Mixed metal node effect in zeolitic imidazolate frameworks

Rasmus S.K. Madsen, Malwina Stepniewska, Yongjian Yang, Ang Qiao, Wessel M.W. Winters, Chao Zhou, Jakob König, John C. Mauro, Yuanzheng Yue

Research output: Contribution to journalArticlepeer-review

7 Scopus citations

Abstract

We synthesized two series of bimetallic (zinc and cobalt) zeolitic imidazolate frameworks (ZIF-62) under different solvothermal conditions. It is found that the structure of the derived ZIF crystals is highly sensitive to synthesis conditions. One series possesses the standard ZIF-62 structure, whereas the other has a mixed structure composed of both the standard structure and an unknown one. The standard series exhibits a slight negative deviation from linearity of melting temperature (Tm) and glass transition temperature (Tg) with the substitution of Co for Zn. In contrast, the new series displays a stronger negative deviation. These negative deviations from linearity indicate the mixed metal node effect in bimetallic ZIF-62 due to the structural mismatch between Co2+ and Zn2+ and to the difference in their electronic configurations. The new series involves both cobalt-rich and zinc-rich phases, whereas the standard one shows one homogeneous phase. Density functional theory calculations predict that the substitution of Co for Zn increases the bulk modulus of the ZIF crystals. This work indicates that the structure, melting behaviour, and mechanical properties of ZIFs can be tuned by metal node substitution and by varying the synthetic conditions. Both series of ZIFs have higher glass forming abilities due to their higher Tg/Tm ratios (0.77-0.84) compared to most good glass formers.

Original languageEnglish (US)
Pages (from-to)10815-10824
Number of pages10
JournalRSC Advances
Volume12
Issue number17
DOIs
StatePublished - Apr 7 2022

All Science Journal Classification (ASJC) codes

  • General Chemistry
  • General Chemical Engineering

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