Liu Xin, Xia Yongkang, Dong Jiaqian, Zong Ruilong, Bai Xiaojuan
Beijing Energy Conservation & Sustainable Urban and Rural Development Provincial and Ministry Co-construction Collaboration Innovation Center, Beijing University of Civil Engineering and Architecture, Beijing, 100044, China.
Key Laboratory of Urban Stormwater System and Water Environment, Ministry of Education, Beijing University of Civil Engineering and Architecture, Beijing, 100044, China.
Small. 2025 Sep;21(37):e05911. doi: 10.1002/smll.202505911. Epub 2025 Jul 30.
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 HO production at 1672 µmol g h 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. 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.
为了应对水生系统中的抗生素污染，本研究通过分子尺寸控制策略设计了具有有序孔隙率的尺寸可控多孔有机聚合物（POPs）。二维POP利用高度平面化的三嗪基团作为电子受体，通过亚胺键与噻吩电子供体相连，形成供体-受体结构。三嗪基团的强共平面性显著增大了分子二面角，有利于形成具有增强层间共轭的有序π-π堆积层状结构。相比之下，以甲烷为中心单元构建的三维POP由于空间位阻，共平面性和电子耦合降低。对比研究表明，二维POP的平面层状结构有效地促进了激子解离（激子结合能仅为2.01 eV），实现了连续的电子供应和稳定的催化性能。三维POP在无牺牲剂条件下，以1672 μmol g⁻¹ h⁻¹的速率实现了连续的HO生成，通过光自芬顿过程实现了布洛芬的高效降解，降解速率常数提高到0.034 min⁻¹。本研究从分子结构单元的空间构型调控角度阐明了二维供体-受体型POPs在光催化体系中的结构优势，为设计先进的水处理材料提供了思路。
