Using Supercritical CO<sub>2</sub> in the Preparation of Metal-Organic Frameworks: Investigating Effects on Crystallisation
In this report, we explore the use of supercritical CO<sub>2</sub> (scCO<sub>2</sub>) in the synthesis of well-known metal-organic frameworks (MOFs) including Zn-MOF-74 and UiO-66, as well as on the preparation of [Cu<sub>24</sub>(OH-<i>m</i>BDC)<su...
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| Format: | Article |
| Language: | English |
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MDPI AG
2019-12-01
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| Series: | Crystals |
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| Online Access: | https://www.mdpi.com/2073-4352/10/1/17 |
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| author | Huan V. Doan Fei Cheng Thandeka Dyirakumunda Mark R. J. Elsegood Jiamin Chin Oliver Rowe Carl Redshaw Valeska P. Ting |
| author_facet | Huan V. Doan Fei Cheng Thandeka Dyirakumunda Mark R. J. Elsegood Jiamin Chin Oliver Rowe Carl Redshaw Valeska P. Ting |
| author_sort | Huan V. Doan |
| collection | DOAJ |
| description | In this report, we explore the use of supercritical CO<sub>2</sub> (scCO<sub>2</sub>) in the synthesis of well-known metal-organic frameworks (MOFs) including Zn-MOF-74 and UiO-66, as well as on the preparation of [Cu<sub>24</sub>(OH-<i>m</i>BDC)<sub>24</sub>]<sub>n</sub> metal-organic polyhedra (MOPs) and two new MOF structures {[Zn<sub>2</sub>(L<sup>1</sup>)(DPE)]∙4H<sub>2</sub>O}<sub>n</sub> and {[Zn<sub>3</sub>(L<sup>1</sup>)<sub>3</sub>(4,4′-azopy)]∙7.5H<sub>2</sub>O}<sub>n</sub>, where BTC = benzene-1,3,5-tricarboxylate, BDC = benzene-1,4-dicarboxylate, L<sup>1</sup> = 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 °C). The objective of the work was to see if the same or different products would result from the scCO<sub>2</sub> 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 scCO<sub>2</sub> to these systems, it was shown that the use of scCO<sub>2</sub> can have an effect on crystallinity, crystal size and morphology. |
| first_indexed | 2024-04-14T01:40:26Z |
| format | Article |
| id | doaj.art-839868bc2bb8413f8ca2ff7e3d485d46 |
| institution | Directory Open Access Journal |
| issn | 2073-4352 |
| language | English |
| last_indexed | 2024-04-14T01:40:26Z |
| publishDate | 2019-12-01 |
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| record_format | Article |
| series | Crystals |
| spelling | doaj.art-839868bc2bb8413f8ca2ff7e3d485d462022-12-22T02:19:47ZengMDPI AGCrystals2073-43522019-12-011011710.3390/cryst10010017cryst10010017Using Supercritical CO<sub>2</sub> in the Preparation of Metal-Organic Frameworks: Investigating Effects on CrystallisationHuan V. Doan0Fei Cheng1Thandeka Dyirakumunda2Mark R. J. Elsegood3Jiamin Chin4Oliver Rowe5Carl Redshaw6Valeska P. Ting7Department of Mechanical Engineering, University of Bristol, Bristol BS8 1TR, UKDepartment of Chemistry & Biochemistry, University of Hull, Cottingham Rd, Hull HU6 7RX, UKChemistry Department, Loughborough University, Loughborough, Leicestershire LE11 3TU, UKChemistry Department, Loughborough University, Loughborough, Leicestershire LE11 3TU, UKDepartment of Physical Chemistry, Faculty of Chemistry, University of Vienna, 1090 Vienna, AustriaEnergy Materials Laboratory, School of Chemistry, University of East Anglia, Norwich NR4 7TJ, UKDepartment of Chemistry & Biochemistry, University of Hull, Cottingham Rd, Hull HU6 7RX, UKDepartment of Mechanical Engineering, University of Bristol, Bristol BS8 1TR, UKIn this report, we explore the use of supercritical CO<sub>2</sub> (scCO<sub>2</sub>) in the synthesis of well-known metal-organic frameworks (MOFs) including Zn-MOF-74 and UiO-66, as well as on the preparation of [Cu<sub>24</sub>(OH-<i>m</i>BDC)<sub>24</sub>]<sub>n</sub> metal-organic polyhedra (MOPs) and two new MOF structures {[Zn<sub>2</sub>(L<sup>1</sup>)(DPE)]∙4H<sub>2</sub>O}<sub>n</sub> and {[Zn<sub>3</sub>(L<sup>1</sup>)<sub>3</sub>(4,4′-azopy)]∙7.5H<sub>2</sub>O}<sub>n</sub>, where BTC = benzene-1,3,5-tricarboxylate, BDC = benzene-1,4-dicarboxylate, L<sup>1</sup> = 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 °C). The objective of the work was to see if the same or different products would result from the scCO<sub>2</sub> 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 scCO<sub>2</sub> to these systems, it was shown that the use of scCO<sub>2</sub> can have an effect on crystallinity, crystal size and morphology.https://www.mdpi.com/2073-4352/10/1/17metal-organic frameworksupercritical co<sub>2</sub>crystallisation |
| spellingShingle | Huan V. Doan Fei Cheng Thandeka Dyirakumunda Mark R. J. Elsegood Jiamin Chin Oliver Rowe Carl Redshaw Valeska P. Ting Using Supercritical CO<sub>2</sub> in the Preparation of Metal-Organic Frameworks: Investigating Effects on Crystallisation Crystals metal-organic framework supercritical co<sub>2</sub> crystallisation |
| title | Using Supercritical CO<sub>2</sub> in the Preparation of Metal-Organic Frameworks: Investigating Effects on Crystallisation |
| title_full | Using Supercritical CO<sub>2</sub> in the Preparation of Metal-Organic Frameworks: Investigating Effects on Crystallisation |
| title_fullStr | Using Supercritical CO<sub>2</sub> in the Preparation of Metal-Organic Frameworks: Investigating Effects on Crystallisation |
| title_full_unstemmed | Using Supercritical CO<sub>2</sub> in the Preparation of Metal-Organic Frameworks: Investigating Effects on Crystallisation |
| title_short | Using Supercritical CO<sub>2</sub> in the Preparation of Metal-Organic Frameworks: Investigating Effects on Crystallisation |
| title_sort | using supercritical co sub 2 sub in the preparation of metal organic frameworks investigating effects on crystallisation |
| topic | metal-organic framework supercritical co<sub>2</sub> crystallisation |
| url | https://www.mdpi.com/2073-4352/10/1/17 |
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