Elucidation of the Formation Mechanism of Metal–Organic Frameworks via in-Situ Raman and FTIR Spectroscopy under Solvothermal Conditions

The metal–organic framework MIL-53­(Al) serves as a model system in this study. Its formation mechanism in N,N-dimethylformamide (DMF) is elucidated through simultaneous FTIR and Raman spectroscopy and turbidity measurements collected under in-situ synthesis conditions in a custom-designed solvother...

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Veröffentlicht in:Journal of physical chemistry. C 2018-06, Vol.122 (23), p.12267-12278
Hauptverfasser: Embrechts, Heidemarie, Kriesten, Martin, Hoffmann, Kilian, Peukert, Wolfgang, Hartmann, Martin, Distaso, Monica
Format: Artikel
Sprache:eng
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Zusammenfassung:The metal–organic framework MIL-53­(Al) serves as a model system in this study. Its formation mechanism in N,N-dimethylformamide (DMF) is elucidated through simultaneous FTIR and Raman spectroscopy and turbidity measurements collected under in-situ synthesis conditions in a custom-designed solvothermal reactor coupled with reaction sampling. Different synthesis steps are followed over synthesis time including a prenucleation building unit (PNBU) consisting of one linker molecule and one aluminum atom, the assembly of the PNBUs to MIL-53 nuclei in solution, the decomposition of DMF to formic acid and dimethylammonium, and finally the precipitation of the crystalline MOF phase. The rearrangement of the PNBU to form MIL-53 is identified as the rate-limiting reaction step responsible for the long induction time at low temperatures (
ISSN:1932-7447
1932-7455
DOI:10.1021/acs.jpcc.8b02484