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. 2023 May:95:106377.
doi: 10.1016/j.ultsonch.2023.106377. Epub 2023 Mar 21.

From crystal phase mixture to pure metal-organic frameworks - Tuning pore and structure properties

Przemysław J Jodłowski  1 , Grzegorz Kurowski  2 , Klaudia Dymek  2 , Marcin Oszajca  3 , Witold Piskorz  3 , Kornelia Hyjek  2 , Anna Wach  4 , Anna Pajdak  5 , Michal Mazur  6 , Daniel N Rainer  6 , Dominik Wierzbicki  7 , Piotr Jeleń  8 , Maciej Sitarz  8
Affiliations

From crystal phase mixture to pure metal-organic frameworks - Tuning pore and structure properties

Przemysław J Jodłowski et al. Ultrason Sonochem. 2023 May.

Abstract

In this study, a sonochemical route for the preparation of a new Hf-MIL-140A metal-organic framework from a mixture of UiO-66/MIL-140A is presented. The sonochemical synthesis route not only allows the phase-pure MIL-140A structure to be obtained but also induces structural defects in the MIL-140A structure. The synergic effect between the sonochemical irradiation and the presence of a highly acidic environment results in the generation of slit-like defects in the crystal structure, which increases specific surface area and pore volume. The BET-specific surface area in the case of sonochemically derived Zr-MIL-140A reaches 653.3 m2/g, which is 1.5 times higher than that obtained during conventional synthesis. The developed Hf-MIL-140A structure is isostructural to Zr-MIL-140A, which was confirmed by synchrotron X-ray powder diffraction (SR-XRD) and by continuous rotation electron diffraction (cRED) analysis. The obtained MOF materials have high thermal and chemical stability, which makes them promising candidates for applications such as gas adsorption, radioactive waste removal, catalysis, and drug delivery.

Keywords: Hf-MIL-140A; Metal–organic frameworks; Sonochemistry; UiO-66.

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Conflict of interest statement

Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper.

Figures

None
Graphical abstract
Fig. 1
Fig. 1
Crystal structure of Hf-MIL-140A; (B) Inorganic building unit of Hf-MIL-140A; Hf - green, O - red, C - graphite, H - black.
Fig. 2
Fig. 2
Rietveld plots for (A) Hf-MIL-140A and (B) Zr-MIL-140A; SR-PXRD wavelength used: λHF-MIL-140A = 0.70805 Å, λZr-MIL-140A = 1.00410 Å; insets - enhancement of the lower intensity regions.
Fig. 3
Fig. 3
(A) N2 adsorption isotherms and (B) DFT pore size distribution of MIL-140A samples.
Fig. 4
Fig. 4
SEM images of Hf-MIL-140A, (A) × 25 k, (B) × 40 k, (C) × 200 k.
Fig. 5
Fig. 5
STEM images of Hf-MIL-140A sample.
Fig. 6
Fig. 6
(A) FTIR and (B) µRaman spectra of MIL-140A samples.
Fig. 7
Fig. 7
(A) In situ high temperature PXRD results for Hf-MIL-140A synthesized by sonochemical route, (B) PXRD diffraction patterns for 24-hour stability test in different media for Hf-MIL-140A.
Fig. 8
Fig. 8
X-ray absorption spectroscopy data for (Me – Zr or Hf)-MIL-140A samples. Normalized XANES spectra at (A) Zr K-edge of Zr-based materials and (B) Hf L3-edge of Hf-based materials. Results of the EXAFS fitting: module of the Fourier transform (phase-corrected) of the EXAFS signal for (C) Zr-MIL-140A and (D) Hf-MIL-140A; experimental data are shown as solid line, whereas fitted curves are presented as dotted line.
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References

    1. Taddei M. When defects turn into virtues: The curious case of zirconium-based metal-organic frameworks. Coord. Chem. Rev. 2017;343:1–24. doi: 10.1016/j.ccr.2017.04.010. - DOI
    1. Leubner S., Bengtsson V.E.G., Synnatschke K., Gosch J., Koch A., Reinsch H., Xu H., Backes C., Zou X., Stock N. Synthesis and Exfoliation of a New Layered Mesoporous Zr-MOF Comprising Hexa- A nd Dodecanuclear Clusters as Well as a Small Organic Linker Molecule. J. Am. Chem. Soc. 2020;142(37):15995–16000. - PubMed
    1. Yaghi O.M., Li H. Hydrothermal Synthesis of a Metal-Organic Framework Containing Large Rectangular Channels. J. Am. Chem. Soc. 1995;117:10401–10402. doi: 10.1021/ja00146a033. - DOI
    1. Cavka J.H., Jakobsen S., Olsbye U., Guillou N., Lamberti C., Bordiga S., Lillerud K.P. A new zirconium inorganic building brick forming metal organic frameworks with exceptional stability. J. Am. Chem. Soc. 2008;130(42):13850–13851. - PubMed
    1. Mondloch J.E., Bury W., Fairen-Jimenez D., Kwon S., DeMarco E.J., Weston M.H., Sarjeant A.A., Nguyen S.T., Stair P.C., Snurr R.Q., Farha O.K., Hupp J.T. Vapor-phase metalation by atomic layer deposition in a metal-organic framework. J. Am. Chem. Soc. 2013;135(28):10294–10297. - PubMed