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...

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Main Authors: Wang, Shihuai, Wu, Tai, Wu, Shuyang, Guo, Jingjing, He, Ting, Wu, Yinglong, Yuan, Wei, Zhang, Zhengyang, Hua, Yong, Zhao, Yanli
Other Authors: School of Chemistry, Chemical Engineering and Biotechnology
Format: Article
Language:English
Published: 2023
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Online Access:https://hdl.handle.net/10356/171334
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Institution: Nanyang Technological University
Language: English
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spelling sg-ntu-dr.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
institution Nanyang Technological University
building NTU Library
continent Asia
country Singapore
Singapore
content_provider NTU Library
collection DR-NTU
language English
topic Chemistry
Alcohol Oxidation
Cobaloxime
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
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.
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
format Article
author Wang, Shihuai
Wu, Tai
Wu, Shuyang
Guo, Jingjing
He, Ting
Wu, Yinglong
Yuan, Wei
Zhang, Zhengyang
Hua, Yong
Zhao, Yanli
author_sort Wang, Shihuai
title 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_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_sort cobaloxime-integrated covalent organic frameworks for photocatalytic hydrogen evolution coupled with alcohol oxidation
publishDate 2023
url https://hdl.handle.net/10356/171334
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