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Unraveling the thermodynamic criteria for size-dependent spontaneous phase separation in soft porous crystals
Soft porous crystals (SPCs) harbor a great potential as functional nanoporous materials owing to their stimuli-induced and tuneable morphing between different crystalline phases. These large-amplitude phase transitions are often assumed to occur cooperatively throughout the whole material, which the...
Autores principales: | , , |
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Formato: | Online Artículo Texto |
Lenguaje: | English |
Publicado: |
Nature Publishing Group UK
2019
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Materias: | |
Acceso en línea: | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC6813293/ https://www.ncbi.nlm.nih.gov/pubmed/31649249 http://dx.doi.org/10.1038/s41467-019-12754-w |
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author | Rogge, Sven M. J. Waroquier, Michel Van Speybroeck, Veronique |
author_facet | Rogge, Sven M. J. Waroquier, Michel Van Speybroeck, Veronique |
author_sort | Rogge, Sven M. J. |
collection | PubMed |
description | Soft porous crystals (SPCs) harbor a great potential as functional nanoporous materials owing to their stimuli-induced and tuneable morphing between different crystalline phases. These large-amplitude phase transitions are often assumed to occur cooperatively throughout the whole material, which thereby retains its perfect crystalline order. Here, we disprove this paradigm through mesoscale first-principles based molecular dynamics simulations, demonstrating that morphological transitions do induce spatial disorder under the form of interfacial defects and give rise to yet unidentified phase coexistence within a given sample. We hypothesize that this phase coexistence can be stabilized by carefully tuning the experimental control variables through, e.g., temperature or pressure quenching. The observed spatial disorder helps to rationalize yet elusive phenomena in SPCs, such as the impact of crystal downsizing on their flexible nature, thereby identifying the crystal size as a crucial design parameter for stimuli-responsive devices based on SPC nanoparticles and thin films. |
format | Online Article Text |
id | pubmed-6813293 |
institution | National Center for Biotechnology Information |
language | English |
publishDate | 2019 |
publisher | Nature Publishing Group UK |
record_format | MEDLINE/PubMed |
spelling | pubmed-68132932019-10-28 Unraveling the thermodynamic criteria for size-dependent spontaneous phase separation in soft porous crystals Rogge, Sven M. J. Waroquier, Michel Van Speybroeck, Veronique Nat Commun Article Soft porous crystals (SPCs) harbor a great potential as functional nanoporous materials owing to their stimuli-induced and tuneable morphing between different crystalline phases. These large-amplitude phase transitions are often assumed to occur cooperatively throughout the whole material, which thereby retains its perfect crystalline order. Here, we disprove this paradigm through mesoscale first-principles based molecular dynamics simulations, demonstrating that morphological transitions do induce spatial disorder under the form of interfacial defects and give rise to yet unidentified phase coexistence within a given sample. We hypothesize that this phase coexistence can be stabilized by carefully tuning the experimental control variables through, e.g., temperature or pressure quenching. The observed spatial disorder helps to rationalize yet elusive phenomena in SPCs, such as the impact of crystal downsizing on their flexible nature, thereby identifying the crystal size as a crucial design parameter for stimuli-responsive devices based on SPC nanoparticles and thin films. Nature Publishing Group UK 2019-10-24 /pmc/articles/PMC6813293/ /pubmed/31649249 http://dx.doi.org/10.1038/s41467-019-12754-w Text en © The Author(s) 2019 Open Access This article is licensed under a Creative Commons Attribution 4.0 International License, which permits use, sharing, adaptation, distribution and reproduction in any medium or format, as long as you give appropriate credit to the original author(s) and the source, provide a link to the Creative Commons license, and indicate if changes were made. The images or other third party material in this article are included in the article’s Creative Commons license, unless indicated otherwise in a credit line to the material. If material is not included in the article’s Creative Commons license and your intended use is not permitted by statutory regulation or exceeds the permitted use, you will need to obtain permission directly from the copyright holder. To view a copy of this license, visit http://creativecommons.org/licenses/by/4.0/. |
spellingShingle | Article Rogge, Sven M. J. Waroquier, Michel Van Speybroeck, Veronique Unraveling the thermodynamic criteria for size-dependent spontaneous phase separation in soft porous crystals |
title | Unraveling the thermodynamic criteria for size-dependent spontaneous phase separation in soft porous crystals |
title_full | Unraveling the thermodynamic criteria for size-dependent spontaneous phase separation in soft porous crystals |
title_fullStr | Unraveling the thermodynamic criteria for size-dependent spontaneous phase separation in soft porous crystals |
title_full_unstemmed | Unraveling the thermodynamic criteria for size-dependent spontaneous phase separation in soft porous crystals |
title_short | Unraveling the thermodynamic criteria for size-dependent spontaneous phase separation in soft porous crystals |
title_sort | unraveling the thermodynamic criteria for size-dependent spontaneous phase separation in soft porous crystals |
topic | Article |
url | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC6813293/ https://www.ncbi.nlm.nih.gov/pubmed/31649249 http://dx.doi.org/10.1038/s41467-019-12754-w |
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