Synergistic Stimulation of Metal-Organic Frameworks for Stable Super-cooled Liquid and Quenched Glass

Zheng Yin; Yingbo Zhao; Shuang Wan; Jian Yang; Zhaolin Shi; Si-Xu Peng; Ming-Zhu Chen; Tian-Yi Xie; Teng-Wu Zeng; Osamu Yamamuro; Masami Nirei; Hiroshi Akiba; Yue-Biao Zhang; Hai-Bin Yu; Ming-Hua Zeng

doi:10.1021/jacs.2c04532

Synergistic Stimulation of Metal-Organic Frameworks for Stable Super-cooled Liquid and Quenched Glass

J Am Chem Soc. 2022 Jul 27;144(29):13021-13025. doi: 10.1021/jacs.2c04532. Epub 2022 Jun 24.

Authors

Zheng Yin^{1

2

3}, Yingbo Zhao⁴, Shuang Wan², Jian Yang², Zhaolin Shi⁴, Si-Xu Peng², Ming-Zhu Chen¹, Tian-Yi Xie¹, Teng-Wu Zeng⁴, Osamu Yamamuro⁵, Masami Nirei⁵, Hiroshi Akiba⁵, Yue-Biao Zhang⁴, Hai-Bin Yu⁶, Ming-Hua Zeng^{1

2

7}

Affiliations

¹ State Key Laboratory for Chemistry and Molecular Engineering of Medicinal Resources, School of Chemistry and Pharmaceutical Sciences, Guangxi Normal University, Guilin 541004, P. R. China.
² Hubei Collaborative Innovation Center for Advanced Organic Chemical Materials, Ministry of Education Key Laboratory for the Synthesis and Application of Organic Functional Molecules, College of Chemistry and Chemical Engineering, Hubei University, Wuhan 430062, P. R. China.
³ College of Chemistry and Chemical Engineering, Xi'an Key Laboratory of Advanced Performance Materials and Polymers, Shaanxi University of Science and Technology, Xi'an 710021, P. R. China.
⁴ Shanghai Key Laboratory of High-Resolution Electron Microscopy, School of Physical Science and Technology, Shanghai Tech University, Shanghai 201210, P. R. China.
⁵ Neutron Science Laboratory, Institute for Solid State Physics, The University of Tokyo, 5-1-5 Kashiwanoha, Kashiwa, Chiba 277-8581, Japan.
⁶ Wuhan National High Magnetic Field Center, Huazhong University of Science and Technology, Wuhan 430074, P. R. China.
⁷ Guangxi Key Laboratory of Electrochemical and Magneto-Chemical Function Materia, College of Chemistry and Bioengi-neering, Guilin University of Technology, Guilin 541004, P. R. China.

PMID: 35748600
DOI: 10.1021/jacs.2c04532

Abstract

Metal-organic framework (MOF) glasses are a fascinating new class of materials, yet their prosperity has been impeded by the scarcity of known examples and limited vitrification methods. In the work described in this report, we applied synergistic stimuli of vapor hydration and thermal dehydration to introduce structural disorders in interpenetrated dia-net MOF, which facilitate the formation of stable super-cooled liquid and quenched glass. The material after stimulus has a glass transition temperature (T_g) of 560 K, far below the decomposition temperature of 695 K. When heated, the perturbed MOF enters a super-cooled liquid phase that is stable for a long period of time (>10⁴ s), across a broad temperature range (26 K), and has a large fragility index of 83. Quenching the super-cooled liquid gives rise to porous MOF glass with maintained framework connectivity, confirmed by EXAFS and PDF analysis. This method provides a fundamentally new route to obtain glassy materials from MOFs that cannot be melted without causing decomposition.