Cobaloxime-integrated covalent organic frameworks for photocatalytic hydrogen evolution coupled with alcohol oxidation
We report an azide-functionalized cobaloxime proton-reduction catalyst covalently tethered into the Wurster-type covalent organic frameworks (COFs). The cobaloxime-modified COF photocatalysts exhibit enhanced photocatalytic activity for hydrogen evolution reaction (HER) in alcohol-containing solutio...
| Main Authors: | , , , , , , , , , |
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| Format: | Journal Article |
| Language: | English |
| Published: |
2023
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| Online Access: | https://hdl.handle.net/10356/171334 |
| _version_ | 1811677769042493440 |
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| author | Wang, Shihuai Wu, Tai Wu, Shuyang Guo, Jingjing He, Ting Wu, Yinglong Yuan, Wei Zhang, Zhengyang Hua, Yong Zhao, Yanli |
| author2 | School of Chemistry, Chemical Engineering and Biotechnology |
| author_facet | School of Chemistry, Chemical Engineering and Biotechnology Wang, Shihuai Wu, Tai Wu, Shuyang Guo, Jingjing He, Ting Wu, Yinglong Yuan, Wei Zhang, Zhengyang Hua, Yong Zhao, Yanli |
| author_sort | Wang, Shihuai |
| collection | NTU |
| description | We report an azide-functionalized cobaloxime proton-reduction catalyst covalently tethered into the Wurster-type covalent organic frameworks (COFs). The cobaloxime-modified COF photocatalysts exhibit enhanced photocatalytic activity for hydrogen evolution reaction (HER) in alcohol-containing solution with no presence of a typical sacrificial agent. The best performing cobaloxime-modified COF hybrid catalyzes hydrogen production with an average HER rate up to 38 μmol h-1 in ethanol/phosphate buffer solution under 4 h illumination. Ultrafast transient optical spectroscopy characterizations and charge carrier analysis reveal that the alcohol contents functioning as hole scavengers could be oxidized by the photogenerated holes of COFs to form aldehydes and protons. The consumption of the photogenerated holes thus suppresses exciton recombination of COFs and improves the ratio of free electrons that were effectively utilized to drive catalytic reaction for HER. This work demonstrates a great potential of COF-catalyzed HER using alcohol solvents as hole scavengers and provides an example toward realizing the accessibility to the scope of reaction conditions and a greener route for energy conversion. |
| first_indexed | 2024-10-01T02:42:37Z |
| format | Journal Article |
| id | ntu-10356/171334 |
| institution | Nanyang Technological University |
| language | English |
| last_indexed | 2024-10-01T02:42:37Z |
| publishDate | 2023 |
| record_format | dspace |
| spelling | ntu-10356/1713342024-03-22T15:31:38Z Cobaloxime-integrated covalent organic frameworks for photocatalytic hydrogen evolution coupled with alcohol oxidation Wang, Shihuai Wu, Tai Wu, Shuyang Guo, Jingjing He, Ting Wu, Yinglong Yuan, Wei Zhang, Zhengyang Hua, Yong Zhao, Yanli School of Chemistry, Chemical Engineering and Biotechnology Chemistry Alcohol Oxidation Cobaloxime We report an azide-functionalized cobaloxime proton-reduction catalyst covalently tethered into the Wurster-type covalent organic frameworks (COFs). The cobaloxime-modified COF photocatalysts exhibit enhanced photocatalytic activity for hydrogen evolution reaction (HER) in alcohol-containing solution with no presence of a typical sacrificial agent. The best performing cobaloxime-modified COF hybrid catalyzes hydrogen production with an average HER rate up to 38 μmol h-1 in ethanol/phosphate buffer solution under 4 h illumination. Ultrafast transient optical spectroscopy characterizations and charge carrier analysis reveal that the alcohol contents functioning as hole scavengers could be oxidized by the photogenerated holes of COFs to form aldehydes and protons. The consumption of the photogenerated holes thus suppresses exciton recombination of COFs and improves the ratio of free electrons that were effectively utilized to drive catalytic reaction for HER. This work demonstrates a great potential of COF-catalyzed HER using alcohol solvents as hole scavengers and provides an example toward realizing the accessibility to the scope of reaction conditions and a greener route for energy conversion. Agency for Science, Technology and Research (A*STAR) Ministry of Education (MOE) Submitted/Accepted version S.W. gratefully acknowledges a postdoc grant from the Knut and Alice Wallenberg Foundation of Sweden. Y.H. thanks High-Level Talents Introduction in Yunnan Province (C619300A010), and the Fund for Excellent Young Scholars of Yunnan (202001AW070008) for financial support. Z.Z. thanks the Singapore Agency for Science, Technology and Research (A*STAR) AME YIRG grant (A2084c0065) and MTC IRG grant (M21K2c0110). Y.Z. thanks the financial support from the Ministry of Education Singapore under its Academic Research Funds (RG85/22, RG3/21 and MOET2EP10120-0003). 2023-10-19T03:32:46Z 2023-10-19T03:32:46Z 2023 Journal Article Wang, S., Wu, T., Wu, S., Guo, J., He, T., Wu, Y., Yuan, W., Zhang, Z., Hua, Y. & Zhao, Y. (2023). Cobaloxime-integrated covalent organic frameworks for photocatalytic hydrogen evolution coupled with alcohol oxidation. Angewandte Chemie International Edition, 62(44), e202311082-. https://dx.doi.org/10.1002/anie.202311082 1433-7851 https://hdl.handle.net/10356/171334 10.1002/anie.202311082 37698088 2-s2.0-85171430832 44 62 e202311082 en A2084c0065 M21K2c0110 RG85/22 RG3/21 MOET2EP10120-0003 Angewandte Chemie International Edition © 2023 Wiley-VCH GmbH. All rights reserved. This article may be downloaded for personal use only. Any other use requires prior permission of the copyright holder. The Version of Record is available online at http://doi.org/10.1002/anie.202311082. application/pdf |
| spellingShingle | Chemistry Alcohol Oxidation Cobaloxime Wang, Shihuai Wu, Tai Wu, Shuyang Guo, Jingjing He, Ting Wu, Yinglong Yuan, Wei Zhang, Zhengyang Hua, Yong Zhao, Yanli Cobaloxime-integrated covalent organic frameworks for photocatalytic hydrogen evolution coupled with alcohol oxidation |
| title | Cobaloxime-integrated covalent organic frameworks for photocatalytic hydrogen evolution coupled with alcohol oxidation |
| title_full | Cobaloxime-integrated covalent organic frameworks for photocatalytic hydrogen evolution coupled with alcohol oxidation |
| title_fullStr | Cobaloxime-integrated covalent organic frameworks for photocatalytic hydrogen evolution coupled with alcohol oxidation |
| title_full_unstemmed | Cobaloxime-integrated covalent organic frameworks for photocatalytic hydrogen evolution coupled with alcohol oxidation |
| title_short | Cobaloxime-integrated covalent organic frameworks for photocatalytic hydrogen evolution coupled with alcohol oxidation |
| title_sort | cobaloxime integrated covalent organic frameworks for photocatalytic hydrogen evolution coupled with alcohol oxidation |
| topic | Chemistry Alcohol Oxidation Cobaloxime |
| url | https://hdl.handle.net/10356/171334 |
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