined Electrolytes

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