Dual donor-acceptor covalent organic frameworks for hydrogen peroxide photosynthesis

Chencheng Qin; Xiaodong Wu; Lin Tang; Xiaohong Chen; Miao Li; Yi Mou; Bo Su; Sibo Wang; Chengyang Feng; Jiawei Liu; Xingzhong Yuan; Yanli Zhao; Hou Wang

doi:10.1038/s41467-023-40991-7

Dual donor-acceptor covalent organic frameworks for hydrogen peroxide photosynthesis

Chencheng Qin, Xiaodong Wu, Lin Tang, Xiaohong Chen, Miao Li, Yi Mou, Bo Su, Sibo Wang, Chengyang Feng, Jiawei Liu, Xingzhong Yuan, Yanli Zhao, Hou Wang

Physical Sciences and Engineering

Research output: Contribution to journal › Article › peer-review

166 Scopus citations

Abstract

Constructing photocatalytically active and stable covalent organic frameworks containing both oxidative and reductive reaction centers remain a challenge. In this study, benzotrithiophene-based covalent organic frameworks with spatially separated redox centers are rationally designed for the photocatalytic production of hydrogen peroxide from water and oxygen without sacrificial agents. The triazine-containing framework demonstrates high selectivity for H2O2 photogeneration, with a yield rate of 2111 μM h−1 (21.11 μmol h−1 and 1407 μmol g−1 h−1) and a solar-to-chemical conversion efficiency of 0.296%. Codirectional charge transfer and large energetic differences between linkages and linkers are verified in the double donor-acceptor structures of periodic frameworks. The active sites are mainly concentrated on the electron-acceptor fragments near the imine bond, which regulate the electron distribution of adjacent carbon atoms to optimally reduce the Gibbs free energy of O2* and OOH* intermediates during the formation of H2O2.

Original language	English (US)
Journal	Nature Communications
Volume	14
Issue number	1
DOIs	https://doi.org/10.1038/s41467-023-40991-7
State	Published - Aug 28 2023

Bibliographical note

KAUST Repository Item: Exported on 2023-09-01
Acknowledgements: The authors gratefully acknowledge the financial support provided by the National Natural Science Foundation of China (No. 22178091 (H.W.), 72088101 (X.C.), 51708195 (H.W.), 51739004 (X.Y.) and 52202367 (X.W.), the Provincial Natural Science Foundation of Hunan (No. 2023JJ10012 (H.W.)), the Science and Technology Innovation Program of Hunan Province (No. 2022RC1120 (H.W.)), the National Key Research and Development Program of China (No. 2021YFC1910400 (L.T.)), the Nature Science Foundation of Jiangsu Province (No. BK20200711 (X.W.)), the Key Laboratory of Advanced Functional Composites Technology (No. 6142906210508 (X.W.)), the Fundamental Research Funds for the Central Universities (No. 531118010675 (H.W.)), and the Ministry of Education Singapore under its Academic Research Funds (No. RG3/21, RG85/22, and MOET2EP10120-0003 (Y.Z.)).

ASJC Scopus subject areas

General Biochemistry, Genetics and Molecular Biology
General Chemistry
General Physics and Astronomy

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10.1038/s41467-023-40991-7

https://repository.kaust.edu.sa/bitstream/10754/693903/1/s41467-023-40991-7.pdf

Cite this

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title = "Dual donor-acceptor covalent organic frameworks for hydrogen peroxide photosynthesis",

abstract = "Constructing photocatalytically active and stable covalent organic frameworks containing both oxidative and reductive reaction centers remain a challenge. In this study, benzotrithiophene-based covalent organic frameworks with spatially separated redox centers are rationally designed for the photocatalytic production of hydrogen peroxide from water and oxygen without sacrificial agents. The triazine-containing framework demonstrates high selectivity for H2O2 photogeneration, with a yield rate of 2111 μM h−1 (21.11 μmol h−1 and 1407 μmol g−1 h−1) and a solar-to-chemical conversion efficiency of 0.296%. Codirectional charge transfer and large energetic differences between linkages and linkers are verified in the double donor-acceptor structures of periodic frameworks. The active sites are mainly concentrated on the electron-acceptor fragments near the imine bond, which regulate the electron distribution of adjacent carbon atoms to optimally reduce the Gibbs free energy of O2* and OOH* intermediates during the formation of H2O2.",

author = "Chencheng Qin and Xiaodong Wu and Lin Tang and Xiaohong Chen and Miao Li and Yi Mou and Bo Su and Sibo Wang and Chengyang Feng and Jiawei Liu and Xingzhong Yuan and Yanli Zhao and Hou Wang",

note = "KAUST Repository Item: Exported on 2023-09-01 Acknowledgements: The authors gratefully acknowledge the financial support provided by the National Natural Science Foundation of China (No. 22178091 (H.W.), 72088101 (X.C.), 51708195 (H.W.), 51739004 (X.Y.) and 52202367 (X.W.), the Provincial Natural Science Foundation of Hunan (No. 2023JJ10012 (H.W.)), the Science and Technology Innovation Program of Hunan Province (No. 2022RC1120 (H.W.)), the National Key Research and Development Program of China (No. 2021YFC1910400 (L.T.)), the Nature Science Foundation of Jiangsu Province (No. BK20200711 (X.W.)), the Key Laboratory of Advanced Functional Composites Technology (No. 6142906210508 (X.W.)), the Fundamental Research Funds for the Central Universities (No. 531118010675 (H.W.)), and the Ministry of Education Singapore under its Academic Research Funds (No. RG3/21, RG85/22, and MOET2EP10120-0003 (Y.Z.)).",

year = "2023",

month = aug,

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doi = "10.1038/s41467-023-40991-7",

language = "English (US)",

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T1 - Dual donor-acceptor covalent organic frameworks for hydrogen peroxide photosynthesis

AU - Qin, Chencheng

AU - Wu, Xiaodong

AU - Tang, Lin

AU - Chen, Xiaohong

AU - Li, Miao

AU - Mou, Yi

AU - Su, Bo

AU - Wang, Sibo

AU - Feng, Chengyang

AU - Liu, Jiawei

AU - Yuan, Xingzhong

AU - Zhao, Yanli

AU - Wang, Hou

N1 - KAUST Repository Item: Exported on 2023-09-01 Acknowledgements: The authors gratefully acknowledge the financial support provided by the National Natural Science Foundation of China (No. 22178091 (H.W.), 72088101 (X.C.), 51708195 (H.W.), 51739004 (X.Y.) and 52202367 (X.W.), the Provincial Natural Science Foundation of Hunan (No. 2023JJ10012 (H.W.)), the Science and Technology Innovation Program of Hunan Province (No. 2022RC1120 (H.W.)), the National Key Research and Development Program of China (No. 2021YFC1910400 (L.T.)), the Nature Science Foundation of Jiangsu Province (No. BK20200711 (X.W.)), the Key Laboratory of Advanced Functional Composites Technology (No. 6142906210508 (X.W.)), the Fundamental Research Funds for the Central Universities (No. 531118010675 (H.W.)), and the Ministry of Education Singapore under its Academic Research Funds (No. RG3/21, RG85/22, and MOET2EP10120-0003 (Y.Z.)).

PY - 2023/8/28

Y1 - 2023/8/28

N2 - Constructing photocatalytically active and stable covalent organic frameworks containing both oxidative and reductive reaction centers remain a challenge. In this study, benzotrithiophene-based covalent organic frameworks with spatially separated redox centers are rationally designed for the photocatalytic production of hydrogen peroxide from water and oxygen without sacrificial agents. The triazine-containing framework demonstrates high selectivity for H2O2 photogeneration, with a yield rate of 2111 μM h−1 (21.11 μmol h−1 and 1407 μmol g−1 h−1) and a solar-to-chemical conversion efficiency of 0.296%. Codirectional charge transfer and large energetic differences between linkages and linkers are verified in the double donor-acceptor structures of periodic frameworks. The active sites are mainly concentrated on the electron-acceptor fragments near the imine bond, which regulate the electron distribution of adjacent carbon atoms to optimally reduce the Gibbs free energy of O2* and OOH* intermediates during the formation of H2O2.

AB - Constructing photocatalytically active and stable covalent organic frameworks containing both oxidative and reductive reaction centers remain a challenge. In this study, benzotrithiophene-based covalent organic frameworks with spatially separated redox centers are rationally designed for the photocatalytic production of hydrogen peroxide from water and oxygen without sacrificial agents. The triazine-containing framework demonstrates high selectivity for H2O2 photogeneration, with a yield rate of 2111 μM h−1 (21.11 μmol h−1 and 1407 μmol g−1 h−1) and a solar-to-chemical conversion efficiency of 0.296%. Codirectional charge transfer and large energetic differences between linkages and linkers are verified in the double donor-acceptor structures of periodic frameworks. The active sites are mainly concentrated on the electron-acceptor fragments near the imine bond, which regulate the electron distribution of adjacent carbon atoms to optimally reduce the Gibbs free energy of O2* and OOH* intermediates during the formation of H2O2.

UR - http://hdl.handle.net/10754/693903

UR - https://www.nature.com/articles/s41467-023-40991-7

U2 - 10.1038/s41467-023-40991-7

DO - 10.1038/s41467-023-40991-7

M3 - Article

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SN - 2041-1723

VL - 14

JO - Nature Communications

JF - Nature Communications

IS - 1

ER -

Dual donor-acceptor covalent organic frameworks for hydrogen peroxide photosynthesis

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