Anthraquinone-modulated oxygen disproportionation enables highly selective singlet oxygen generation for pollutant degradation

Photocatalytic oxygen activation offers a sustainable technology for singlet oxygen (1O2) synthesis toward the degradation of wastewater contaminants. However, the conventional single O2 activation favors the kinetic desorption of key *O2–/*OOH intermediates, limiting their selective disproportionation to 1O2. Herein, by constructing spatially adjacent C=O sites in anthraquinone-modified covalent organic frameworks (TpDQ-COF), we present a bimolecular oxygen activation pathway that promotes rapid *O2⁻/*OOH disproportionation for selective photocatalytic 1O2 generation. Under visible light irradiation, the TpDQ-COF achieved a highly 1O2 photosynthesis yield of 622.8 μmol L–1 h–1 with 86.3% selectivity, approximately 19.6 times higher than that of TpDA-COF without anthraquinone. Using bisphenol A (BPA) as a model pollutant, the TpDQ-COF achieved nearly 90% degradation within 2 h, concurrently producing value-added small-molecule chemicals. Combined theoretical calculations and in situ Raman spectroscopy revealed that the adjacent C=O groups within anthraquinone of TpDQ-COF accelerate the separation of photoinduced electron–hole (e––h⁺) and O2 adsorption, while simultaneously promoting the *O2–/OOH production and disproportionation, thereby selectively yielding 1O2. This work establishes an anthraquinone-modulated bimolecular oxygen coactivation strategy, providing guidance for the precise control of 1O2 photosynthesis.