D‐A‐A Conjugated Polymer with Built‐in Electric Field Enhanced Electron Utilization for Photocatalytic H₂O₂ Synthesis

Conjugated organic polymers exhibit significant potential for photocatalytic H 2 O 2 production but face limitations in exciton dissociation and reaction kinetics. In this study, inspired by the directional electron transport in natural photosynthesis, a donor‐acceptor–acceptor (D‐A1‐A2)‐type polymer, TpMaTAE is designed. The large molecular dipole between the acetylene donor and triazine and carbonyl dual‐acceptor leads to the formation of a strong built‐in electric‐field, which not only reduced the exciton binding energy but also facilitated the unidirectional migration of photogenerated electrons. Meanwhile, the carbonyl groups, serving as redox‐active moieties with electron‐storing capabilities, play a pivotal role in extending the lifetime of charge carriers, therefore enhancing the hot‐carriers utilization and suppressing the charge recombination. Benefiting from these advantages, under simulated solar irradiation, TpMaTAE demonstrates a remarkable solar‐to‐chemical conversion efficiency of 1.03% and an oxygen utilization efficiency of 93.1% utilizing air and water.