Synthesis of millimeter-scale ZIF-8 single crystals and their reversible crystal structure changes

Azhar Alowasheeir; Nagy L Torad; Toru Asahi; Saad M Alshehri; Tansir Ahamad; Yoshio Bando; Miharu Eguchi; Yusuke Yamauchi; Yukana Terasawa; Minsu Han

doi:10.1080/14686996.2023.2292485

Synthesis of millimeter-scale ZIF-8 single crystals and their reversible crystal structure changes

Sci Technol Adv Mater. 2024 Jan 19;25(1):2292485. doi: 10.1080/14686996.2023.2292485. eCollection 2024.

Authors

Azhar Alowasheeir¹, Nagy L Torad^{2

3

4}, Toru Asahi⁵, Saad M Alshehri⁶, Tansir Ahamad⁶, Yoshio Bando^{6

7}, Miharu Eguchi^{5

8}, Yusuke Yamauchi^{1

8}, Yukana Terasawa^{9

10}, Minsu Han⁸

Affiliations

¹ Department of Materials Process Engineering, Graduate School of Engineering, Nagoya University, Nagoya, Japan.
² Chemistry Department, Faculty of Science, Tanta University, Tanta, Egypt.
³ Department of Chemistry, Khalifa University, Abu Dhabi, United Arab Emirates.
⁴ Advanced Materials Chemistry Center (AMCC), Khalifa University, Abu Dhabi, United Arab Emirates.
⁵ School of Advanced Science and Engineering, Waseda University, Shinjuku-ku, Tokyo, Japan.
⁶ Chemistry Department, College of Science, King Saud University, Riyadh, Saudi Arabia.
⁷ Australian Institute for Innovative Materials, University of Wollongong, North Wollongong, New South Wales, Australia.
⁸ Australian Institute for Bioengineering and Nanotechnology (AIBN), The University of Queensland, Brisbane, Queensland, Australia.
⁹ Kagami Memorial Research Institute for Materials Science and Technology, Waseda University, Shinjuku-ku, Tokyo, Japan.
¹⁰ Faculty of Advanced Science and Technology, Kumamoto University, Kumamoto-shi, Kumamoto, Japan.

Abstract

Among various metal-organic frameworks (MOFs), the zeolitic imidazole framework (ZIF), constructed by the regular arrangement of 2-methylimidazole and metal ions, has garnered significant attention due to its distinctive crystals and pore structures. Variations in the sizes and shapes of ZIF crystals have been reported by changing the synthesis parameters, such as the molar ratios of organic ligands to metal ions, choice of solvents, and temperatures. Nonetheless, the giant ZIF-8 single crystals beyond the typical range have rarely been reported. Herein, we present the synthesis of millimeter-scale single crystal ZIF-8 using the solvothermal method in N,N-diethylformamide. The resulting 1-mm single crystal is carefully characterized through N₂ adsorption-desorption isotherms, scanning electron microscopy, and other analytical techniques. Additionally, single-crystal X-ray diffraction is employed to comprehensively investigate the framework's mobility at various temperatures.

Keywords: Millimeter-scale ZIF-8; single crystal; single crystal X-ray diffraction; solvothermal.

Plain language summary

Millimeter-sized ZIF-8 single crystals were synthesized using the solvothermal method. These crystals exhibit a notable BET surface area of 1681 m²∙g⁻¹ and demonstrate a reversible change in their crystal structure.

Grants and funding

This work utilized the XtaLAB Synergy-S research equipment and Thermo Plus TG8120, provided through the MEXT Project for promoting public utilization of advanced research infrastructure (Program for supporting construction of core facilities) under Grant Number JPMXS0440500022. This work was supported by the JST-ERATO Yamauchi Materials Space-Tectonics project (JPMJER2003). This work used the Queensland node of the NCRIS-enabled Australian National Fabrication Facility (ANFF). Yoshio Bando and Saad M. Alshehri acknowledge the financial support provided by the Distinguished Scientist Fellowship Program (DSFP) of the King Saud University, Riyadh, King of Saudi Arabia.