Design of the hybrid metal-organic frameworks as potential supramolecular piezo-/ferroelectrics

Yao Sun; Junfeng Gao; Yuan Cheng; Yong Wei Zhang; Kaiyang Zeng

doi:10.1021/acs.jpcc.8b08442

Design of the hybrid metal-organic frameworks as potential supramolecular piezo-/ferroelectrics

Yao Sun, Junfeng Gao, Yuan Cheng, Yong Wei Zhang, Kaiyang Zeng

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

26 Citations (Scopus)

Abstract

Metal-organic framework (MOF) UiO-66 nanocrystals were previously believed to be piezo-/ferroelectrically inactive because of their centrosymmetric lattice symmetries [Fm3?m (225)] revealed by Powder X-ray diffraction. However, via the nanoscale probing studies through the delicate dual AC resonance tracking piezoresponse force microscopy and piezoresponse force spectroscopy characterizations, our work for the first time demonstrates that UiO-66 nanocrystals show certain piezo-/ferroelectric responses. The compelling experimental and theoretical analyses disclose that the structure of UiO-66 may not be the highly centrosymmetric Fm3?m (225) but a reduced symmetry form. In addition, UiO-66(Hf)-type MOF nanocrystals possess stronger piezoresponses and better ferroelectric switching behaviors than their counterparts UiO-66(Zr)-type nanocrystals. Our study can further enrich the structural understanding of UiO-66 MOF and also suggests possible design of promising electronic properties of the MOFs by judicious selection of metal ions and functional ligands.

Original language	English
Pages (from-to)	3122-3129
Number of pages	8
Journal	Journal of Physical Chemistry C
Volume	123
Issue number	5
DOIs	https://doi.org/10.1021/acs.jpcc.8b08442
Publication status	Published - 7 Feb 2019
Externally published	Yes

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title = "Design of the hybrid metal-organic frameworks as potential supramolecular piezo-/ferroelectrics",

abstract = "Metal-organic framework (MOF) UiO-66 nanocrystals were previously believed to be piezo-/ferroelectrically inactive because of their centrosymmetric lattice symmetries [Fm3?m (225)] revealed by Powder X-ray diffraction. However, via the nanoscale probing studies through the delicate dual AC resonance tracking piezoresponse force microscopy and piezoresponse force spectroscopy characterizations, our work for the first time demonstrates that UiO-66 nanocrystals show certain piezo-/ferroelectric responses. The compelling experimental and theoretical analyses disclose that the structure of UiO-66 may not be the highly centrosymmetric Fm3?m (225) but a reduced symmetry form. In addition, UiO-66(Hf)-type MOF nanocrystals possess stronger piezoresponses and better ferroelectric switching behaviors than their counterparts UiO-66(Zr)-type nanocrystals. Our study can further enrich the structural understanding of UiO-66 MOF and also suggests possible design of promising electronic properties of the MOFs by judicious selection of metal ions and functional ligands.",

author = "Yao Sun and Junfeng Gao and Yuan Cheng and Zhang, {Yong Wei} and Kaiyang Zeng",

note = "Funding Information: This work is supported by Ministry of Education (Singapore) through National University of Singapore under the Academic Research Grant (AcRF) R-265-000-495-112. The authors acknowledge Dr. Dan Zhao and Dr. Zhigang Hu from Department of Chemical and Biomolecular Engineering, National University of Singapore, for the material supply. The author Y.S. thanks the postgraduate scholarship from National University of Singapore. Y.C. and Y.-W.Z. are grateful for the support from the Agency for Science, Technology and Research (A*STAR) and from A*STAR Computational Resource Centre, Singapore (ACRC). J. G. thanks the Start-Up grant of DUT (3005-852069) and the computational support from the Supercomputing Center of Dalian University of Technology. The computational work for this article was partially performed on resources of the National Supercomputing Centre, Singapore. Publisher Copyright: Copyright {\textcopyright} 2019 American Chemical Society.",

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AU - Sun, Yao

AU - Gao, Junfeng

AU - Cheng, Yuan

AU - Zhang, Yong Wei

AU - Zeng, Kaiyang

N1 - Funding Information: This work is supported by Ministry of Education (Singapore) through National University of Singapore under the Academic Research Grant (AcRF) R-265-000-495-112. The authors acknowledge Dr. Dan Zhao and Dr. Zhigang Hu from Department of Chemical and Biomolecular Engineering, National University of Singapore, for the material supply. The author Y.S. thanks the postgraduate scholarship from National University of Singapore. Y.C. and Y.-W.Z. are grateful for the support from the Agency for Science, Technology and Research (A*STAR) and from A*STAR Computational Resource Centre, Singapore (ACRC). J. G. thanks the Start-Up grant of DUT (3005-852069) and the computational support from the Supercomputing Center of Dalian University of Technology. The computational work for this article was partially performed on resources of the National Supercomputing Centre, Singapore. Publisher Copyright: Copyright © 2019 American Chemical Society.

PY - 2019/2/7

Y1 - 2019/2/7

N2 - Metal-organic framework (MOF) UiO-66 nanocrystals were previously believed to be piezo-/ferroelectrically inactive because of their centrosymmetric lattice symmetries [Fm3?m (225)] revealed by Powder X-ray diffraction. However, via the nanoscale probing studies through the delicate dual AC resonance tracking piezoresponse force microscopy and piezoresponse force spectroscopy characterizations, our work for the first time demonstrates that UiO-66 nanocrystals show certain piezo-/ferroelectric responses. The compelling experimental and theoretical analyses disclose that the structure of UiO-66 may not be the highly centrosymmetric Fm3?m (225) but a reduced symmetry form. In addition, UiO-66(Hf)-type MOF nanocrystals possess stronger piezoresponses and better ferroelectric switching behaviors than their counterparts UiO-66(Zr)-type nanocrystals. Our study can further enrich the structural understanding of UiO-66 MOF and also suggests possible design of promising electronic properties of the MOFs by judicious selection of metal ions and functional ligands.

AB - Metal-organic framework (MOF) UiO-66 nanocrystals were previously believed to be piezo-/ferroelectrically inactive because of their centrosymmetric lattice symmetries [Fm3?m (225)] revealed by Powder X-ray diffraction. However, via the nanoscale probing studies through the delicate dual AC resonance tracking piezoresponse force microscopy and piezoresponse force spectroscopy characterizations, our work for the first time demonstrates that UiO-66 nanocrystals show certain piezo-/ferroelectric responses. The compelling experimental and theoretical analyses disclose that the structure of UiO-66 may not be the highly centrosymmetric Fm3?m (225) but a reduced symmetry form. In addition, UiO-66(Hf)-type MOF nanocrystals possess stronger piezoresponses and better ferroelectric switching behaviors than their counterparts UiO-66(Zr)-type nanocrystals. Our study can further enrich the structural understanding of UiO-66 MOF and also suggests possible design of promising electronic properties of the MOFs by judicious selection of metal ions and functional ligands.

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Design of the hybrid metal-organic frameworks as potential supramolecular piezo-/ferroelectrics

Abstract

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