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The impact of crystal size and temperature on the adsorption-induced flexibility of the Zr-based metal–organic framework DUT-98
In this contribution we analyze the influence of adsorption cycling, crystal size, and temperature on the switching behavior of the flexible Zr-based metal–organic framework DUT-98. We observe a shift in the gate-opening pressure upon cycling of adsorption experiments for micrometer-sized crystals a...
Autores principales: | , , , , , , |
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Formato: | Online Artículo Texto |
Lenguaje: | English |
Publicado: |
Beilstein-Institut
2019
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Materias: | |
Acceso en línea: | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC6719731/ https://www.ncbi.nlm.nih.gov/pubmed/31501745 http://dx.doi.org/10.3762/bjnano.10.169 |
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author | Krause, Simon Bon, Volodymyr Du, Hongchu Dunin-Borkowski, Rafal E Stoeck, Ulrich Senkovska, Irena Kaskel, Stefan |
author_facet | Krause, Simon Bon, Volodymyr Du, Hongchu Dunin-Borkowski, Rafal E Stoeck, Ulrich Senkovska, Irena Kaskel, Stefan |
author_sort | Krause, Simon |
collection | PubMed |
description | In this contribution we analyze the influence of adsorption cycling, crystal size, and temperature on the switching behavior of the flexible Zr-based metal–organic framework DUT-98. We observe a shift in the gate-opening pressure upon cycling of adsorption experiments for micrometer-sized crystals and assign this to a fragmentation of the crystals. In a series of samples, the average crystal size of DUT-98 crystals was varied from 120 µm to 50 nm and the obtained solids were characterized by X-ray diffraction, infrared spectroscopy, as well as scanning and transmission electron microscopy. We analyzed the adsorption behavior by nitrogen and water adsorption at 77 K and 298 K, respectively, and show that adsorption-induced flexibility is only observed for micrometer-sized crystals. Nanometer-sized crystals were found to exhibit reversible type I adsorption behavior upon adsorption of nitrogen and exhibit a crystal-size-dependent steep water uptake of up to 20 mmol g(−1) at 0.5 p/p(0) with potential for water harvesting and heat pump applications. We furthermore investigate the temperature-induced structural transition by in situ powder X-ray diffraction. At temperatures beyond 110 °C, the open-pore state of the nanometer-sized DUT-98 crystals is found to irreversibly transform to a closed-pore state. The connection of crystal fragmentation upon adsorption cycling and the crystal size dependence of the adsorption-induced flexibility is an important finding for evaluation of these materials in future adsorption-based applications. This work thus extends the limited amount of studies on crystal size effects in flexible MOFs and hopefully motivates further investigations in this field. |
format | Online Article Text |
id | pubmed-6719731 |
institution | National Center for Biotechnology Information |
language | English |
publishDate | 2019 |
publisher | Beilstein-Institut |
record_format | MEDLINE/PubMed |
spelling | pubmed-67197312019-09-09 The impact of crystal size and temperature on the adsorption-induced flexibility of the Zr-based metal–organic framework DUT-98 Krause, Simon Bon, Volodymyr Du, Hongchu Dunin-Borkowski, Rafal E Stoeck, Ulrich Senkovska, Irena Kaskel, Stefan Beilstein J Nanotechnol Full Research Paper In this contribution we analyze the influence of adsorption cycling, crystal size, and temperature on the switching behavior of the flexible Zr-based metal–organic framework DUT-98. We observe a shift in the gate-opening pressure upon cycling of adsorption experiments for micrometer-sized crystals and assign this to a fragmentation of the crystals. In a series of samples, the average crystal size of DUT-98 crystals was varied from 120 µm to 50 nm and the obtained solids were characterized by X-ray diffraction, infrared spectroscopy, as well as scanning and transmission electron microscopy. We analyzed the adsorption behavior by nitrogen and water adsorption at 77 K and 298 K, respectively, and show that adsorption-induced flexibility is only observed for micrometer-sized crystals. Nanometer-sized crystals were found to exhibit reversible type I adsorption behavior upon adsorption of nitrogen and exhibit a crystal-size-dependent steep water uptake of up to 20 mmol g(−1) at 0.5 p/p(0) with potential for water harvesting and heat pump applications. We furthermore investigate the temperature-induced structural transition by in situ powder X-ray diffraction. At temperatures beyond 110 °C, the open-pore state of the nanometer-sized DUT-98 crystals is found to irreversibly transform to a closed-pore state. The connection of crystal fragmentation upon adsorption cycling and the crystal size dependence of the adsorption-induced flexibility is an important finding for evaluation of these materials in future adsorption-based applications. This work thus extends the limited amount of studies on crystal size effects in flexible MOFs and hopefully motivates further investigations in this field. Beilstein-Institut 2019-08-20 /pmc/articles/PMC6719731/ /pubmed/31501745 http://dx.doi.org/10.3762/bjnano.10.169 Text en Copyright © 2019, Krause et al. https://creativecommons.org/licenses/by/4.0https://www.beilstein-journals.org/bjnano/termsThis is an Open Access article under the terms of the Creative Commons Attribution License (https://creativecommons.org/licenses/by/4.0). Please note that the reuse, redistribution and reproduction in particular requires that the authors and source are credited. The license is subject to the Beilstein Journal of Nanotechnology terms and conditions: (https://www.beilstein-journals.org/bjnano/terms) |
spellingShingle | Full Research Paper Krause, Simon Bon, Volodymyr Du, Hongchu Dunin-Borkowski, Rafal E Stoeck, Ulrich Senkovska, Irena Kaskel, Stefan The impact of crystal size and temperature on the adsorption-induced flexibility of the Zr-based metal–organic framework DUT-98 |
title | The impact of crystal size and temperature on the adsorption-induced flexibility of the Zr-based metal–organic framework DUT-98 |
title_full | The impact of crystal size and temperature on the adsorption-induced flexibility of the Zr-based metal–organic framework DUT-98 |
title_fullStr | The impact of crystal size and temperature on the adsorption-induced flexibility of the Zr-based metal–organic framework DUT-98 |
title_full_unstemmed | The impact of crystal size and temperature on the adsorption-induced flexibility of the Zr-based metal–organic framework DUT-98 |
title_short | The impact of crystal size and temperature on the adsorption-induced flexibility of the Zr-based metal–organic framework DUT-98 |
title_sort | impact of crystal size and temperature on the adsorption-induced flexibility of the zr-based metal–organic framework dut-98 |
topic | Full Research Paper |
url | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC6719731/ https://www.ncbi.nlm.nih.gov/pubmed/31501745 http://dx.doi.org/10.3762/bjnano.10.169 |
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