Harmonizing the Pyrene and Ether Groups in Covalent Triazine Polymers for Highly Effective H ₂ O ₂ Photosynthesis via One‐Step Two‐Electron Oxygen Reduction

Abstract Photocatalytic oxygen reduction to industrially valuable hydrogen peroxide (H 2 O 2 ) in the presence of water without sacrificial agents is highly desirable but challenging in the context of carbon neutrality. As a type of metal‐free photocatalysts, covalent triazine polymers (CTPs) have great potential in photocatalytic H 2 O 2 evolution. In this paper, a strategy is proposed by simultaneously introducing the pyrene (Py) and ether (Et) groups into covalent triazine polymers to fabricate CTP‐Py‐Et. The introduction of pyrene groups increases the material's overall conjugation degree, thereby enhancing visible light absorption. Meanwhile, the stronger electronic ability of the pyrene groups establishes more charge transfer channels through the electron push–pull effect, and more free charges can participate in the photocatalytic H 2 O 2 evolution from water and oxygen. The incorporation of ether groups enhances the migration efficiency of photogenerated charges and effectively boosts the selectivity of the photocatalytic one‐step two‐electron oxygen reduction. Compared with one‐component CTPs (CTP‐Py and CTP‐Et), CTP‐Py‐Et possesses an outstanding photocatalytic H 2 O 2 apparent quantum efficiency of 13.2% at 420 nm and an objective solar‐to‐chemical conversion (SCC) efficiency of 0.52% at 298 K. In certain instances, a high H 2 O 2 concentration (3.22 m m , 1 h) can be obtained through CTP‐Py‐Et, prominently surpassing many reported polymer‐based photocatalysts.