Using supercritical CO2 in the preparation of metal-organic frameworks: Investigating effects on crystallisation

Elsegood, Mark R.J.; Doan, Huan V.; Cheng, Fei; Dyirakumunda, Thandeka; Elsegood, Mark; Chin, Jiamin; Rowe, Oliver; Redshaw, Carl; Ting, Valeska P.

Abstract

© 2019 by the authors. Licensee MDPI, Basel, Switzerland. In this report, we explore the use of supercritical CO2 (scCO2) in the synthesis of well-known metal-organic frameworks (MOFs) including Zn-MOF-74 and UiO-66, as well as on the preparation of [Cu24(OH-mBDC)24]n metal-organic polyhedra (MOPs) and two new MOF structures {[Zn2(L1)(DPE)]∙4H2O}n and {[Zn3(L1)3(4,4’-azopy)]∙7.5H2O}n, where BTC = benzene-1,3,5-tricarboxylate, BDC = benzene-1,4-dicarboxylate, L1 = 4-carboxy-phenylene-methyleneamino-4-benzoate, DPE = 1,2-di(4-pyridyl)ethylene, 4.4’-azopy = 4,4’- azopyridine, and compare the results versus traditional solvothermal preparations at low temperatures (i.e., 40 °Ϲ). The objective of the work was to see if the sames or different products would result from the ssCO2 route versus the solvothermal method. We were interested to see which method produced the highest yield, the cleanest product and what types of morphology resulted. While there was no evidence of additional meso- or macroporosity in these MOFs/MOPs nor any significant improvements in product yields through the addition of scCO2 to these systems, it was shown that the use of scCO2 can have an effect on crystallinity, crystal size and morphology.

Citation

Elsegood, M. R., Doan, H. V., Cheng, F., Dyirakumunda, T., Elsegood, M., Chin, J., Rowe, O., Redshaw, C., & Ting, V. P. (2020). Using supercritical CO2 in the preparation of metal-organic frameworks: Investigating effects on crystallisation. Crystals, 10(1), Article 17. https://doi.org/10.3390/cryst10010017

• Journal Article Type: Article
• Acceptance Date: Dec 30, 2019
• Online Publication Date: Dec 31, 2019
• Publication Date: 2020-01
• Deposit Date: Jan 2, 2020
• Publicly Available Date: Jan 3, 2020
• Journal: Crystals
• Electronic ISSN: 2073-4352
• Publisher: MDPI
• Peer Reviewed: Peer Reviewed
• Volume: 10
• Issue: 1
• Article Number: 17
• DOI: https://doi.org/10.3390/cryst10010017
• Keywords: Metal-organic framework; Supercritical CO2; Crystallisation
• Public URL: https://hull-repository.worktribe.com/output/3340425
• Publisher URL: https://www.mdpi.com/2073-4352/10/1/17
• Contract Date: Jan 3, 2020