Shaping of metal-organic frameworks into mechanically stable monoliths with poly(vinyl alcohol) by phase separation technique

Emrah Hastürk; Carsten Schlüsener; Julian Quodbach; Alexa Schmitz; Christoph Janiak

doi:10.1016/j.micromeso.2019.02.011

Shaping of metal-organic frameworks into mechanically stable monoliths with poly(vinyl alcohol) by phase separation technique

Emrah Hastürk, Carsten Schlüsener, Julian Quodbach, Alexa Schmitz, Christoph Janiak^*

^*Corresponding author for this work

Heinrich Heine University Düsseldorf

Research output: Contribution to journal › Article › Academic › peer-review

Abstract

The metal-organic frameworks (MOFs) Basolite™ A520 (aluminum fumarate, Alfum) and MIL-101(Cr) were shaped into monoliths for the first time using a phase separation technique with the hydrophilic polymer poly(vinyl alcohol) (PVA). These composite materials (MOF@PVA) could be loaded with up to 80 wt% of MOF under retention of crystallinity (verified by powder X-ray diffractometry), porosities (from N₂ and H₂O adsorption) and morphology of MOF particles (verified by scanning electron microscopy). In the MOF@PVA monoliths, the mass-weighted apparent BET surface area from nitrogen sorption studies and the water vapor uptake capacity reproducibly reached 60–100% of the neat MOF values. Alfum@PVA composites with a MOF loading of 50–80 wt% show an increased quantitative porosity. A detailed pore analysis by the t-plot method indicates, however, that only 30–70% of the Alfum-micropore volume were retained during the used phase separation technique. The increased porosity is due to additional mesopores from interfacial voids which were formed between Alfum-particles and the PVA polymer. These additional pores lead to an increase in water capacity compared to the neat/pure MOF. While the neat PVA monoliths show a primarily plastic and elastic behavior, the monoliths with 50 and 65 wt% Alfum exhibit slightly plastic properties and a high resistance against deformation. Higher stresses (up to 0.12 N/m², i.e. up to a force of 63 N) can be exerted together with a lower strain (<0.2%) compared to the PVA monoliths.

Original language	English
Pages (from-to)	277-287
Number of pages	11
Journal	Microporous and Mesoporous Materials
Volume	280
DOIs	https://doi.org/10.1016/j.micromeso.2019.02.011
Publication status	Published - 15 May 2019
Externally published	Yes

Bibliographical note

Funding Information:
The authors gratefully acknowledge the financial support of the Federal German Ministry of Education and Research (BMBF) in the project Optimat under grant no. 03SF0492C . We thank Anna Kira Adam from the Institute of Pharmaceutics and Biopharmaceutics at Heinrich-Heine-Universität Düsseldorf for the measurement of the mechanical stability. We also thank the Institute of Pharmaceutics and Biopharmaceutics for giving us the opportunity to measure mercury porosimetry. We thank the Institute of Organic and Macromolecular Chemistry for the usage of a freeze-drying instrument. We are indebted to Mrs. Anna Christin Kautz for measuring the IR spectra.

Publisher Copyright:
© 2019 Elsevier Inc.

Funding

The authors gratefully acknowledge the financial support of the Federal German Ministry of Education and Research (BMBF) in the project Optimat under grant no. 03SF0492C . We thank Anna Kira Adam from the Institute of Pharmaceutics and Biopharmaceutics at Heinrich-Heine-Universität Düsseldorf for the measurement of the mechanical stability. We also thank the Institute of Pharmaceutics and Biopharmaceutics for giving us the opportunity to measure mercury porosimetry. We thank the Institute of Organic and Macromolecular Chemistry for the usage of a freeze-drying instrument. We are indebted to Mrs. Anna Christin Kautz for measuring the IR spectra.

Keywords

Metal-organic frameworks
Monolith
Phase separation
Poly(vinyl alcohol)
Shaping

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10.1016/j.micromeso.2019.02.011

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title = "Shaping of metal-organic frameworks into mechanically stable monoliths with poly(vinyl alcohol) by phase separation technique",

abstract = "The metal-organic frameworks (MOFs) Basolite{\texttrademark} A520 (aluminum fumarate, Alfum) and MIL-101(Cr) were shaped into monoliths for the first time using a phase separation technique with the hydrophilic polymer poly(vinyl alcohol) (PVA). These composite materials (MOF@PVA) could be loaded with up to 80 wt% of MOF under retention of crystallinity (verified by powder X-ray diffractometry), porosities (from N2 and H2O adsorption) and morphology of MOF particles (verified by scanning electron microscopy). In the MOF@PVA monoliths, the mass-weighted apparent BET surface area from nitrogen sorption studies and the water vapor uptake capacity reproducibly reached 60–100% of the neat MOF values. Alfum@PVA composites with a MOF loading of 50–80 wt% show an increased quantitative porosity. A detailed pore analysis by the t-plot method indicates, however, that only 30–70% of the Alfum-micropore volume were retained during the used phase separation technique. The increased porosity is due to additional mesopores from interfacial voids which were formed between Alfum-particles and the PVA polymer. These additional pores lead to an increase in water capacity compared to the neat/pure MOF. While the neat PVA monoliths show a primarily plastic and elastic behavior, the monoliths with 50 and 65 wt% Alfum exhibit slightly plastic properties and a high resistance against deformation. Higher stresses (up to 0.12 N/m2, i.e. up to a force of 63 N) can be exerted together with a lower strain (<0.2%) compared to the PVA monoliths.",

keywords = "Metal-organic frameworks, Monolith, Phase separation, Poly(vinyl alcohol), Shaping",

author = "Emrah Hast{\"u}rk and Carsten Schl{\"u}sener and Julian Quodbach and Alexa Schmitz and Christoph Janiak",

note = "Funding Information: The authors gratefully acknowledge the financial support of the Federal German Ministry of Education and Research (BMBF) in the project Optimat under grant no. 03SF0492C . We thank Anna Kira Adam from the Institute of Pharmaceutics and Biopharmaceutics at Heinrich-Heine-Universit{\"a}t D{\"u}sseldorf for the measurement of the mechanical stability. We also thank the Institute of Pharmaceutics and Biopharmaceutics for giving us the opportunity to measure mercury porosimetry. We thank the Institute of Organic and Macromolecular Chemistry for the usage of a freeze-drying instrument. We are indebted to Mrs. Anna Christin Kautz for measuring the IR spectra. Publisher Copyright: {\textcopyright} 2019 Elsevier Inc.",

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doi = "10.1016/j.micromeso.2019.02.011",

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AU - Hastürk, Emrah

AU - Schlüsener, Carsten

AU - Quodbach, Julian

AU - Schmitz, Alexa

AU - Janiak, Christoph

N1 - Funding Information: The authors gratefully acknowledge the financial support of the Federal German Ministry of Education and Research (BMBF) in the project Optimat under grant no. 03SF0492C . We thank Anna Kira Adam from the Institute of Pharmaceutics and Biopharmaceutics at Heinrich-Heine-Universität Düsseldorf for the measurement of the mechanical stability. We also thank the Institute of Pharmaceutics and Biopharmaceutics for giving us the opportunity to measure mercury porosimetry. We thank the Institute of Organic and Macromolecular Chemistry for the usage of a freeze-drying instrument. We are indebted to Mrs. Anna Christin Kautz for measuring the IR spectra. Publisher Copyright: © 2019 Elsevier Inc.

PY - 2019/5/15

Y1 - 2019/5/15

N2 - The metal-organic frameworks (MOFs) Basolite™ A520 (aluminum fumarate, Alfum) and MIL-101(Cr) were shaped into monoliths for the first time using a phase separation technique with the hydrophilic polymer poly(vinyl alcohol) (PVA). These composite materials (MOF@PVA) could be loaded with up to 80 wt% of MOF under retention of crystallinity (verified by powder X-ray diffractometry), porosities (from N2 and H2O adsorption) and morphology of MOF particles (verified by scanning electron microscopy). In the MOF@PVA monoliths, the mass-weighted apparent BET surface area from nitrogen sorption studies and the water vapor uptake capacity reproducibly reached 60–100% of the neat MOF values. Alfum@PVA composites with a MOF loading of 50–80 wt% show an increased quantitative porosity. A detailed pore analysis by the t-plot method indicates, however, that only 30–70% of the Alfum-micropore volume were retained during the used phase separation technique. The increased porosity is due to additional mesopores from interfacial voids which were formed between Alfum-particles and the PVA polymer. These additional pores lead to an increase in water capacity compared to the neat/pure MOF. While the neat PVA monoliths show a primarily plastic and elastic behavior, the monoliths with 50 and 65 wt% Alfum exhibit slightly plastic properties and a high resistance against deformation. Higher stresses (up to 0.12 N/m2, i.e. up to a force of 63 N) can be exerted together with a lower strain (<0.2%) compared to the PVA monoliths.

AB - The metal-organic frameworks (MOFs) Basolite™ A520 (aluminum fumarate, Alfum) and MIL-101(Cr) were shaped into monoliths for the first time using a phase separation technique with the hydrophilic polymer poly(vinyl alcohol) (PVA). These composite materials (MOF@PVA) could be loaded with up to 80 wt% of MOF under retention of crystallinity (verified by powder X-ray diffractometry), porosities (from N2 and H2O adsorption) and morphology of MOF particles (verified by scanning electron microscopy). In the MOF@PVA monoliths, the mass-weighted apparent BET surface area from nitrogen sorption studies and the water vapor uptake capacity reproducibly reached 60–100% of the neat MOF values. Alfum@PVA composites with a MOF loading of 50–80 wt% show an increased quantitative porosity. A detailed pore analysis by the t-plot method indicates, however, that only 30–70% of the Alfum-micropore volume were retained during the used phase separation technique. The increased porosity is due to additional mesopores from interfacial voids which were formed between Alfum-particles and the PVA polymer. These additional pores lead to an increase in water capacity compared to the neat/pure MOF. While the neat PVA monoliths show a primarily plastic and elastic behavior, the monoliths with 50 and 65 wt% Alfum exhibit slightly plastic properties and a high resistance against deformation. Higher stresses (up to 0.12 N/m2, i.e. up to a force of 63 N) can be exerted together with a lower strain (<0.2%) compared to the PVA monoliths.

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ER -

Shaping of metal-organic frameworks into mechanically stable monoliths with poly(vinyl alcohol) by phase separation technique

Abstract

Bibliographical note

Funding

Keywords

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