Accounts of Chemical Research, volume 53, issue 12, pages 2869-2878
Thermodynamic and Kinetic Transitions of Liquids in Nanoconfinement
1
Department of Materials Science & Engineering, University of California at Davis, Davis, California 95616, United States
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2
Department of Chemistry, University of Utah, Salt Lake City, Utah 84112, United States
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Publication type: Journal Article
Publication date: 2020-11-13
Journal:
Accounts of Chemical Research
Quartile SCImago
Q1
Quartile WOS
Q1
Impact factor: 18.3
ISSN: 00014842, 15204898
General Chemistry
General Medicine
Abstract
Core principles of chemistry are ubiquitously invoked to shed light on the nature of molecular level interactions in nanoconfined fluids, which play a pivotal role in a wide range of processes in geochemistry, biology, and engineering. A detailed understanding of the physicochemical processes involved in the flow, structural transitions, and freezing or melting behavior of fluids confined within nanometer-sized pores of solid materials is thus of enormous importance for both basic research and technological applications.This Account provides a perspective on new insights into the thermodynamic and kinetic transitions of nanoconfined fluids in their stable and metastable forms. After briefly introducing the unique properties of mesoporous silicas from the SBA, MCM, and FDU families that serve as the confinement matrices, combining highly ordered single and bimodal mesopore architectures with tunable pore sizes in the ∼2-15 nm range and narrow size distributions, recent studies on melting/freezing behavior of water confined in these host matrices are reviewed. While differential scanning calorimetry (DSC) reveals a linear relationship between melting point depression and pore size (independent of the pore shape), as predicted by the Gibbs-Thomson relation, variable temperature 2H wide-line nuclear magnetic resonance (NMR) spectroscopy studies confirm the core-shell model of water and give evidence for a layer-by-layer freezing mechanism, which gives rise to an apparent fragile-to-strong transition in the solidification dynamics.In contrast to the freezing/melting behavior of water, the effect of nanoconfinement on the glass transition of supercooled liquids is nonuniversal and the glass transition temperature Tg can either increase or decrease with the dimensionality and extent of confinement. This nonuniversal behavior is exemplified by the two glass-forming molecular liquids, glycerol and ortho-terphenyl (OTP). While glycerol shows an increase in Tg and a pronounced slowdown of the rotational dynamics of the constituent molecules due to a change in the molecular packing between the bulk and the confined liquid, OTP displays a linear and confining-media-dependent depression of Tg with increased confinement that is strongly influenced by the pore-liquid interface characteristics.This Account concludes with a focus on recent experimental evidence of extreme spatial and dynamical heterogeneity in both freezing and glass transition processes. This discovery was enabled by the unique mesoporous structures of SBA-16 and FDU-5, possessing bimodal architectures with two interconnected pore types of different size and shape (spherical and cylindrical). For the very first time, two melting points for water and two glass transitions for supercooled OTP, corresponding to a specific pore type, were observed. Collectively, these observations strongly suggest a close mechanistic connection between the local fluctuations in the structure and dynamics of nanoconfined liquids. While the findings reviewed in this Account provide new insights into thermodynamic and kinetic transitions of fluids, there remain many unanswered questions regarding the effects of nanoconfinement on the fundamental properties of fluids, which offer exciting future opportunities in chemical research.
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- We do not take into account publications that without a DOI.
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- Statistics recalculated weekly.
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Sen S., Risbud S. H., Bartl M. Thermodynamic and Kinetic Transitions of Liquids in Nanoconfinement // Accounts of Chemical Research. 2020. Vol. 53. No. 12. pp. 2869-2878.
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Sen S., Risbud S. H., Bartl M. Thermodynamic and Kinetic Transitions of Liquids in Nanoconfinement // Accounts of Chemical Research. 2020. Vol. 53. No. 12. pp. 2869-2878.
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TY - JOUR
DO - 10.1021/acs.accounts.0c00502
UR - https://doi.org/10.1021%2Facs.accounts.0c00502
TI - Thermodynamic and Kinetic Transitions of Liquids in Nanoconfinement
T2 - Accounts of Chemical Research
AU - Risbud, Subhash H.
AU - Sen, S.
AU - Bartl, Michael
PY - 2020
DA - 2020/11/13 00:00:00
PB - American Chemical Society (ACS)
SP - 2869-2878
IS - 12
VL - 53
SN - 0001-4842
SN - 1520-4898
ER -
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@article{2020_Sen,
author = {Subhash H. Risbud and S. Sen and Michael Bartl},
title = {Thermodynamic and Kinetic Transitions of Liquids in Nanoconfinement},
journal = {Accounts of Chemical Research},
year = {2020},
volume = {53},
publisher = {American Chemical Society (ACS)},
month = {nov},
url = {https://doi.org/10.1021%2Facs.accounts.0c00502},
number = {12},
pages = {2869--2878},
doi = {10.1021/acs.accounts.0c00502}
}
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Sen, S., et al. “Thermodynamic and Kinetic Transitions of Liquids in Nanoconfinement.” Accounts of Chemical Research, vol. 53, no. 12, Nov. 2020, pp. 2869-2878. https://doi.org/10.1021%2Facs.accounts.0c00502.