Mixed metal node effect in zeolitic imidazolate frameworks.

Autor: Madsen RSK; Department of Chemistry and Bioscience, Aalborg University Aalborg DK9220 Denmark yy@bio.aau.dk., Stepniewska M; Department of Chemistry and Bioscience, Aalborg University Aalborg DK9220 Denmark yy@bio.aau.dk., Yang Y; Department of Materials Science and Engineering, The Pennsylvania State University USA jcm426@psu.edu., Qiao A; Wuhan University of Technology Wuhan 430070 China., Winters WMW; Department of Chemistry and Bioscience, Aalborg University Aalborg DK9220 Denmark yy@bio.aau.dk., Zhou C; Department of Chemistry and Bioscience, Aalborg University Aalborg DK9220 Denmark yy@bio.aau.dk., König J; Advanced Materials Department, Jožef Stefan Institute Ljubljana 1000 Slovenia., Mauro JC; Department of Materials Science and Engineering, The Pennsylvania State University USA jcm426@psu.edu., Yue Y; Department of Chemistry and Bioscience, Aalborg University Aalborg DK9220 Denmark yy@bio.aau.dk.
Jazyk: angličtina
Zdroj: RSC advances [RSC Adv] 2022 Apr 07; Vol. 12 (17), pp. 10815-10824. Date of Electronic Publication: 2022 Apr 07 (Print Publication: 2022).
DOI: 10.1039/d2ra00744d
Abstrakt: 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 ( T m ) and glass transition temperature ( T g ) 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 Co 2+ and Zn 2+ 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 T g / T m ratios (0.77-0.84) compared to most good glass formers.
Competing Interests: The authors declare no competing financial interest.
(This journal is © The Royal Society of Chemistry.)
Databáze: MEDLINE
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