Keto-enol tautomerism as dynamic electron/hole traps promote charge carrier separation for hydrogen peroxide photosynthesis
Abstract Covalent organic frameworks (COFs) are promising photocatalysts for H2O2 photosynthesis, but charge carrier separation remains a critical challenge. Donor-acceptor COFs enhance charge separation, but the slow kinetics of water oxidation and oxygen reduction reactions lead to carrier accumul...
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Nature Portfolio
2025-08-01
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| Series: | Nature Communications |
| Online Access: | https://doi.org/10.1038/s41467-025-62286-9 |
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| author | Fang Ma Tao Gao Xiaodong Sun Chunqiu Han Yongye Wang Anqiang Jiang Ying Zhou Guijie Liang Huiqing Wang Li Wang Binbin Jia Yingping Huang Hongwei Huang Xin Ying Kong Hui Li Niu Huang Tianyi Ma Liqun Ye |
| author_facet | Fang Ma Tao Gao Xiaodong Sun Chunqiu Han Yongye Wang Anqiang Jiang Ying Zhou Guijie Liang Huiqing Wang Li Wang Binbin Jia Yingping Huang Hongwei Huang Xin Ying Kong Hui Li Niu Huang Tianyi Ma Liqun Ye |
| author_sort | Fang Ma |
| collection | DOAJ |
| description | Abstract Covalent organic frameworks (COFs) are promising photocatalysts for H2O2 photosynthesis, but charge carrier separation remains a critical challenge. Donor-acceptor COFs enhance charge separation, but the slow kinetics of water oxidation and oxygen reduction reactions lead to carrier accumulation, thereby decreasing efficiency. Here, we report T-C type COFs (T = trap units, C = catalytic units), demonstrating that units with keto-enol tautomerism can serve as dynamic electron/hole traps (T) to mitigate Coulomb forces. This design effectively facilitates swift charge transfer and extends carrier lifetimes, thereby enhancing reactions at the C units. Imine COFs derived from 2,4,6-trihydroxybenzaldehyde (Tp) outperform those based on 1,3,5-benzenetricarboxaldehyde due to tautomerization. The optimal Tp COF (TpBpy) achieves an H2O2 generation rate of 37.9 μmol h⁻¹ (or 8350 μmol h⁻¹ g⁻¹) under simulated light, and a solar-to-chemical conversion efficiency of 0.038% in a flow reactor under natural sunlight. This work provides molecular design strategies and standard criteria for efficient H2O2 photocatalysts. |
| format | Article |
| id | doaj-art-8dbee4c4d20741b9ad8e16e0451a2850 |
| institution | DOAJ |
| issn | 2041-1723 |
| language | English |
| publishDate | 2025-08-01 |
| publisher | Nature Portfolio |
| record_format | Article |
| series | Nature Communications |
| spelling | doaj-art-8dbee4c4d20741b9ad8e16e0451a28502025-08-20T03:05:06ZengNature PortfolioNature Communications2041-17232025-08-0116111610.1038/s41467-025-62286-9Keto-enol tautomerism as dynamic electron/hole traps promote charge carrier separation for hydrogen peroxide photosynthesisFang Ma0Tao Gao1Xiaodong Sun2Chunqiu Han3Yongye Wang4Anqiang Jiang5Ying Zhou6Guijie Liang7Huiqing Wang8Li Wang9Binbin Jia10Yingping Huang11Hongwei Huang12Xin Ying Kong13Hui Li14Niu Huang15Tianyi Ma16Liqun Ye17College of Materials and Chemical Engineering, Key Laboratory of Inorganic Nonmetallic Crystalline and Energy Conversion Materials, China Three Gorges UniversityCollege of Materials and Chemical Engineering, Key Laboratory of Inorganic Nonmetallic Crystalline and Energy Conversion Materials, China Three Gorges UniversityCollege of Chemistry, Liaoning UniversityCollege of Materials and Chemical Engineering, Key Laboratory of Inorganic Nonmetallic Crystalline and Energy Conversion Materials, China Three Gorges UniversityCollege of Materials and Chemical Engineering, Key Laboratory of Inorganic Nonmetallic Crystalline and Energy Conversion Materials, China Three Gorges UniversityState Key Laboratory of Oil and Gas Reservoir Geology and Exploitation, School of Oil & Natural Gas Engineering, Southwest Petroleum UniversityState Key Laboratory of Oil and Gas Reservoir Geology and Exploitation, School of Oil & Natural Gas Engineering, Southwest Petroleum UniversityHubei Key Laboratory of Low Dimensional Arts and Science, Hubei University of Arts and ScienceCollege of Materials and Chemical Engineering, Key Laboratory of Inorganic Nonmetallic Crystalline and Energy Conversion Materials, China Three Gorges UniversityEngineering Research Center of Eco-environment in Three Gorges Reservoir Region, Ministry of Education, China Three Gorges UniversityCollege of Materials and Chemical Engineering, Key Laboratory of Inorganic Nonmetallic Crystalline and Energy Conversion Materials, China Three Gorges UniversityEngineering Research Center of Eco-environment in Three Gorges Reservoir Region, Ministry of Education, China Three Gorges UniversityBeijing Key Laboratory of Materials Utilization of Nonmetallic Minerals and Solid Wastes, School of Materials Science and Technology, China University of GeosciencesSchool of Chemistry, Chemical Engineering and Biotechnology, Nanyang Technological UniversityCentre for Atomaterials and Nanomanufacturing (CAN), School of Science, RMIT UniversityCollege of Materials and Chemical Engineering, Key Laboratory of Inorganic Nonmetallic Crystalline and Energy Conversion Materials, China Three Gorges UniversityCentre for Atomaterials and Nanomanufacturing (CAN), School of Science, RMIT UniversityCollege of Materials and Chemical Engineering, Key Laboratory of Inorganic Nonmetallic Crystalline and Energy Conversion Materials, China Three Gorges UniversityAbstract Covalent organic frameworks (COFs) are promising photocatalysts for H2O2 photosynthesis, but charge carrier separation remains a critical challenge. Donor-acceptor COFs enhance charge separation, but the slow kinetics of water oxidation and oxygen reduction reactions lead to carrier accumulation, thereby decreasing efficiency. Here, we report T-C type COFs (T = trap units, C = catalytic units), demonstrating that units with keto-enol tautomerism can serve as dynamic electron/hole traps (T) to mitigate Coulomb forces. This design effectively facilitates swift charge transfer and extends carrier lifetimes, thereby enhancing reactions at the C units. Imine COFs derived from 2,4,6-trihydroxybenzaldehyde (Tp) outperform those based on 1,3,5-benzenetricarboxaldehyde due to tautomerization. The optimal Tp COF (TpBpy) achieves an H2O2 generation rate of 37.9 μmol h⁻¹ (or 8350 μmol h⁻¹ g⁻¹) under simulated light, and a solar-to-chemical conversion efficiency of 0.038% in a flow reactor under natural sunlight. This work provides molecular design strategies and standard criteria for efficient H2O2 photocatalysts.https://doi.org/10.1038/s41467-025-62286-9 |
| spellingShingle | Fang Ma Tao Gao Xiaodong Sun Chunqiu Han Yongye Wang Anqiang Jiang Ying Zhou Guijie Liang Huiqing Wang Li Wang Binbin Jia Yingping Huang Hongwei Huang Xin Ying Kong Hui Li Niu Huang Tianyi Ma Liqun Ye Keto-enol tautomerism as dynamic electron/hole traps promote charge carrier separation for hydrogen peroxide photosynthesis Nature Communications |
| title | Keto-enol tautomerism as dynamic electron/hole traps promote charge carrier separation for hydrogen peroxide photosynthesis |
| title_full | Keto-enol tautomerism as dynamic electron/hole traps promote charge carrier separation for hydrogen peroxide photosynthesis |
| title_fullStr | Keto-enol tautomerism as dynamic electron/hole traps promote charge carrier separation for hydrogen peroxide photosynthesis |
| title_full_unstemmed | Keto-enol tautomerism as dynamic electron/hole traps promote charge carrier separation for hydrogen peroxide photosynthesis |
| title_short | Keto-enol tautomerism as dynamic electron/hole traps promote charge carrier separation for hydrogen peroxide photosynthesis |
| title_sort | keto enol tautomerism as dynamic electron hole traps promote charge carrier separation for hydrogen peroxide photosynthesis |
| url | https://doi.org/10.1038/s41467-025-62286-9 |
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