Planar Conjugation Engineering in Triazine‐Based Donor‐Acceptor Porous Organic Polymers for Boosting Photo‐Self‐Fenton Antibiotic Degradation

To combat antibiotic pollution in aquatic systems, this work designed dimension-controlled porous organic polymers (POPs) with ordered porosity via a molecular-dimensional control strategy. The 2D POP utilizes highly planar triazine groups as electron acceptors, which are linked to thiophene electron donors via imine bonds to form a donor-acceptor structure. The strong coplanarity of triazine groups significantly enlarges molecular dihedral angles, facilitating ordered π-π stacked lamellar architecture with enhanced interlayer conjugation. In contrast, the 3D POP constructed with methane as the central unit has reduced coplanarity and electronic coupling due to steric hindrance. Comparative studies are shown that the planar layered structure of the 2D POP effectively promotes exciton dissociation (with an exciton binding energy of only 2.01 eV), achieving continuous electron supply and stable catalytic performance. The 3D POP achieves continuous H₂O₂ production at 1672 µmol g^-1 h^-1 under sacrificial agent-free conditions, enabling efficient degradation of ibuprofen via the photo-self-Fenton process and increasing the degradation rate constant to 0.034 min^-1. This work elucidates the structural superiority of 2D donor-acceptor-type POPs in photocatalytic systems from the perspective of spatial configuration regulation of molecular building blocks, providing insights for designing advanced water-treatment materials.