Melt-quenched glass formation of a family of metal-carboxylate frameworks

Wen-Long Xue; Guo-Qiang Li; Hui Chen; Yu-Chen Han; Li Feng; Lu Wang; Xiao-Ling Gu; Si-Yuan Hu; Yu-Heng Deng; Lei Tan; Martin T Dove; Wei Li; Jiangwei Zhang; Hongliang Dong; Zhiqiang Chen; Wei-Hua Deng; Gang Xu; Guo Wang; Chong-Qing Wan

doi:10.1038/s41467-024-46311-x

Melt-quenched glass formation of a family of metal-carboxylate frameworks

Nat Commun. 2024 Mar 6;15(1):2040. doi: 10.1038/s41467-024-46311-x.

Authors

Wen-Long Xue^#^{1

2}, Guo-Qiang Li^#¹, Hui Chen^#^{1

3}, Yu-Chen Han¹, Li Feng¹, Lu Wang¹, Xiao-Ling Gu¹, Si-Yuan Hu¹, Yu-Heng Deng¹, Lei Tan⁴, Martin T Dove⁵, Wei Li⁶, Jiangwei Zhang⁷, Hongliang Dong⁸, Zhiqiang Chen⁸, Wei-Hua Deng⁹, Gang Xu¹⁰, Guo Wang¹, Chong-Qing Wan^{11

12

13}

Affiliations

¹ Beijing Key Laboratory for Optical Materials and Photonic Devices, Department of Chemistry, Capital Normal University, 100048, Beijing, China.
² Anorganische Chemie, Fakultät für Chemie & Chemische Biologie, Technische Universität Dortmund, Otto-Hahn Straße 6, Dortmund, 44227, Germany.
³ School of Chemistry and Chemical Engineering, Xi'an University of Architecture and Technology, Xi'an, 710055, China.
⁴ Department of Physics, School of Sciences, Wuhan University of Technology, Wuhan, 430070, Hubei, China.
⁵ College of Computer Science, Sichuan University, Chengdu, 610065, Sichuan, China.
⁶ School of Materials Science and Engineering & Tianjin Key Laboratory of Metal and Molecule-Based Material Chemistry, Nankai University, Tianjin, 300350, China. wl276@nankai.edu.cn.
⁷ College of Energy Material and Chemistry, Inner Mongolia University, Hohhot, 010021, China. zjw11@tsinghua.org.cn.
⁸ Center for High Pressure Science and Technology Advanced Research, Pudong, Shanghai, 201203, China.
⁹ State Key Laboratory of Structural Chemistry, and Fujian Provincial Key Laboratory of Materials and Techniques toward Hydrogen Energy, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou, Fujian, 350002, China.
¹⁰ State Key Laboratory of Structural Chemistry, and Fujian Provincial Key Laboratory of Materials and Techniques toward Hydrogen Energy, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou, Fujian, 350002, China. gxu@fjirsm.ac.cn.
¹¹ Beijing Key Laboratory for Optical Materials and Photonic Devices, Department of Chemistry, Capital Normal University, 100048, Beijing, China. wancq@cnu.edu.cn.
¹² State Key Laboratory of Structural Chemistry, and Fujian Provincial Key Laboratory of Materials and Techniques toward Hydrogen Energy, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou, Fujian, 350002, China. wancq@cnu.edu.cn.
¹³ Key Laboratory of Bioorganic Phosphorus Chemistry & Chemical Biology (Ministry of Education), Department of Chemistry, Tsinghua University, 100084, Beijing, China. wancq@cnu.edu.cn.

^# Contributed equally.

Abstract

Metal-organic framework (MOF) glasses are an emerging class of glasses which complement traditional inorganic, organic and metallic counterparts due to their hybrid nature. Although a few zeolitic imidazolate frameworks have been made into glasses, how to melt and quench the largest subclass of MOFs, metal carboxylate frameworks, into glasses remains challenging. Here, we develop a strategy by grafting the zwitterions on the carboxylate ligands and incorporating organic acids in the framework channels to enable the glass formation. The charge delocalization of zwitterion-acid subsystem and the densely filled channels facilitate the coordination bonding mismatch and thus reduce the melting temperature. Following melt-quenching realizes the glass formation of a family of carboxylate MOFs (UiO-67, UiO-68 and DUT-5), which are usually believed to be un-meltable. Our work opens up an avenue for melt-quenching porous molecular solids into glasses.

Abstract

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