Hydroxyl-Decorated Diiron Complex as a [FeFe]-Hydrogenase Active Site Model Complex: Light-Driven Photocatalytic Activity and Heterogenization on Ethylene-Bridged Periodic Mesoporous Organosilica
A biomimetic model complex of the [FeFe]-hydrogenase active site (FeFeOH) with an ethylene bridge and a pendant hydroxyl group has been synthesized, characterized and evaluated as catalyst for the light-driven hydrogen production. The interaction of the hydroxyl group present in the complex with 3-i...
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MDPI AG
2022-02-01
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| Online Access: | https://www.mdpi.com/2073-4344/12/3/254 |
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| author | Juan Amaro-Gahete Dolores Esquivel Mariia V. Pavliuk César Jiménez-Sanchidrián Haining Tian Sascha Ott Francisco J. Romero-Salguero |
| author_facet | Juan Amaro-Gahete Dolores Esquivel Mariia V. Pavliuk César Jiménez-Sanchidrián Haining Tian Sascha Ott Francisco J. Romero-Salguero |
| author_sort | Juan Amaro-Gahete |
| collection | DOAJ |
| description | A biomimetic model complex of the [FeFe]-hydrogenase active site (FeFeOH) with an ethylene bridge and a pendant hydroxyl group has been synthesized, characterized and evaluated as catalyst for the light-driven hydrogen production. The interaction of the hydroxyl group present in the complex with 3-isocyanopropyltriethoxysilane provided a carbamate triethoxysilane bearing a diiron dithiolate complex (NCOFeFe), thus becoming a potentially promising candidate for anchoring on heterogeneous supports. As a proof of concept, the NCOFeFe precursor was anchored by a grafting procedure into a periodic mesoporous organosilica with ethane bridges (EthanePMO@NCOFeFe). Both molecular and heterogenized complexes were tested as catalysts for light-driven hydrogen generation in aqueous solutions. The photocatalytic conditions were optimized for the homogenous complex by varying the reaction time, pH, amount of the catalyst or photosensitizer, photon flux, and the type of light source (light-emitting diode (LED) and Xe lamp). It was shown that the molecular FeFeOH diiron complex achieved a decent turnover number (TON) of 70 after 6 h, while NCOFeFe and EthanePMO@NCOFeFe had slightly lower activities showing TONs of 37 and 5 at 6 h, respectively. |
| first_indexed | 2024-03-09T20:02:16Z |
| format | Article |
| id | doaj.art-d40863f517c64d0aadfb30b48b71429e |
| institution | Directory Open Access Journal |
| issn | 2073-4344 |
| language | English |
| last_indexed | 2024-03-09T20:02:16Z |
| publishDate | 2022-02-01 |
| publisher | MDPI AG |
| record_format | Article |
| series | Catalysts |
| spelling | doaj.art-d40863f517c64d0aadfb30b48b71429e2023-11-24T00:41:52ZengMDPI AGCatalysts2073-43442022-02-0112325410.3390/catal12030254Hydroxyl-Decorated Diiron Complex as a [FeFe]-Hydrogenase Active Site Model Complex: Light-Driven Photocatalytic Activity and Heterogenization on Ethylene-Bridged Periodic Mesoporous OrganosilicaJuan Amaro-Gahete0Dolores Esquivel1Mariia V. Pavliuk2César Jiménez-Sanchidrián3Haining Tian4Sascha Ott5Francisco J. Romero-Salguero6Departamento de Química Orgánica, Edificio Marie Curie, Facultad de Ciencias, Campus Universitario de Rabanales, Instituto Universitario de Nanoquímica (IUNAN), Universidad de Córdoba, 14071 Córdoba, SpainDepartamento de Química Orgánica, Edificio Marie Curie, Facultad de Ciencias, Campus Universitario de Rabanales, Instituto Universitario de Nanoquímica (IUNAN), Universidad de Córdoba, 14071 Córdoba, SpainÅngström Laboratories, Department of Chemistry, Uppsala University, P.O. Box 523, 751 20 Uppsala, SwedenDepartamento de Química Orgánica, Edificio Marie Curie, Facultad de Ciencias, Campus Universitario de Rabanales, Instituto Universitario de Nanoquímica (IUNAN), Universidad de Córdoba, 14071 Córdoba, SpainÅngström Laboratories, Department of Chemistry, Uppsala University, P.O. Box 523, 751 20 Uppsala, SwedenÅngström Laboratories, Department of Chemistry, Uppsala University, P.O. Box 523, 751 20 Uppsala, SwedenDepartamento de Química Orgánica, Edificio Marie Curie, Facultad de Ciencias, Campus Universitario de Rabanales, Instituto Universitario de Nanoquímica (IUNAN), Universidad de Córdoba, 14071 Córdoba, SpainA biomimetic model complex of the [FeFe]-hydrogenase active site (FeFeOH) with an ethylene bridge and a pendant hydroxyl group has been synthesized, characterized and evaluated as catalyst for the light-driven hydrogen production. The interaction of the hydroxyl group present in the complex with 3-isocyanopropyltriethoxysilane provided a carbamate triethoxysilane bearing a diiron dithiolate complex (NCOFeFe), thus becoming a potentially promising candidate for anchoring on heterogeneous supports. As a proof of concept, the NCOFeFe precursor was anchored by a grafting procedure into a periodic mesoporous organosilica with ethane bridges (EthanePMO@NCOFeFe). Both molecular and heterogenized complexes were tested as catalysts for light-driven hydrogen generation in aqueous solutions. The photocatalytic conditions were optimized for the homogenous complex by varying the reaction time, pH, amount of the catalyst or photosensitizer, photon flux, and the type of light source (light-emitting diode (LED) and Xe lamp). It was shown that the molecular FeFeOH diiron complex achieved a decent turnover number (TON) of 70 after 6 h, while NCOFeFe and EthanePMO@NCOFeFe had slightly lower activities showing TONs of 37 and 5 at 6 h, respectively.https://www.mdpi.com/2073-4344/12/3/254[FeFe]-hydrogenaseperiodic mesoporous organosilicabiomimetic chemistryartificial photosynthesislight-driven hydrogen evolution |
| spellingShingle | Juan Amaro-Gahete Dolores Esquivel Mariia V. Pavliuk César Jiménez-Sanchidrián Haining Tian Sascha Ott Francisco J. Romero-Salguero Hydroxyl-Decorated Diiron Complex as a [FeFe]-Hydrogenase Active Site Model Complex: Light-Driven Photocatalytic Activity and Heterogenization on Ethylene-Bridged Periodic Mesoporous Organosilica Catalysts [FeFe]-hydrogenase periodic mesoporous organosilica biomimetic chemistry artificial photosynthesis light-driven hydrogen evolution |
| title | Hydroxyl-Decorated Diiron Complex as a [FeFe]-Hydrogenase Active Site Model Complex: Light-Driven Photocatalytic Activity and Heterogenization on Ethylene-Bridged Periodic Mesoporous Organosilica |
| title_full | Hydroxyl-Decorated Diiron Complex as a [FeFe]-Hydrogenase Active Site Model Complex: Light-Driven Photocatalytic Activity and Heterogenization on Ethylene-Bridged Periodic Mesoporous Organosilica |
| title_fullStr | Hydroxyl-Decorated Diiron Complex as a [FeFe]-Hydrogenase Active Site Model Complex: Light-Driven Photocatalytic Activity and Heterogenization on Ethylene-Bridged Periodic Mesoporous Organosilica |
| title_full_unstemmed | Hydroxyl-Decorated Diiron Complex as a [FeFe]-Hydrogenase Active Site Model Complex: Light-Driven Photocatalytic Activity and Heterogenization on Ethylene-Bridged Periodic Mesoporous Organosilica |
| title_short | Hydroxyl-Decorated Diiron Complex as a [FeFe]-Hydrogenase Active Site Model Complex: Light-Driven Photocatalytic Activity and Heterogenization on Ethylene-Bridged Periodic Mesoporous Organosilica |
| title_sort | hydroxyl decorated diiron complex as a fefe hydrogenase active site model complex light driven photocatalytic activity and heterogenization on ethylene bridged periodic mesoporous organosilica |
| topic | [FeFe]-hydrogenase periodic mesoporous organosilica biomimetic chemistry artificial photosynthesis light-driven hydrogen evolution |
| url | https://www.mdpi.com/2073-4344/12/3/254 |
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