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...
Saved in:
| Main Authors: | , , , , , , |
|---|---|
| Format: | Article |
| Language: | English |
| Published: |
Nature Portfolio
2025-07-01
|
| Series: | Nature Communications |
| Online Access: | https://doi.org/10.1038/s41467-025-61452-3 |
| Tags: |
Add Tag
No Tags, Be the first to tag this record!
|
| Summary: | 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. |
|---|---|
| ISSN: | 2041-1723 |