Wang Zhuo-Qin, Li Meng-Hao, Liang Shuang, Kong Yuxiang, Wang Chunyu, Li Lu, Xu Ji-Jing, Yang Ying-Wei
College of Chemistry, Jilin University, 2699 Qianjin Street, Changchun 130012, P. R. China.
State Key Laboratory of Inorganic Synthesis and Preparative Chemistry, College of Chemistry, Jilin University, 2699 Qianjin Street, Changchun 130012, P. R. China.
J Am Chem Soc. 2025 Apr 23;147(16):13618-13628. doi: 10.1021/jacs.5c00768. Epub 2025 Apr 10.
Porous organic polymers have emerged as promising materials for energy conversion, pollutant adsorption, and heterogeneous catalysis because of their tunable pore structures and high surface areas. However, most porous organic polymers are still limited by insufficient conjugation and inefficient electron-hole separation, hindering the tunability of their photoelectric properties and overall functionality. By integrating macrocyclic compounds as a new building block, which feature electron-rich cavities and rigid ring structures, into the polymer network, the resulting conjugated macrocycle polymers are expected to provide an innovative approach to enrich the photoelectric functionalities of porous organic polymers. Herein, an enaminone-based pillararene photocatalyst, TpAP[5], is constructed by covalently linking functionalized pillar[5]arene to conjugated macrocycle polymers through Schiff base condensation for efficient photocatalytic reactions. This material demonstrates exceptional performance in the photocatalytic production of hydrogen peroxide, achieving a rate of 2343 μmol g h. In-depth investigations reveal that the incorporation of pillararenes enables synergistic catalysis of water oxidation and oxygen reduction reactions and significantly enhances catalyst stability by regulating molecular tautomerization. This work opens new avenues for designing high-performance multifunctional conjugated macrocycle polymers with significant potential for clean energy conversion.
多孔有机聚合物因其可调节的孔结构和高比表面积，已成为能源转换、污染物吸附和多相催化领域颇具前景的材料。然而，大多数多孔有机聚合物仍受限于共轭不足和电子-空穴分离效率低下，这阻碍了其光电性能和整体功能的可调节性。通过将具有富电子空腔和刚性环结构的大环化合物作为新的结构单元整合到聚合物网络中，有望得到的共轭大环聚合物为丰富多孔有机聚合物的光电功能提供一种创新方法。在此，通过席夫碱缩合将功能化的柱[5]芳烃与共轭大环聚合物共价连接，构建了一种基于烯胺酮的柱芳烃光催化剂TpAP[5]，用于高效光催化反应。该材料在光催化过氧化氢生产中表现出优异性能，产率达到2343 μmol g⁻¹ h⁻¹。深入研究表明，柱芳烃的引入能够实现水氧化和氧还原反应的协同催化，并通过调节分子互变异构显著提高催化剂稳定性。这项工作为设计具有清洁能源转换巨大潜力的高性能多功能共轭大环聚合物开辟了新途径。
