Enhancing photocatalytic efficiency through surface modification to manipulate internal electron-hole distribution

Abstract In this study, we synthesized ten g-C3N4-based covalent organic frameworks (COFs) and identified CN-306 as the most effective catalyst for visible-light-driven hydrogen peroxide (H2O2) production. Systematic optimization revealed that increasing ethanol proportions in the reaction medium si...

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Main Authors: Hong Tu, Bihong Tian, Shunshun Chen, Jingyi Xu, Jianrong Yang, Zhichao Zhao, Shunhong Chen, Jian Wu
Format: Article
Language:English
Published: Nature Portfolio 2025-05-01
Series:npj Clean Water
Online Access:https://doi.org/10.1038/s41545-025-00480-4
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author Hong Tu
Bihong Tian
Shunshun Chen
Jingyi Xu
Jianrong Yang
Zhichao Zhao
Shunhong Chen
Jian Wu
author_facet Hong Tu
Bihong Tian
Shunshun Chen
Jingyi Xu
Jianrong Yang
Zhichao Zhao
Shunhong Chen
Jian Wu
author_sort Hong Tu
collection DOAJ
description Abstract In this study, we synthesized ten g-C3N4-based covalent organic frameworks (COFs) and identified CN-306 as the most effective catalyst for visible-light-driven hydrogen peroxide (H2O2) production. Systematic optimization revealed that increasing ethanol proportions in the reaction medium significantly enhanced H2O2 yield, achieving a remarkable production rate of 5352 μmol g−1h−1 with a surface quantum efficiency of 7.27% at λ = 420 nm. Intriguingly, mechanistic investigations uncovered that excessive generation of singlet oxygen (1O2) acts as a critical inhibitory factor, impeding H2O2 accumulation. Multimodal characterization techniques combined with density functional theory (DFT) calculations were employed to unravel the origin of CN-306’s superior performance. Theoretical analyses demonstrated that CN-306 exhibits enhanced electron-hole separation efficiency, attributed to its reduced energy gap between the highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO), which facilitates photocarrier migration and suppresses detrimental recombination. Furthermore, this work elucidates the structure-function relationships governing site-specific functional group modifications in COFs and their profound influence on photocatalytic activity. These findings provide molecular-level insights into rational catalyst design for optimizing surface structures and advancing solar-driven H2O2 synthesis applications.
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issn 2059-7037
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spelling doaj-art-0212ac61c635429ab49e508491b4e8452025-08-20T03:16:33ZengNature Portfolionpj Clean Water2059-70372025-05-018111010.1038/s41545-025-00480-4Enhancing photocatalytic efficiency through surface modification to manipulate internal electron-hole distributionHong Tu0Bihong Tian1Shunshun Chen2Jingyi Xu3Jianrong Yang4Zhichao Zhao5Shunhong Chen6Jian Wu7State Key Laboratory of Green Pesticide, Guizhou UniversityState Key Laboratory of Green Pesticide, Guizhou UniversityState Key Laboratory of Green Pesticide, Guizhou UniversityState Key Laboratory of Green Pesticide, Guizhou UniversityState Key Laboratory of Green Pesticide, Guizhou UniversityState Key Laboratory of Green Pesticide, Guizhou UniversityState Key Laboratory of Green Pesticide, Guizhou UniversityState Key Laboratory of Green Pesticide, Guizhou UniversityAbstract In this study, we synthesized ten g-C3N4-based covalent organic frameworks (COFs) and identified CN-306 as the most effective catalyst for visible-light-driven hydrogen peroxide (H2O2) production. Systematic optimization revealed that increasing ethanol proportions in the reaction medium significantly enhanced H2O2 yield, achieving a remarkable production rate of 5352 μmol g−1h−1 with a surface quantum efficiency of 7.27% at λ = 420 nm. Intriguingly, mechanistic investigations uncovered that excessive generation of singlet oxygen (1O2) acts as a critical inhibitory factor, impeding H2O2 accumulation. Multimodal characterization techniques combined with density functional theory (DFT) calculations were employed to unravel the origin of CN-306’s superior performance. Theoretical analyses demonstrated that CN-306 exhibits enhanced electron-hole separation efficiency, attributed to its reduced energy gap between the highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO), which facilitates photocarrier migration and suppresses detrimental recombination. Furthermore, this work elucidates the structure-function relationships governing site-specific functional group modifications in COFs and their profound influence on photocatalytic activity. These findings provide molecular-level insights into rational catalyst design for optimizing surface structures and advancing solar-driven H2O2 synthesis applications.https://doi.org/10.1038/s41545-025-00480-4
spellingShingle Hong Tu
Bihong Tian
Shunshun Chen
Jingyi Xu
Jianrong Yang
Zhichao Zhao
Shunhong Chen
Jian Wu
Enhancing photocatalytic efficiency through surface modification to manipulate internal electron-hole distribution
npj Clean Water
title Enhancing photocatalytic efficiency through surface modification to manipulate internal electron-hole distribution
title_full Enhancing photocatalytic efficiency through surface modification to manipulate internal electron-hole distribution
title_fullStr Enhancing photocatalytic efficiency through surface modification to manipulate internal electron-hole distribution
title_full_unstemmed Enhancing photocatalytic efficiency through surface modification to manipulate internal electron-hole distribution
title_short Enhancing photocatalytic efficiency through surface modification to manipulate internal electron-hole distribution
title_sort enhancing photocatalytic efficiency through surface modification to manipulate internal electron hole distribution
url https://doi.org/10.1038/s41545-025-00480-4
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