Revealing the Mechanism of Exciton Spontaneous Separation at Room Temperature for Efficient Photocatalytic Hydrogen Peroxide Synthesis

Abstract The photocatalytic synthesis of hydrogen peroxide (H 2 O 2 ) at room temperature has garnered significant attention as an environmentally friendly alternative to traditional anthraquinone oxidation processes. However, the low exciton dissociation efficiency at room temperature often hinders photocatalytic performance. In this study, it is demonstrated that tuning the substitution sites of electron donors in Donor‐Acceptor (D‐A) conjugated polymers can significantly enhance exciton dissociation by reducing exciton activation energy, which facilitates the spontaneous separation of excitons at room temperature. For comparison, materials with exciton separation energies ≈89 meV exhibit a hydrogen peroxide production rate of 2692 µmol·g −1 ·h −1 . In contrast, the main material developed in this work, O‐PTAQ, demonstrates a substantially lower exciton separation energy of 22 meV, resulting in a hydrogen peroxide production rate of 4989 µmol·g −1 ·h −1 under ambient conditions, outperforming most reported organic semiconductors. This enhancement is attributed to the increased electron delocalization in the electron donors, which lowers exciton activation energy to promote efficient exciton separation. The findings highlight the critical role of molecular‐level structural tuning in enhancing exciton dissociation, providing a promising strategy for the development of high‐efficiency photocatalysts for sustainable H 2 O 2 production.