Elucidating molecular scale interactions underlying the freezing behavior of salt solutions in silica nanopores

Mohammed, Sohaib; Asgar, Hassnain; Jia, Yang; Hazra, Rituparna; Ochonma, Prince; Benmore, Chris J.; Gadikota, Greeshma

doi:10.1039/D4CP04622F

Elucidating molecular scale interactions underlying the freezing behavior of salt solutions in silica nanopores

Journal Article · Mon Mar 10 00:00:00 EDT 2025 · Physical Chemistry Chemical Physics. PCCP

DOI:https://doi.org/10.1039/D4CP04622F· OSTI ID:2559019

^[1]; ^[1]; ^[1]; ^[1]; ^[1]; Benmore, Chris J. ^[2]; ^[1]

Cornell Univ., Ithaca, NY (United States)
Argonne National Laboratory (ANL), Argonne, IL (United States). Advanced Photon Source (APS)

Elucidating the influence of nanoscale confinement on the freezing behavior of salt solutions is of fundamental interest to environmental security and materials science and engineering. Specific structural information such as the coordination environment of ions in confined aqueous medium, effects on the extended hexagonal network of water molecules and their mutual non-bonding interactions in confinement are sparse in the literature along with the change in the dynamical characteristics of water in the presence of ions. To address these knowledge gaps, the current study is focused on investigating the influence of reduced dimensionality arising from nanoscale confinement on the structural evolution of salt solutions on freezing and the associated fluid–surface interactions. In this regard, operando wide-angle X-ray scattering (WAXS) measurements and classical molecular dynamics (MD) simulations are conducted with water and 0.5 M CaCl₂, MgCl₂ and KCl solutions confined in 4 nm sized SBA-15 silica pores upon cooling from 300 K to 200 K. The freezing point of the salt solutions is depressed to 235 K which is about 10 K lower than that of confined water. The translational dynamics of confined salt solutions indicates shifts in the fragile-to-strong dynamical crossover to a lower temperature compared to pure water. The strong electrostatic attraction between the cations and the surrounding water molecules contributes to the freezing point depression in confined salt solutions. These insights unlock the molecular-scale basis and mechanisms underlying the freezing behavior of confined salt solutions.

View Journal Article

Research Organization:: Argonne National Laboratory (ANL), Argonne, IL (United States). Advanced Photon Source (APS); Energy Frontier Research Centers (EFRC) (United States). Multi-scale Fluid-Solid Interactions in Architected and Natural Materials (MUSE)

Sponsoring Organization:: USDOE; USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: AC02-06CH11357; SC0019285

OSTI ID:: 2559019

Alternate ID(s):: OSTI ID: 2574329

Journal Information:: Physical Chemistry Chemical Physics. PCCP, Journal Name: Physical Chemistry Chemical Physics. PCCP Journal Issue: 18 Vol. 27; ISSN 1463-9076; ISSN 1463-9084

Publisher:: Royal Society of ChemistryCopyright Statement

Country of Publication:: United States

Language:: English

References (78)

Predicting hydration energies for multivalent ions Andersson, Martin P.; Stipp, Susan L. S. Journal of Computational Chemistry, Vol. 35, Issue 28 https://doi.org/10.1002/jcc.23733	journal	September 2014
Analysis of molecular dynamics of moist wood components by applying the stretched-exponential function Nakao, Sayaka; Nakano, Takato Journal of Materials Science, Vol. 46, Issue 14 https://doi.org/10.1007/s10853-011-5385-z	journal	February 2011
The heat capacity of water in silica pores Etzler, Frank M.; White, Pamela J. Journal of Colloid and Interface Science, Vol. 120, Issue 1 https://doi.org/10.1016/0021-9797(87)90326-2	journal	November 1987
Charge density-dependent strength of hydration and biological structure Collins, K. D. Biophysical Journal, Vol. 72, Issue 1 https://doi.org/10.1016/S0006-3495(97)78647-8	journal	January 1997
Colloidal crystals as templates for porous materials Velev, Orlin D.; Lenhoff, Abraham M. Current Opinion in Colloid & Interface Science, Vol. 5, Issue 1-2 https://doi.org/10.1016/S1359-0294(00)00039-X	journal	March 2000
Preparation of porous materials with ordered hole structure Hoa, Marcus Liew Kai; Lu, Meihua; Zhang, Yong Advances in Colloid and Interface Science, Vol. 121, Issue 1-3 https://doi.org/10.1016/j.cis.2006.05.029	journal	September 2006
NMR measurements of permafrost: unfrozen water assay, pore-scale distribution of ice, and hydraulic permeability of sediments Kleinberg, R. L.; Griffin, D. D. Cold Regions Science and Technology, Vol. 42, Issue 1 https://doi.org/10.1016/j.coldregions.2004.12.002	journal	June 2005
Heterogeneous nucleation of ice from supercooled NaCl solution confined in porous cement paste Zeng, Qiang; Li, Kefei; Fen-Chong, Teddy Journal of Crystal Growth, Vol. 409 https://doi.org/10.1016/j.jcrysgro.2014.09.045	journal	January 2015
A shift from the isobaric to the isochoric thermodynamic state can reduce energy consumption and augment temperature stability in frozen food storage Powell-Palm, Matthew J.; Rubinsky, Boris Journal of Food Engineering, Vol. 251 https://doi.org/10.1016/j.jfoodeng.2019.02.001	journal	June 2019
Effects of salts of the Hofmeister series on the hydrogen bond network of water Nucci, Nathaniel V.; Vanderkooi, Jane M. Journal of Molecular Liquids, Vol. 143, Issue 2-3 https://doi.org/10.1016/j.molliq.2008.07.010	journal	October 2008
Molecular dynamics study on relaxation of supercooled liquid water at different cooling rates Pingua, Nandlal; Gautam, Arvind K. Materials Today Communications, Vol. 39 https://doi.org/10.1016/j.mtcomm.2024.108777	journal	June 2024
Extended range X-ray pair distribution functions Benmore, C. J.; Alderman, O. L. G.; Robinson, D. Nuclear Instruments and Methods in Physics Research Section A: Accelerators, Spectrometers, Detectors and Associated Equipment, Vol. 955 https://doi.org/10.1016/j.nima.2019.163318	journal	March 2020
GROMACS: High performance molecular simulations through multi-level parallelism from laptops to supercomputers Abraham, Mark James; Murtola, Teemu; Schulz, Roland SoftwareX, Vol. 1-2 https://doi.org/10.1016/j.softx.2015.06.001	journal	September 2015
Confined Water: Structure, Dynamics, and Thermodynamics Chakraborty, Sudip; Kumar, Hemant; Dasgupta, Chandan Accounts of Chemical Research, Vol. 50, Issue 9 https://doi.org/10.1021/acs.accounts.6b00617	journal	August 2017
Confined Water as Model of Supercooled Water Cerveny, Silvina; Mallamace, Francesco; Swenson, Jan Chemical Reviews, Vol. 116, Issue 13 https://doi.org/10.1021/acs.chemrev.5b00609	journal	March 2016
Water—The Most Anomalous Liquid Pettersson, Lars Gunnar Moody; Henchman, Richard Humfry; Nilsson, Anders Chemical Reviews, Vol. 116, Issue 13 https://doi.org/10.1021/acs.chemrev.6b00363	journal	April 2016
Interfacial and Confinement-Mediated Organization of Gas Hydrates, Water, Organic Fluids, and Nanoparticles for the Utilization of Subsurface Energy and Geological Resources Mohammed, Sohaib; Asgar, Hassnain; Deo, Milind Energy & Fuels, Vol. 35, Issue 6 https://doi.org/10.1021/acs.energyfuels.0c04287	journal	February 2021
Following the Crystallization of Amorphous Ice after Ultrafast Laser Heating Ladd-Parada, Marjorie; Amann-Winkel, Katrin; Kim, Kyung Hwan The Journal of Physical Chemistry B, Vol. 126, Issue 11 https://doi.org/10.1021/acs.jpcb.1c10906	journal	March 2022
Kinetics of Ice Nucleation Confined in Nanoporous Alumina Suzuki, Yasuhito; Steinhart, Martin; Butt, Hans-Jürgen The Journal of Physical Chemistry B, Vol. 119, Issue 35 https://doi.org/10.1021/acs.jpcb.5b06295	journal	August 2015
Water in a Soft Confinement: Structure of Water in Amorphous Sorbitol Shalaev, Evgenyi; Soper, Alan K. The Journal of Physical Chemistry B, Vol. 120, Issue 29 https://doi.org/10.1021/acs.jpcb.6b06157	journal	July 2016
Influence of Pore Wall Hydrophobicity on Freezing and Melting of Confined Water Morishige, Kunimitsu The Journal of Physical Chemistry C, Vol. 122, Issue 9 https://doi.org/10.1021/acs.jpcc.8b00538	journal	January 2018
Enhancing and Impeding Heterogeneous Ice Nucleation through Nanogrooves Li, Chu; Tao, Ran; Luo, Shuang The Journal of Physical Chemistry C, Vol. 122, Issue 45 https://doi.org/10.1021/acs.jpcc.8b07779	journal	October 2018
Phase Transitions of Ice in Aqueous Salt Solutions within Nanometer-Sized Pores Jantsch, Evelyn; Weinberger, Christian; Tiemann, Michael The Journal of Physical Chemistry C, Vol. 123, Issue 40 https://doi.org/10.1021/acs.jpcc.9b06527	journal	September 2019
Structure and Dynamics of Confined Liquids: Challenges and Perspectives for the X-ray Surface Forces Apparatus Weiss, Henning; Cheng, Hsiu-Wei; Mars, Julian Langmuir, Vol. 35, Issue 51 https://doi.org/10.1021/acs.langmuir.9b01215	journal	October 2019
Highly Confined Water: Two-Dimensional Ice, Amorphous Ice, and Clathrate Hydrates Zhao, Wen-Hui; Wang, Lu; Bai, Jaeil Accounts of Chemical Research, Vol. 47, Issue 8 https://doi.org/10.1021/ar5001549	journal	July 2014
Heat capacity of water at extremes of supercooling and superheating Angell, C. A.; Sichina, W. J.; Oguni, M. The Journal of Physical Chemistry, Vol. 86, Issue 6 https://doi.org/10.1021/j100395a032	journal	March 1982
How Ions Affect the Structure of Water Hribar, Barbara; Southall, Noel T.; Vlachy, Vojko Journal of the American Chemical Society, Vol. 124, Issue 41 https://doi.org/10.1021/ja026014h	journal	October 2002
Role of Nanoscale Interfacial Proximity in Contact Freezing in Water Hussain, Sarwar; Haji-Akbari, Amir Journal of the American Chemical Society, Vol. 143, Issue 5 https://doi.org/10.1021/jacs.0c10663	journal	January 2021
Is Ice Nucleation by Organic Crystals Nonclassical? An Assessment of the Monolayer Hypothesis of Ice Nucleation Metya, Atanu K.; Molinero, Valeria Journal of the American Chemical Society, Vol. 143, Issue 12 https://doi.org/10.1021/jacs.0c12012	journal	March 2021
First-Principles Molecular Dynamics Simulations of the Spontaneous Freezing Transition of 2D Water in a Nanoslit Jiang, Jian; Gao, Yurui; Zhu, Weiduo Journal of the American Chemical Society, Vol. 143, Issue 21 https://doi.org/10.1021/jacs.1c03243	journal	May 2021
Spontaneous Freezing of Water between 233 and 235 K Is Not Due to Homogeneous Nucleation Xue, Han; Fu, Yang; Lu, Youhua Journal of the American Chemical Society, Vol. 143, Issue 34 https://doi.org/10.1021/jacs.1c04055	journal	August 2021
Molecular Models of Hydroxide, Oxyhydroxide, and Clay Phases and the Development of a General Force Field Cygan, Randall T.; Liang, Jian-Jie; Kalinichev, Andrey G. The Journal of Physical Chemistry B, Vol. 108, Issue 4 https://doi.org/10.1021/jp0363287	journal	January 2004
Effects of Confinement on Water Structure and Dynamics: A Molecular Simulation Study Hirunsit, P.; Balbuena, P. B. The Journal of Physical Chemistry C, Vol. 111, Issue 4 https://doi.org/10.1021/jp063718v	journal	February 2007
Dynamic Crossovers and Stepwise Solidification of Confined Water: A ² H NMR Study Sattig, M.; Vogel, M. The Journal of Physical Chemistry Letters, Vol. 5, Issue 1 https://doi.org/10.1021/jz402539r	journal	December 2013
Ordered porous materials for emerging applications Davis, Mark E. Nature, Vol. 417, Issue 6891, p. 813-821 https://doi.org/10.1038/nature00785	journal	June 2002
Ultrafast X-ray probing of water structure below the homogeneous ice nucleation temperature Sellberg, J. A.; Huang, C.; McQueen, T. A. Nature, Vol. 510, Issue 7505 https://doi.org/10.1038/nature13266	journal	June 2014
Enhanced heterogeneous ice nucleation by special surface geometry Bi, Yuanfei; Cao, Boxiao; Li, Tianshu Nature Communications, Vol. 8, Issue 1 https://doi.org/10.1038/ncomms15372	journal	May 2017
Phase transitions in confined water nanofilms Han, Sungho; Choi, M. Y.; Kumar, Pradeep Nature Physics, Vol. 6, Issue 9 https://doi.org/10.1038/nphys1708	journal	July 2010
How ice grows from premelting films and water droplets Sibley, David N.; Llombart, Pablo; Noya, Eva G. Nature Communications, Vol. 12, Issue 1 https://doi.org/10.1038/s41467-020-20318-6	journal	January 2021
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
Layer-by-Layer Freezing of Nanoconfined Water Xia, Yiqing; Cho, Hyeyoung; Deo, Milind Scientific Reports, Vol. 10, Issue 1 https://doi.org/10.1038/s41598-020-62137-1	journal	March 2020
A continuum of amorphous ices between low-density and high-density amorphous ice Eltareb, Ali; Lopez, Gustavo E.; Giovambattista, Nicolas Communications Chemistry, Vol. 7, Issue 1 https://doi.org/10.1038/s42004-024-01117-2	journal	February 2024
Freezing water at constant volume and under confinement Powell-Palm, Matthew J.; Rubinsky, Boris; Sun, Wenhao Communications Physics, Vol. 3, Issue 1 https://doi.org/10.1038/s42005-020-0303-9	journal	February 2020
Ferroelectric hexagonal and rhombic monolayer ice phases Zhao, Wen-Hui; Bai, Jaeil; Yuan, Lan-Feng Chem. Sci., Vol. 5, Issue 5 https://doi.org/10.1039/C3SC53368A	journal	January 2014
NMR studies on the temperature-dependent dynamics of confined water Sattig, Matthias; Reutter, Stefan; Fujara, Franz Phys. Chem. Chem. Phys., Vol. 16, Issue 36 https://doi.org/10.1039/C4CP02057J	journal	January 2014
Evolution of confined ice nano structures at different levels of pore filling: a synchrotron based X-ray diffraction study Thangswamy, Muthulakshmi; Maheshwari, Priya; Dutta, Dhanadeep Physical Chemistry Chemical Physics, Vol. 22, Issue 25 https://doi.org/10.1039/D0CP01988G	journal	January 2020
Structure of ice confined in silica nanopores Mohammed, Sohaib; Asgar, Hassnain; Benmore, Chris J. Physical Chemistry Chemical Physics, Vol. 23, Issue 22 https://doi.org/10.1039/D1CP00686J	journal	January 2021
The pressure induced phase diagram of double-layer ice under confinement: a first-principles study Jyothirmai, M. V.; Abraham, B. Moses; Singh, Jayant K. Physical Chemistry Chemical Physics, Vol. 24, Issue 27 https://doi.org/10.1039/D2CP01470J	journal	January 2022
Beyond crystallography: the study of disorder, nanocrystallinity and crystallographically challenged materials with pair distribution functions Billinge, Simon J. L.; Kanatzidis, M. G. Chemical Communications, Issue 7 https://doi.org/10.1039/b309577k	journal	January 2004
Melting and freezing of water in cylindrical silica nanopores Jähnert, S.; Vaca Chávez, F.; Schaumann, G. E. Physical Chemistry Chemical Physics, Vol. 10, Issue 39 https://doi.org/10.1039/b809438c	journal	January 2008
Novel ice structures in carbon nanopores: pressure enhancement effect of confinement Jazdzewska, Monika; Śliwinska-Bartkowiak, Małgorzata M.; Beskrovnyy, Anatoly I. Physical Chemistry Chemical Physics, Vol. 13, Issue 19 https://doi.org/10.1039/c0cp02797a	journal	January 2011
Multiple relaxation processes versus the fragile-to-strong transition in confined water Bruni, F.; Mancinelli, R.; Ricci, M. A. Physical Chemistry Chemical Physics, Vol. 13, Issue 44 https://doi.org/10.1039/c1cp22029b	journal	January 2011
Density minimum of confined water at low temperatures: a combined study by small-angle scattering of X-rays and neutrons Erko, M.; Wallacher, D.; Hoell, A. Physical Chemistry Chemical Physics, Vol. 14, Issue 11 https://doi.org/10.1039/c2cp24075k	journal	January 2012
Glass transition and layering effects in confined water: A computer simulation study Gallo, P.; Rovere, M.; Spohr, E. The Journal of Chemical Physics, Vol. 113, Issue 24 https://doi.org/10.1063/1.1328073	journal	December 2000
Fragile-to-strong liquid transition in deeply supercooled confined water Faraone, A.; Liu, L.; Mou, C. -Y. The Journal of Chemical Physics, Vol. 121, Issue 22 https://doi.org/10.1063/1.1832595	journal	January 2004
The melting temperature of the most common models of water Vega, C.; Sanz, E.; Abascal, J. L. F. The Journal of Chemical Physics, Vol. 122, Issue 11 https://doi.org/10.1063/1.1862245	journal	March 2005
Isothermal compressibility of supercooled water and evidence for a thermodynamic singularity at −45°C Speedy, R. J.; Angell, C. A. The Journal of Chemical Physics, Vol. 65, Issue 3 https://doi.org/10.1063/1.433153	journal	August 1976
The Nose–Hoover thermostat Evans, D. J.; Holian, B. L. The Journal of Chemical Physics, Vol. 83, Issue 8 https://doi.org/10.1063/1.449071	journal	October 1985
Particle mesh Ewald: An N ⋅log( N ) method for Ewald sums in large systems Darden, Tom; York, Darrin; Pedersen, Lee The Journal of Chemical Physics, Vol. 98, Issue 12 https://doi.org/10.1063/1.464397	journal	June 1993
A five-site model for liquid water and the reproduction of the density anomaly by rigid, nonpolarizable potential functions Mahoney, Michael W.; Jorgensen, William L. The Journal of Chemical Physics, Vol. 112, Issue 20 https://doi.org/10.1063/1.481505	journal	May 2000
Solute strongly impacts freezing under confinement Ginot, Félix; Lenavetier, Théo; Dedovets, Dmytro Applied Physics Letters, Vol. 116, Issue 25 https://doi.org/10.1063/5.0008925	journal	June 2020
Potential energy functions for atomic-level simulations of water and organic and biomolecular systems Jorgensen, W. L.; Tirado-Rives, J. Proceedings of the National Academy of Sciences, Vol. 102, Issue 19 https://doi.org/10.1073/pnas.0408037102	journal	May 2005
Evidence of the existence of the low-density liquid phase in supercooled, confined water Mallamace, F.; Broccio, M.; Corsaro, C. Proceedings of the National Academy of Sciences, Vol. 104, Issue 2 https://doi.org/10.1073/pnas.0607138104	journal	December 2006
Rating antifreeze proteins: Not a breeze Haji-Akbari, Amir Proceedings of the National Academy of Sciences, Vol. 113, Issue 14 https://doi.org/10.1073/pnas.1602196113	journal	March 2016
Origin of the emergent fragile-to-strong transition in supercooled water Shi, Rui; Russo, John; Tanaka, Hajime Proceedings of the National Academy of Sciences, Vol. 115, Issue 38 https://doi.org/10.1073/pnas.1807821115	journal	September 2018
Pore condensation and freezing is responsible for ice formation below water saturation for porous particles David, Robert O.; Marcolli, Claudia; Fahrni, Jonas Proceedings of the National Academy of Sciences, Vol. 116, Issue 17 https://doi.org/10.1073/pnas.1813647116	journal	April 2019
Mode-distribution analysis of quasielastic neutron scattering and application to liquid water Kikuchi, Tatsuya; Nakajima, Kenji; Ohira-Kawamura, Seiko Physical Review E, Vol. 87, Issue 6 https://doi.org/10.1103/PhysRevE.87.062314	journal	June 2013
Freezing of Water Confined at the Nanoscale Alabarse, F. G.; Haines, J.; Cambon, O. Physical Review Letters, Vol. 109, Issue 3 https://doi.org/10.1103/PhysRevLett.109.035701	journal	July 2012
The physics of premelted ice and its geophysical consequences Dash, J. G.; Rempel, A. W.; Wettlaufer, J. S. Reviews of Modern Physics, Vol. 78, Issue 3 https://doi.org/10.1103/RevModPhys.78.695	journal	July 2006
A comparison of various commonly used correlation functions for describing total scattering Keen, David A. Journal of Applied Crystallography, Vol. 34, Issue 2 https://doi.org/10.1107/S0021889800019993	journal	April 2001
PDFgetX2: a GUI-driven program to obtain the pair distribution function from X-ray powder diffraction data Qiu, Xiangyun; Thompson, Jeroen W.; Billinge, Simon J. L. Journal of Applied Crystallography, Vol. 37, Issue 4, p. 678-678 https://doi.org/10.1107/S0021889804011744	journal	July 2004
Nika : software for two-dimensional data reduction Ilavsky, Jan Journal of Applied Crystallography, Vol. 45, Issue 2 https://doi.org/10.1107/S0021889812004037	journal	March 2012
Water Freezes Differently on Positively and Negatively Charged Surfaces of Pyroelectric Materials Ehre, D.; Lavert, E.; Lahav, M. Science, Vol. 327, Issue 5966 https://doi.org/10.1126/science.1178085	journal	February 2010
Anomalously low dielectric constant of confined water Fumagalli, L.; Esfandiar, A.; Fabregas, R. Science, Vol. 360, Issue 6395 https://doi.org/10.1126/science.aat4191	journal	June 2018
Experimental observation of the liquid-liquid transition in bulk supercooled water under pressure Kim, Kyung Hwan; Amann-Winkel, Katrin; Giovambattista, Nicolas Science, Vol. 370, Issue 6519 https://doi.org/10.1126/science.abb9385	journal	November 2020
Structure and dynamics of water confined in silica hydrogels: X-ray scattering and dielectric spectroscopy studies Cammarata, M.; Levantino, M.; Cupane, A. The European Physical Journal E, Vol. 12, Issue S1 https://doi.org/10.1140/epjed/e2003-01-016-2	journal	November 2003
New Approaches to Cryopreservation of Cells, Tissues, and Organs Taylor, Michael J.; Weegman, Bradley P.; Baicu, Simona C. Transfusion Medicine and Hemotherapy, Vol. 46, Issue 3 https://doi.org/10.1159/000499453	journal	January 2019
Temperature and Size Effects on Structural and Dynamical Properties of Water Confined in 1 – 10 nm-scale Pores Using Proton NMR Spectroscopy Fukatsu, Yuta; Morikawa, Kyojiro; Ikeda, Yasuhisa Analytical Sciences, Vol. 33, Issue 8 https://doi.org/10.2116/analsci.33.903	journal	August 2017

Similar Records

Confinement-Driven Heterogeneous Benzene Crystallization in Silica Nanopores

Journal Article · Sun Jul 31 20:00:00 EDT 2022 · Energy and Fuels · OSTI ID:1970713

Structure of ice confined in silica nanopores

Journal Article · Sun May 16 20:00:00 EDT 2021 · Physical Chemistry Chemical Physics. PCCP · OSTI ID:1808583

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
X-ray scattering
freezing behavior
nanoscale confinement
salt solutions

Elucidating molecular scale interactions underlying the freezing behavior of salt solutions in silica nanopores

Citation Formats

References (78)

Similar Records

Related Subjects