Nitrogen-Rich Tetrazole–Amide-Functionalised Zn Metal–Organic Framework as Catalyst for Efficient Catalytic CO<sub>2</sub> Cycloaddition with Epoxides
In this study, we report the design, synthesis, and catalytic application of the novel nitrogen-rich Zn(II) MOF [Zn<sub>2</sub>(μ<sub>3</sub>-1κ<i>N</i>,<i>2</i>κ<i>N</i>′,<i>3</i>κ<i>O</i>-HL)<sub>2</sub>...
| Main Authors: | , , , , , , |
|---|---|
| Format: | Article |
| Language: | English |
| Published: |
MDPI AG
2023-12-01
|
| Series: | Catalysts |
| Subjects: | |
| Online Access: | https://www.mdpi.com/2073-4344/14/1/6 |
| _version_ | 1797344443191263232 |
|---|---|
| author | Anup Paul Ismayil M. Garazade Anirban Karmakar Rais Ahmad Khan Maria Fátima C. Guedes da Silva Ana V. M. Nunes Armando J. L. Pombeiro |
| author_facet | Anup Paul Ismayil M. Garazade Anirban Karmakar Rais Ahmad Khan Maria Fátima C. Guedes da Silva Ana V. M. Nunes Armando J. L. Pombeiro |
| author_sort | Anup Paul |
| collection | DOAJ |
| description | In this study, we report the design, synthesis, and catalytic application of the novel nitrogen-rich Zn(II) MOF [Zn<sub>2</sub>(μ<sub>3</sub>-1κ<i>N</i>,<i>2</i>κ<i>N</i>′,<i>3</i>κ<i>O</i>-HL)<sub>2</sub>(DMF)<sub>2</sub>]<sub>n</sub>·nH<sub>2</sub>O (HL<sup>2−</sup> = 4-((4-(1H-tetrazol-5-yl)phenyl)carbamoyl)benzoate), denoted as <b>ZnMOF</b>, for the efficient conversion of carbon dioxide (CO<sub>2</sub>) to cyclic carbonates via cycloaddition with epoxides. It was synthesised from a tetrazole appended amide-functionalised pro-ligand (<b>H<sub>3</sub>L</b>) and Zn(NO<sub>3</sub>)<sub>2</sub>·6H<sub>2</sub>O under hydrothermal conditions. The synthesised material was characterised namely by elemental analysis, infrared spectroscopy, powder X-ray diffraction (PXRD), and single-crystal X-ray diffraction analyses. The catalytic potential of <b>ZnMOF</b> was investigated in the CO<sub>2</sub> cycloaddition reaction with various epoxides, with conversions ranging from 17% to 99%. The catalyst retained its activity across multiple reaction cycles, demonstrating its stability and reusability. The influence of co-catalysts on the reaction was explored, with tetrabutylammonium bromide (TBABr) emerging as the most effective one. A plausible reaction mechanism is proposed. |
| first_indexed | 2024-03-08T11:02:31Z |
| format | Article |
| id | doaj.art-c29b2a5185c044f88c58f6ad1dbc6dfe |
| institution | Directory Open Access Journal |
| issn | 2073-4344 |
| language | English |
| last_indexed | 2024-03-08T11:02:31Z |
| publishDate | 2023-12-01 |
| publisher | MDPI AG |
| record_format | Article |
| series | Catalysts |
| spelling | doaj.art-c29b2a5185c044f88c58f6ad1dbc6dfe2024-01-26T15:39:23ZengMDPI AGCatalysts2073-43442023-12-01141610.3390/catal14010006Nitrogen-Rich Tetrazole–Amide-Functionalised Zn Metal–Organic Framework as Catalyst for Efficient Catalytic CO<sub>2</sub> Cycloaddition with EpoxidesAnup Paul0Ismayil M. Garazade1Anirban Karmakar2Rais Ahmad Khan3Maria Fátima C. Guedes da Silva4Ana V. M. Nunes5Armando J. L. Pombeiro6Centro de Química Estrutura, Institute of Molecular Sciences, Instituto Superior Técnico, Universidade de Lisboa, Av. Rovisco Pais, 1049-001 Lisboa, PortugalCentro de Química Estrutura, Institute of Molecular Sciences, Instituto Superior Técnico, Universidade de Lisboa, Av. Rovisco Pais, 1049-001 Lisboa, PortugalCentro de Química Estrutura, Institute of Molecular Sciences, Instituto Superior Técnico, Universidade de Lisboa, Av. Rovisco Pais, 1049-001 Lisboa, PortugalDepartment of Chemistry, King Saud University, Riyadh 11451, Saudi ArabiaCentro de Química Estrutura, Institute of Molecular Sciences, Instituto Superior Técnico, Universidade de Lisboa, Av. Rovisco Pais, 1049-001 Lisboa, PortugalLAQV-REQUIMTE, Departamento de Química, Faculdade de Ciências e Tecnologia, Universidade Nova de Lisboa, 2829-516 Caparica, PortugalCentro de Química Estrutura, Institute of Molecular Sciences, Instituto Superior Técnico, Universidade de Lisboa, Av. Rovisco Pais, 1049-001 Lisboa, PortugalIn this study, we report the design, synthesis, and catalytic application of the novel nitrogen-rich Zn(II) MOF [Zn<sub>2</sub>(μ<sub>3</sub>-1κ<i>N</i>,<i>2</i>κ<i>N</i>′,<i>3</i>κ<i>O</i>-HL)<sub>2</sub>(DMF)<sub>2</sub>]<sub>n</sub>·nH<sub>2</sub>O (HL<sup>2−</sup> = 4-((4-(1H-tetrazol-5-yl)phenyl)carbamoyl)benzoate), denoted as <b>ZnMOF</b>, for the efficient conversion of carbon dioxide (CO<sub>2</sub>) to cyclic carbonates via cycloaddition with epoxides. It was synthesised from a tetrazole appended amide-functionalised pro-ligand (<b>H<sub>3</sub>L</b>) and Zn(NO<sub>3</sub>)<sub>2</sub>·6H<sub>2</sub>O under hydrothermal conditions. The synthesised material was characterised namely by elemental analysis, infrared spectroscopy, powder X-ray diffraction (PXRD), and single-crystal X-ray diffraction analyses. The catalytic potential of <b>ZnMOF</b> was investigated in the CO<sub>2</sub> cycloaddition reaction with various epoxides, with conversions ranging from 17% to 99%. The catalyst retained its activity across multiple reaction cycles, demonstrating its stability and reusability. The influence of co-catalysts on the reaction was explored, with tetrabutylammonium bromide (TBABr) emerging as the most effective one. A plausible reaction mechanism is proposed.https://www.mdpi.com/2073-4344/14/1/6tetrazoleamide functionalisedMOFCO<sub>2</sub>epoxides |
| spellingShingle | Anup Paul Ismayil M. Garazade Anirban Karmakar Rais Ahmad Khan Maria Fátima C. Guedes da Silva Ana V. M. Nunes Armando J. L. Pombeiro Nitrogen-Rich Tetrazole–Amide-Functionalised Zn Metal–Organic Framework as Catalyst for Efficient Catalytic CO<sub>2</sub> Cycloaddition with Epoxides Catalysts tetrazole amide functionalised MOF CO<sub>2</sub> epoxides |
| title | Nitrogen-Rich Tetrazole–Amide-Functionalised Zn Metal–Organic Framework as Catalyst for Efficient Catalytic CO<sub>2</sub> Cycloaddition with Epoxides |
| title_full | Nitrogen-Rich Tetrazole–Amide-Functionalised Zn Metal–Organic Framework as Catalyst for Efficient Catalytic CO<sub>2</sub> Cycloaddition with Epoxides |
| title_fullStr | Nitrogen-Rich Tetrazole–Amide-Functionalised Zn Metal–Organic Framework as Catalyst for Efficient Catalytic CO<sub>2</sub> Cycloaddition with Epoxides |
| title_full_unstemmed | Nitrogen-Rich Tetrazole–Amide-Functionalised Zn Metal–Organic Framework as Catalyst for Efficient Catalytic CO<sub>2</sub> Cycloaddition with Epoxides |
| title_short | Nitrogen-Rich Tetrazole–Amide-Functionalised Zn Metal–Organic Framework as Catalyst for Efficient Catalytic CO<sub>2</sub> Cycloaddition with Epoxides |
| title_sort | nitrogen rich tetrazole amide functionalised zn metal organic framework as catalyst for efficient catalytic co sub 2 sub cycloaddition with epoxides |
| topic | tetrazole amide functionalised MOF CO<sub>2</sub> epoxides |
| url | https://www.mdpi.com/2073-4344/14/1/6 |
| work_keys_str_mv | AT anuppaul nitrogenrichtetrazoleamidefunctionalisedznmetalorganicframeworkascatalystforefficientcatalyticcosub2subcycloadditionwithepoxides AT ismayilmgarazade nitrogenrichtetrazoleamidefunctionalisedznmetalorganicframeworkascatalystforefficientcatalyticcosub2subcycloadditionwithepoxides AT anirbankarmakar nitrogenrichtetrazoleamidefunctionalisedznmetalorganicframeworkascatalystforefficientcatalyticcosub2subcycloadditionwithepoxides AT raisahmadkhan nitrogenrichtetrazoleamidefunctionalisedznmetalorganicframeworkascatalystforefficientcatalyticcosub2subcycloadditionwithepoxides AT mariafatimacguedesdasilva nitrogenrichtetrazoleamidefunctionalisedznmetalorganicframeworkascatalystforefficientcatalyticcosub2subcycloadditionwithepoxides AT anavmnunes nitrogenrichtetrazoleamidefunctionalisedznmetalorganicframeworkascatalystforefficientcatalyticcosub2subcycloadditionwithepoxides AT armandojlpombeiro nitrogenrichtetrazoleamidefunctionalisedznmetalorganicframeworkascatalystforefficientcatalyticcosub2subcycloadditionwithepoxides |