Efficient solar energy-driven conversion of CO₂ to valuable chemicals is challenging. Here we design an imidazolium-based ionic conjugated microporous polymer (ImI-CMP), which unblocks readily intramolecular charge transfer and triggers CO₂ photoreduction. Under visible light irradiation, ImI-CMP incorporated with Co (II) species exhibits a high CO production rate of 2953 μmol g⁻¹ h⁻¹ and a turnover frequency of 30.8 h⁻¹; these numbers are competitive to that of the best porous organic polymers. The mechanism studies reveal that two factors play key roles in the outstanding photocatalytic performance. First, the imidazolium motifs on the ImI-CMP enhance the activation of CO₂. Second, π-conjugation structure and the built-in electric field allow ultrafast intramolecular photoinduced electron transfer in the ImI-CMP. This work provides a new strategy for designing high-performance organic photocatalysts for CO₂ reduction by combining cationic imidazolium motifs and π-conjugation structures.

太阳能驱动的 CO ₂向有价值化学品的高效转化具有挑战性。在这里，我们设计了一种基于咪唑鎓的离子共轭微孔聚合物 (ImI-CMP)，它可以轻松解除分子内电​​荷转移并触发 CO _{2 光}还原。在可见光照射下，与Co (II) 物种结合的ImI-CMP 表现出2953 μmol g ^-1 h ^-1的高CO 产率和30.8 h ^-1的转换频率；这些数字可与最好的多孔有机聚合物相媲美。机理研究表明，两个因素在出色的光催化性能中起着关键作用。首先，ImI-CMP 上的咪唑基团增强了 CO ₂的活化. 其次，π-共轭结构和内置电场允许在 ImI-CMP 中进行超快的分子内光致电子转移。这项工作为通过结合阳离子咪唑鎓基序和π-共轭结构设计用于CO ₂还原的高性能有机光催化剂提供了一种新策略。