Enhancing photocatalytic performance of covalent organic frameworks via ionic polarization
Abstract Covalent organic frameworks have emerged as a thriving family in the realm of photocatalysis recently, yet with concerns about their high exciton dissociation energy and sluggish charge transfer. Herein, a strategy to enhance the built-in electric field of series β-keto-enamine-based covale...
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| Format: | Article |
| Language: | English |
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Nature Portfolio
2024-11-01
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| Series: | Nature Communications |
| Online Access: | https://doi.org/10.1038/s41467-024-53834-w |
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| author | Jiahe Zhang Xiaoning Li Haijun Hu Hongwei Huang Hui Li Xiaodong Sun Tianyi Ma |
| author_facet | Jiahe Zhang Xiaoning Li Haijun Hu Hongwei Huang Hui Li Xiaodong Sun Tianyi Ma |
| author_sort | Jiahe Zhang |
| collection | DOAJ |
| description | Abstract Covalent organic frameworks have emerged as a thriving family in the realm of photocatalysis recently, yet with concerns about their high exciton dissociation energy and sluggish charge transfer. Herein, a strategy to enhance the built-in electric field of series β-keto-enamine-based covalent organic frameworks by ionic polarization method is proposed. The ionic polarization is achieved through a distinctive post-synthetic quaternization reaction which can endow the covalent organic frameworks with separated charge centers comprising cationic skeleton and iodide counter-anions. The stronger built-in electric field generated between their cationic framework and iodide anions promotes charge transfer and exciton dissociation efficiency. Moreover, the introduced iodide anions not only serve as reaction centers with lowered H* formation energy barrier, but also act as electron extractant suppressing the recombination of electron-hole pairs. Therefore, the photocatalytic performance of the covalent organic frameworks shows notable improvement, among which the CH3I-TpPa-1 can deliver an high H2 production rate up to 9.21 mmol g−1 h−1 without any co-catalysts, representing a 42-fold increase compared to TpPa-1, being comparable to or possibly exceeding the current covalent organic framework photocatalysts with the addition of Pt co-catalysts. |
| format | Article |
| id | doaj-art-d88f9d240e734b828d6ca0940c51bda4 |
| institution | Kabale University |
| issn | 2041-1723 |
| language | English |
| publishDate | 2024-11-01 |
| publisher | Nature Portfolio |
| record_format | Article |
| series | Nature Communications |
| spelling | doaj-art-d88f9d240e734b828d6ca0940c51bda42024-11-10T12:33:47ZengNature PortfolioNature Communications2041-17232024-11-0115111010.1038/s41467-024-53834-wEnhancing photocatalytic performance of covalent organic frameworks via ionic polarizationJiahe Zhang0Xiaoning Li1Haijun Hu2Hongwei Huang3Hui Li4Xiaodong Sun5Tianyi Ma6Institute of Clean Energy Chemistry, Key Laboratory for Green Synthesis and Preparative Chemistry of Advanced Materials, College of Chemistry, Liaoning UniversityCentre for Atomaterials and Nanomanufacturing (CAN), School of Science, RMIT UniversityInstitute of Clean Energy Chemistry, Key Laboratory for Green Synthesis and Preparative Chemistry of Advanced Materials, College of Chemistry, Liaoning UniversityBeijing Key Laboratory of Materials Utilization of Nonmetallic Minerals and Solid Wastes, National Laboratory of Mineral Materials, School of Materials Science and Technology, China University of GeosciencesCentre for Atomaterials and Nanomanufacturing (CAN), School of Science, RMIT UniversityInstitute of Clean Energy Chemistry, Key Laboratory for Green Synthesis and Preparative Chemistry of Advanced Materials, College of Chemistry, Liaoning UniversityCentre for Atomaterials and Nanomanufacturing (CAN), School of Science, RMIT UniversityAbstract Covalent organic frameworks have emerged as a thriving family in the realm of photocatalysis recently, yet with concerns about their high exciton dissociation energy and sluggish charge transfer. Herein, a strategy to enhance the built-in electric field of series β-keto-enamine-based covalent organic frameworks by ionic polarization method is proposed. The ionic polarization is achieved through a distinctive post-synthetic quaternization reaction which can endow the covalent organic frameworks with separated charge centers comprising cationic skeleton and iodide counter-anions. The stronger built-in electric field generated between their cationic framework and iodide anions promotes charge transfer and exciton dissociation efficiency. Moreover, the introduced iodide anions not only serve as reaction centers with lowered H* formation energy barrier, but also act as electron extractant suppressing the recombination of electron-hole pairs. Therefore, the photocatalytic performance of the covalent organic frameworks shows notable improvement, among which the CH3I-TpPa-1 can deliver an high H2 production rate up to 9.21 mmol g−1 h−1 without any co-catalysts, representing a 42-fold increase compared to TpPa-1, being comparable to or possibly exceeding the current covalent organic framework photocatalysts with the addition of Pt co-catalysts.https://doi.org/10.1038/s41467-024-53834-w |
| spellingShingle | Jiahe Zhang Xiaoning Li Haijun Hu Hongwei Huang Hui Li Xiaodong Sun Tianyi Ma Enhancing photocatalytic performance of covalent organic frameworks via ionic polarization Nature Communications |
| title | Enhancing photocatalytic performance of covalent organic frameworks via ionic polarization |
| title_full | Enhancing photocatalytic performance of covalent organic frameworks via ionic polarization |
| title_fullStr | Enhancing photocatalytic performance of covalent organic frameworks via ionic polarization |
| title_full_unstemmed | Enhancing photocatalytic performance of covalent organic frameworks via ionic polarization |
| title_short | Enhancing photocatalytic performance of covalent organic frameworks via ionic polarization |
| title_sort | enhancing photocatalytic performance of covalent organic frameworks via ionic polarization |
| url | https://doi.org/10.1038/s41467-024-53834-w |
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