近日，美国康奈尔大学Phillip J. Milner团队揭示了聚合物的连通性决定了固态下的光电催化活性。2025年8月13日，《自然-化学》杂志发表了这一成果。

惰性底物如氯芳烃的还原功能化是与环境修复和有机合成相关的关键但具有挑战性的转化。结合电和光是一种新兴的策略，可以获得单电子转移到氯芳烃所需的深度还原电位，但这种方法受到稳定性差和机制模糊的限制。

研究组展示了异相光电催化主题氧化还原活性二甲苯聚合物的氯芳烃还原。他们发现，光电催化活性随着二甲苯和氧化还原活性聚合物主链的变化而显著变化。特别是，一种柔性的、非共轭的苝酰亚胺聚合物优于所有其他测试的光电催化剂。瞬态吸收光谱分析表明，双还原过二亚胺与卤代芳烃底物之间的预络合作用是生产催化的关键。总体而言，这项工作突出了多相光电催化主题不溶性氧化活性有机材料，并为固态光电催化活性提供了关键的结构-性质见解，为可持续合成的下一代材料的开发提供了信息。

附：英文原文

Title: Polymer connectivity governs electrophotocatalytic activity in the solid state

Author: Ling, Jianheng, Vonder Haar, Amy L., Colley, Kiser Z., Kim, Juno, Musser, Andrew J., Milner, Phillip J.

Issue&Volume: 2025-08-13

Abstract: The reductive functionalization of inert substrates such as chloroarenes is a critical yet challenging transformation relevant to both environmental remediation and organic synthesis. Combining electricity and light is an emerging strategy to access the deeply reducing potentials required for single electron transfer to chloroarenes, yet this approach is limited by poor stability and mechanistic ambiguity. Here we demonstrate heterogeneous electrophotocatalysis using redox-active rylene diimide polymers for the reduction of chloroarenes. We find that the electrophotocatalytic activity varies dramatically as a function of the rylene diimide and the redox-inactive polymer backbone. In particular, a flexible, non-conjugated perylenediimide polymer outperforms all other tested electrophotocatalysts. Transient absorption spectroscopy reveals that precomplexation between the doubly reduced perylenediimide and the haloarene substrate is key to productive catalysis. Overall, this work highlights heterogeneous electrophotocatalysis using insoluble redox-active organic materials and provides critical structure–property insights into solid-state electrophotocatalytic activity, informing the development of next-generation materials for sustainable synthesis.

DOI: 10.1038/s41557-025-01897-7

Source: https://www.nature.com/articles/s41557-025-01897-7