Enhanced hydrogen peroxide photosynthesis via charge-complementary π-electron sites
Abstract Organic photocatalysts with porphyrin conjugated chromophore core are promising for artificial hydrogen peroxide (H2O2) photosynthesis, but the lack of bottom-up paradigm for oxygen (O2) adsorption sites hinders their activity. Here, we introduce imidazole groups as π-electron sites with ch...
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| Format: | Article |
| Language: | English |
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Nature Portfolio
2025-07-01
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| Series: | Nature Communications |
| Online Access: | https://doi.org/10.1038/s41467-025-61452-3 |
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| _version_ | 1849234983299842048 |
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| author | Yan Guo Qixin Zhou Li Wang Ziqi Deng David Lee Phillips Chuyang Y. Tang Yongfa Zhu |
| author_facet | Yan Guo Qixin Zhou Li Wang Ziqi Deng David Lee Phillips Chuyang Y. Tang Yongfa Zhu |
| author_sort | Yan Guo |
| collection | DOAJ |
| description | Abstract Organic photocatalysts with porphyrin conjugated chromophore core are promising for artificial hydrogen peroxide (H2O2) photosynthesis, but the lack of bottom-up paradigm for oxygen (O2) adsorption sites hinders their activity. Here, we introduce imidazole groups as π-electron sites with charge-complementarity to the O2 molecules, enhancing O2 binding via sub-atomically mirrored electrostatic cooperative π-π dispersion forces. In situ spectroscopy and theory reveal that the ~2 Å linear δ+-δ−-δ+ domain of the imidazole substituent exhibits 2.8-folds stronger O2 adsorption than neutral π-electron substituents, accompanied by the generation of energetically peroxide intermediates. Consequently, imidazole-substituted porphyrin photocatalysts achieve a solar-to-chemical conversion efficiency of 1.85% using only H2O and O2. In scalable membranes with photocatalysts, enabling daily photosynthetic production of 80 L m−2 of Fenton-applicable H2O2 solution. This work offers a strategy to modulate the electrostatic distribution of oxygen photoreduction sites, providing insights into overcoming gas activation rate-limiting steps in photocatalytic processes. |
| format | Article |
| id | doaj-art-2d3fa57e1ba149ec98e52b718da32c31 |
| institution | Kabale University |
| issn | 2041-1723 |
| language | English |
| publishDate | 2025-07-01 |
| publisher | Nature Portfolio |
| record_format | Article |
| series | Nature Communications |
| spelling | doaj-art-2d3fa57e1ba149ec98e52b718da32c312025-08-20T04:02:56ZengNature PortfolioNature Communications2041-17232025-07-0116111110.1038/s41467-025-61452-3Enhanced hydrogen peroxide photosynthesis via charge-complementary π-electron sitesYan Guo0Qixin Zhou1Li Wang2Ziqi Deng3David Lee Phillips4Chuyang Y. Tang5Yongfa Zhu6Department of Civil Engineering, The University of Hong KongDepartment of Chemistry, Tsinghua UniversityDepartment of Civil Engineering, The University of Hong KongDepartment of Chemistry, The University of Hong KongDepartment of Chemistry, The University of Hong KongDepartment of Civil Engineering, The University of Hong KongDepartment of Chemistry, Tsinghua UniversityAbstract Organic photocatalysts with porphyrin conjugated chromophore core are promising for artificial hydrogen peroxide (H2O2) photosynthesis, but the lack of bottom-up paradigm for oxygen (O2) adsorption sites hinders their activity. Here, we introduce imidazole groups as π-electron sites with charge-complementarity to the O2 molecules, enhancing O2 binding via sub-atomically mirrored electrostatic cooperative π-π dispersion forces. In situ spectroscopy and theory reveal that the ~2 Å linear δ+-δ−-δ+ domain of the imidazole substituent exhibits 2.8-folds stronger O2 adsorption than neutral π-electron substituents, accompanied by the generation of energetically peroxide intermediates. Consequently, imidazole-substituted porphyrin photocatalysts achieve a solar-to-chemical conversion efficiency of 1.85% using only H2O and O2. In scalable membranes with photocatalysts, enabling daily photosynthetic production of 80 L m−2 of Fenton-applicable H2O2 solution. This work offers a strategy to modulate the electrostatic distribution of oxygen photoreduction sites, providing insights into overcoming gas activation rate-limiting steps in photocatalytic processes.https://doi.org/10.1038/s41467-025-61452-3 |
| spellingShingle | Yan Guo Qixin Zhou Li Wang Ziqi Deng David Lee Phillips Chuyang Y. Tang Yongfa Zhu Enhanced hydrogen peroxide photosynthesis via charge-complementary π-electron sites Nature Communications |
| title | Enhanced hydrogen peroxide photosynthesis via charge-complementary π-electron sites |
| title_full | Enhanced hydrogen peroxide photosynthesis via charge-complementary π-electron sites |
| title_fullStr | Enhanced hydrogen peroxide photosynthesis via charge-complementary π-electron sites |
| title_full_unstemmed | Enhanced hydrogen peroxide photosynthesis via charge-complementary π-electron sites |
| title_short | Enhanced hydrogen peroxide photosynthesis via charge-complementary π-electron sites |
| title_sort | enhanced hydrogen peroxide photosynthesis via charge complementary π electron sites |
| url | https://doi.org/10.1038/s41467-025-61452-3 |
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