Synthesis of Pore‐Wall‐Modified Stable COF/TiO2 Heterostructures via Site‐Specific Nucleation for an Enhanced Photoreduction of Carbon Dioxide
Abstract Constructing stable heterostructures with appropriate active site architectures in covalent organic frameworks (COFs) can improve the active site accessibility and facilitate charge transfer, thereby increasing the catalytic efficiency. Herein, a pore‐wall modification strategy is proposed...
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| Format: | Article |
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Wiley
2023-05-01
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| Series: | Advanced Science |
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| Online Access: | https://doi.org/10.1002/advs.202300073 |
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| author | Akkammagari Putta Rangappa Dharani Praveen Kumar Khai H. Do Jinming Wang Yuexing Zhang Tae Kyu Kim |
| author_facet | Akkammagari Putta Rangappa Dharani Praveen Kumar Khai H. Do Jinming Wang Yuexing Zhang Tae Kyu Kim |
| author_sort | Akkammagari Putta Rangappa |
| collection | DOAJ |
| description | Abstract Constructing stable heterostructures with appropriate active site architectures in covalent organic frameworks (COFs) can improve the active site accessibility and facilitate charge transfer, thereby increasing the catalytic efficiency. Herein, a pore‐wall modification strategy is proposed to achieve regularly arranged TiO2 nanodots (≈1.82 nm) in the pores of COFs via site‐specific nucleation. The site‐specific nucleation strategy stabilizes the TiO2 nanodots as well as enables the controlled growth of TiO2 throughout the COFs’ matrix. In a typical process, the pore wall is modified and site‐specific nucleation is induced between the metal precursors and the organic walls of the COFs through a careful ligand selection, and the strongly bonded metal precursors drive the confined growth of ultrasmall TiO2 nanodots during the subsequent hydrolysis. This will result in remarkably improved surface reactions, owing to the superior catalytic activity of TiO2 nanodots functionalized to COFs through strong NTiO bonds. Furthermore, density functional theory studies reveal that pore‐wall modification is beneficial for inducing strong interactions between the COF and TiO2 and results in a large energy transfer via the NTiO bonds. This work highlights the feasibility of developing stable COF and metal oxide based heterostructures via organic wall modifications to produce carbon fuels by artificial photosynthesis. |
| format | Article |
| id | doaj-art-939d1933967a44ca83c8a69e0b6e4626 |
| institution | DOAJ |
| issn | 2198-3844 |
| language | English |
| publishDate | 2023-05-01 |
| publisher | Wiley |
| record_format | Article |
| series | Advanced Science |
| spelling | doaj-art-939d1933967a44ca83c8a69e0b6e46262025-08-20T03:04:57ZengWileyAdvanced Science2198-38442023-05-011014n/an/a10.1002/advs.202300073Synthesis of Pore‐Wall‐Modified Stable COF/TiO2 Heterostructures via Site‐Specific Nucleation for an Enhanced Photoreduction of Carbon DioxideAkkammagari Putta Rangappa0Dharani Praveen Kumar1Khai H. Do2Jinming Wang3Yuexing Zhang4Tae Kyu Kim5Department of Chemistry Yonsei University Seoul 03722 Republic of KoreaDepartment of Chemistry Yonsei University Seoul 03722 Republic of KoreaDepartment of Chemistry Yonsei University Seoul 03722 Republic of KoreaDepartment of Chemistry Yonsei University Seoul 03722 Republic of KoreaCollege of Chemistry and Chemical Engineering Dezhou University Dezhou 253023 ChinaDepartment of Chemistry Yonsei University Seoul 03722 Republic of KoreaAbstract Constructing stable heterostructures with appropriate active site architectures in covalent organic frameworks (COFs) can improve the active site accessibility and facilitate charge transfer, thereby increasing the catalytic efficiency. Herein, a pore‐wall modification strategy is proposed to achieve regularly arranged TiO2 nanodots (≈1.82 nm) in the pores of COFs via site‐specific nucleation. The site‐specific nucleation strategy stabilizes the TiO2 nanodots as well as enables the controlled growth of TiO2 throughout the COFs’ matrix. In a typical process, the pore wall is modified and site‐specific nucleation is induced between the metal precursors and the organic walls of the COFs through a careful ligand selection, and the strongly bonded metal precursors drive the confined growth of ultrasmall TiO2 nanodots during the subsequent hydrolysis. This will result in remarkably improved surface reactions, owing to the superior catalytic activity of TiO2 nanodots functionalized to COFs through strong NTiO bonds. Furthermore, density functional theory studies reveal that pore‐wall modification is beneficial for inducing strong interactions between the COF and TiO2 and results in a large energy transfer via the NTiO bonds. This work highlights the feasibility of developing stable COF and metal oxide based heterostructures via organic wall modifications to produce carbon fuels by artificial photosynthesis.https://doi.org/10.1002/advs.202300073CO2 reductioncovalent organic frameworkNTiO bondphotocatalysispore‐wall modificationsite‐specific nucleation |
| spellingShingle | Akkammagari Putta Rangappa Dharani Praveen Kumar Khai H. Do Jinming Wang Yuexing Zhang Tae Kyu Kim Synthesis of Pore‐Wall‐Modified Stable COF/TiO2 Heterostructures via Site‐Specific Nucleation for an Enhanced Photoreduction of Carbon Dioxide Advanced Science CO2 reduction covalent organic framework NTiO bond photocatalysis pore‐wall modification site‐specific nucleation |
| title | Synthesis of Pore‐Wall‐Modified Stable COF/TiO2 Heterostructures via Site‐Specific Nucleation for an Enhanced Photoreduction of Carbon Dioxide |
| title_full | Synthesis of Pore‐Wall‐Modified Stable COF/TiO2 Heterostructures via Site‐Specific Nucleation for an Enhanced Photoreduction of Carbon Dioxide |
| title_fullStr | Synthesis of Pore‐Wall‐Modified Stable COF/TiO2 Heterostructures via Site‐Specific Nucleation for an Enhanced Photoreduction of Carbon Dioxide |
| title_full_unstemmed | Synthesis of Pore‐Wall‐Modified Stable COF/TiO2 Heterostructures via Site‐Specific Nucleation for an Enhanced Photoreduction of Carbon Dioxide |
| title_short | Synthesis of Pore‐Wall‐Modified Stable COF/TiO2 Heterostructures via Site‐Specific Nucleation for an Enhanced Photoreduction of Carbon Dioxide |
| title_sort | synthesis of pore wall modified stable cof tio2 heterostructures via site specific nucleation for an enhanced photoreduction of carbon dioxide |
| topic | CO2 reduction covalent organic framework NTiO bond photocatalysis pore‐wall modification site‐specific nucleation |
| url | https://doi.org/10.1002/advs.202300073 |
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