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Nano Research 2021, 14(2): 404-410 https://doi.org/10.1007/s12274-020-2792-y
Research Article | Issue | Published: 08 May 2020

Large anisotropic negative thermal expansion in Cu-TDPAT metal-organic framework: A combined in situ X-ray diffraction and DRIFTS study

Show Author's Information Mehrdad Asgari1,  Ilia Kochetygov1,  Hassan Abedini1,2,  Wendy L. Queen1,( )
Institut des Sciences et Ingénierie Chimiques, École Polytechnique Fédérale de Lausanne (EPFL) - Valais Wallis, CH-1951 Sion, Switzerland
Gas Engineering Department, Faculty of Petroleum, Petroleum University of Technology (PUT), Ahwaz 61991-71183, Iran
Keywords:
metal-organic frameworks, negative thermal expansion, Cu-TDPAT, in situ diffraction, in situ diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS)
Topics:
Fourier transform infrared spectroscopyMetalsOrganic frameworks OrganometallicsSingle crystalsX-ray crystallographyX-ray diffraction
An erratum to this article is available online at https://doi.org/10.1007/s12274-020-2973-8
Cite this article:
Asgari M, Kochetygov I, Abedini H, et al. Large anisotropic negative thermal expansion in Cu-TDPAT metal-organic framework: A combined in situ X-ray diffraction and DRIFTS study. Nano Research, 2021, 14(2): 404-410. https://doi.org/10.1007/s12274-020-2792-y
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Abstract Full text Electronic supplementary material About this article

Cu-TDPAT (H6TDPAT = 2,4,6-tris(3,5-dicarboxylphenylamino)-1,3,5-triazine), a stable nanoporous metal-organic framework with rht topology, has sparked broad interest as an adsorbent for several chemical separation processes. In this work, in situ synchrotron diffraction experiments followed by sequential LeBail refinements reveal that Cu-TDPAT shows unusually large anisotropic negative thermal expansion (NTE). The PASCal crystallography tool, used to analyze the magnitude of the NTE, reveals an average volumetric thermal expansion coefficient αV = -20.3 MK-1. This value is significantly higher than the one reported for Cu-BTC (also known as HKUST-1), which contains the same Cu-paddlewheel building unit, αV ≈ -12 MK-1. In situ synchrotron single crystal X-ray diffraction and in situ diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) were employed to shed light on the NTE mechanism. Using these two methods, we were able to elucidate the three main structural motions that are responsible for the NTE effect. The more pronounced NTE behavior of Cu-TDPAT is attributed to the lower symmetry combined with the more complex ligand structure when compared to Cu-BTC. The knowledge obtained in this work is important for understanding the behavior of the adsorbent under transient variable temperature conditions in fixed adsorption beds.


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Electronic supplementary material
About this article

Large anisotropic negative thermal expansion in Cu-TDPAT metal-organic framework: A combined in situ X-ray diffraction and DRIFTS study

Show Author's information Mehrdad Asgari1, Ilia Kochetygov1, Hassan Abedini1,2, Wendy L. Queen1,( )
Institut des Sciences et Ingénierie Chimiques, École Polytechnique Fédérale de Lausanne (EPFL) - Valais Wallis, CH-1951 Sion, Switzerland
Gas Engineering Department, Faculty of Petroleum, Petroleum University of Technology (PUT), Ahwaz 61991-71183, Iran

Abstract

Cu-TDPAT (H6TDPAT = 2,4,6-tris(3,5-dicarboxylphenylamino)-1,3,5-triazine), a stable nanoporous metal-organic framework with rht topology, has sparked broad interest as an adsorbent for several chemical separation processes. In this work, in situ synchrotron diffraction experiments followed by sequential LeBail refinements reveal that Cu-TDPAT shows unusually large anisotropic negative thermal expansion (NTE). The PASCal crystallography tool, used to analyze the magnitude of the NTE, reveals an average volumetric thermal expansion coefficient αV = -20.3 MK-1. This value is significantly higher than the one reported for Cu-BTC (also known as HKUST-1), which contains the same Cu-paddlewheel building unit, αV ≈ -12 MK-1. In situ synchrotron single crystal X-ray diffraction and in situ diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) were employed to shed light on the NTE mechanism. Using these two methods, we were able to elucidate the three main structural motions that are responsible for the NTE effect. The more pronounced NTE behavior of Cu-TDPAT is attributed to the lower symmetry combined with the more complex ligand structure when compared to Cu-BTC. The knowledge obtained in this work is important for understanding the behavior of the adsorbent under transient variable temperature conditions in fixed adsorption beds.

Keywords: metal-organic frameworks, negative thermal expansion, Cu-TDPAT, in situ diffraction, in situ diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS)

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Publication history
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Acknowledgements

Publication history

Received: 07 February 2020
Accepted: 01 April 2020
Published: 08 May 2020
Issue date: February 2021

Copyright

© Tsinghua University Press and Springer-Verlag GmbH Germany, part of Springer Nature

Acknowledgements

This work was supported by the Swiss National Science Foundation under Grant PYAPP2_160581. M. A. acknowledges the Swiss Commission for Technology and Innovation (CTI) (the SCCER EIP-Efficiency of Industrial Processes) for financial support. We also acknowledge the Swiss-Norwegian Beam Line BM01 at European Synchrotron Radiation Facility (ESRF) for the beamtime allocation and Dr. Dmitry Chernyshov, Dr. Iurii Dovgaliuk, Dr. Olga Trukhina and Mr. Vikram Karve for the assistance on the beamline, BM01. M. A. also thanks Dr. Pascal Schouwink for assistance on X-ray diffraction experiments at EPFL Valais.

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