Ground-state charge transfer in single-molecule junctions covalent organic frameworks for boosting photocatalytic hydrogen evolution

Abstract Ground-state charge transfer plays a vital role in improving the photocatalytic performance of D-A type covalent organic frameworks. However, limited studies have explored the modulation of photocatalytic performance in COFs-based photocatalysts through ground-state charge transfer. Here we...

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Main Authors: Rongchen Shen, Can Huang, Lei Hao, Guijie Liang, Peng Zhang, Qiang Yue, Xin Li
Format: Article
Language:English
Published: Nature Portfolio 2025-03-01
Series:Nature Communications
Online Access:https://doi.org/10.1038/s41467-025-57662-4
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author Rongchen Shen
Can Huang
Lei Hao
Guijie Liang
Peng Zhang
Qiang Yue
Xin Li
author_facet Rongchen Shen
Can Huang
Lei Hao
Guijie Liang
Peng Zhang
Qiang Yue
Xin Li
author_sort Rongchen Shen
collection DOAJ
description Abstract Ground-state charge transfer plays a vital role in improving the photocatalytic performance of D-A type covalent organic frameworks. However, limited studies have explored the modulation of photocatalytic performance in COFs-based photocatalysts through ground-state charge transfer. Here we show the formation of extremely intense ground-state charge transfer via a unique covalent bonding approach. We transform three-dimensional stacked COF-based S-scheme heterojunctions (FOOCOF-PDIU) into co-planar single-molecule junctions (FOOCOF-PDI). This co-planar single-molecule junction structure exhibits strong ground-state charge transfer compared to the traditional randomly stacked heterojunctions and individual COFs. Ground-state charge transfer induces charge redistribution and dipole moment formation, which enhances the built-in electric field intensity in single-molecule junctions. This enhanced built-in electric field promotes exciton dissociation and charge separation, resulting in improved photocatalytic efficiency. Therefore, a stable molecule-decorated COF with broad light absorption has been successfully obtained, whose hydrogen evolution rate can reach 265 mmol g−1 h−1. This work opens an avenue for exploiting photocatalytic mechanisms in COFs based on ground-state charge transfer effects.
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issn 2041-1723
language English
publishDate 2025-03-01
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spelling doaj-art-7c1a71c655bf49249bdb90a6438c8b6b2025-08-20T02:56:11ZengNature PortfolioNature Communications2041-17232025-03-0116111010.1038/s41467-025-57662-4Ground-state charge transfer in single-molecule junctions covalent organic frameworks for boosting photocatalytic hydrogen evolutionRongchen Shen0Can Huang1Lei Hao2Guijie Liang3Peng Zhang4Qiang Yue5Xin Li6Institute of Biomass Engineering, Key Laboratory of Energy Plants Resource and Utilization, Ministry of Agriculture and Rural Affairs, South China Agricultural UniversityInstitute of Biomass Engineering, Key Laboratory of Energy Plants Resource and Utilization, Ministry of Agriculture and Rural Affairs, South China Agricultural UniversityInstitute of Biomass Engineering, Key Laboratory of Energy Plants Resource and Utilization, Ministry of Agriculture and Rural Affairs, South China Agricultural UniversityHubei Key Laboratory of Low Dimensional Optoelectronic Materials and Devices, Hubei University of Arts and ScienceState Centre for International Cooperation on Designer Low-Carbon & Environmental Materials (CDLCEM), School of Materials Science and Engineering, Zhengzhou UniversityGuangdong Provincial Key Laboratory of Utilization and Conservation of Food and Medicinal Resources in Northern Region, Shaoguan UniversityInstitute of Biomass Engineering, Key Laboratory of Energy Plants Resource and Utilization, Ministry of Agriculture and Rural Affairs, South China Agricultural UniversityAbstract Ground-state charge transfer plays a vital role in improving the photocatalytic performance of D-A type covalent organic frameworks. However, limited studies have explored the modulation of photocatalytic performance in COFs-based photocatalysts through ground-state charge transfer. Here we show the formation of extremely intense ground-state charge transfer via a unique covalent bonding approach. We transform three-dimensional stacked COF-based S-scheme heterojunctions (FOOCOF-PDIU) into co-planar single-molecule junctions (FOOCOF-PDI). This co-planar single-molecule junction structure exhibits strong ground-state charge transfer compared to the traditional randomly stacked heterojunctions and individual COFs. Ground-state charge transfer induces charge redistribution and dipole moment formation, which enhances the built-in electric field intensity in single-molecule junctions. This enhanced built-in electric field promotes exciton dissociation and charge separation, resulting in improved photocatalytic efficiency. Therefore, a stable molecule-decorated COF with broad light absorption has been successfully obtained, whose hydrogen evolution rate can reach 265 mmol g−1 h−1. This work opens an avenue for exploiting photocatalytic mechanisms in COFs based on ground-state charge transfer effects.https://doi.org/10.1038/s41467-025-57662-4
spellingShingle Rongchen Shen
Can Huang
Lei Hao
Guijie Liang
Peng Zhang
Qiang Yue
Xin Li
Ground-state charge transfer in single-molecule junctions covalent organic frameworks for boosting photocatalytic hydrogen evolution
Nature Communications
title Ground-state charge transfer in single-molecule junctions covalent organic frameworks for boosting photocatalytic hydrogen evolution
title_full Ground-state charge transfer in single-molecule junctions covalent organic frameworks for boosting photocatalytic hydrogen evolution
title_fullStr Ground-state charge transfer in single-molecule junctions covalent organic frameworks for boosting photocatalytic hydrogen evolution
title_full_unstemmed Ground-state charge transfer in single-molecule junctions covalent organic frameworks for boosting photocatalytic hydrogen evolution
title_short Ground-state charge transfer in single-molecule junctions covalent organic frameworks for boosting photocatalytic hydrogen evolution
title_sort ground state charge transfer in single molecule junctions covalent organic frameworks for boosting photocatalytic hydrogen evolution
url https://doi.org/10.1038/s41467-025-57662-4
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