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Research Article

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

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
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An erratum to this article is available online at:
https://doi.org/10.1007/s12274-020-2973-8

Graphical Abstract

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

negative thermal expansionmetal-organic frameworksCu-TDPATin situ diffractionin situ diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS)

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Nano Research
Volume 14 Issue 2,
February 2021
Pages 404-410
DOI: 10.1007/s12274-020-2792-y
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
Topics:
Fourier transform infrared spectroscopyMetalsOrganic frameworks OrganometallicsSingle crystalsX-ray crystallographyX-ray diffraction

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Received: 07 February 2020
Accepted: 01 April 2020
Published: 08 May 2020
© Tsinghua University Press and Springer-Verlag GmbH Germany, part of Springer Nature
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