Stoichiometry-driven electronic heterogeneity in covalent organic frameworks for coupled H<sub>2</sub>O<sub>2</sub> photoproduction and chemoselective fragrance upgrading.
basic_science · Level V
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- Also identified by DOI 10.1038/s41467-026-76734-7.
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Abstract
Coupling H<sub>2</sub>O<sub>2</sub> photoproduction with value-added organic transformations avoids the sluggish kinetics of water oxidation, yet integrating both processes within one photocatalyst remains challenging. Here, we report stoichiometry-driven electronic heterogeneity in covalent organic frameworks (COFs) as a strategy for simultaneous H<sub>2</sub>O<sub>2</sub> photoproduction and chemoselective fragrance upgrading. Adjusting monomer stoichiometry with distinct geometric symmetries perturbs local structural symmetry, generating electronically differentiated microenvironments within the COF skeleton. The optimized PTPD-COF1 achieves a H<sub>2</sub>O<sub>2</sub> photosynthetic rate of 10.4 mmol g<sup>-1</sup> h<sup>-1</sup> in pure water, surpassing its binary analogues, and delivers coupled rates of 36.1, 53.2, and 21.6 mmol g<sup>-1</sup> h<sup>-1</sup> with near-quantitative, chemoselective conversion of cinnamyl, anisyl, and o-anisyl alcohols into fragrances. Theoretical analysis shows the modulated electronic environment enhances local dipole moments and lowers carrier effective masses, altering energy barriers for *OOH/*OH formation and C-H cleavage. In this work, stoichiometry-driven electronic heterogeneity is established as a design principle for multifunctional organic photocatalysts.