Heterogeneous photocatalysts (PCs) have garnered attention for their sustainability and cost-effectiveness. Despite the existence of various types of these PCs, their synthesis often involves complex, multi-step procedures and laborious purification. Herein, we propose a simple method for attaching small-molecule photocatalytic species onto crosslinked 3-D polymer networks as insoluble scaffolds to create robust heterogeneous PCs. The highly swellable poly(ethylene glycol)-based ChemMatrix (CM) resin, known for its amphiphilic properties and high functional group loading, facilitated the covalent immobilization of the photoredox dye Eosin Y (EY), but also streamlined functionalization with Ir(III) complexes. The resulting heterogeneous CM-EY demonstrated efficient photocatalytic performance in open-to-air dual photoredox catalysis of atom transfer radical polymerization (photo-ATRP) under green light. This was confirmed by the well-controlled synthesis of polymers with molecular masses ranging from 20 kDa to 300 kDa and low dispersities. Furthermore, CM-EY exhibited excellent photostability and recyclability over multiple cycles of ATRP. The heterogeneous catalysis of photo-ATRP provided high temporal control and enabled benign conditions for synthesizing protein-polymer hybrids (PPH). When combined with the initiator-modified CM (CM-BIB), CM-EY facilitated the solid-phase synthesis of homopolymers and block copolymers with recyclable performance. However, the coordinatively bound Ir@CM showed decreased catalytic activity and efficiency toward photoredox dehalogenation due to the leaching of active species during recycling. This study highlights the advantages of the covalent linking of catalysts to solid supports over non-covalent interactions, underscoring the potential of functionalized polymer resin as a promising scaffold. Such an approach offers customization and tunability, presenting opportunities for innovation in green chemistry.

中文翻译：

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耐氧光氧化还原原子转移自由基聚合和小分子脱卤的非均相催化


异相光催化剂 （PC） 因其可持续性和成本效益而受到关注。尽管存在各种类型的 PC，但它们的合成通常涉及复杂的多步骤程序和费力的纯化。在此，我们提出了一种简单的方法，将小分子光催化物质作为不溶性支架连接到交联的 3-D 聚合物网络上，以创建强大的异质 PC。高度溶胀的聚乙二醇基 ChemMatrix （CM） 树脂以其两亲性和高官能团负载量而闻名，促进了光氧化还原染料 Eosin Y （EY） 的共价固定化，但也简化了 Ir（III） 配合物的功能化。所得的非均相 CM-EY 在绿光下原子转移自由基聚合 （photo-ATRP） 的开放空气双光氧化还原催化中表现出高效的光催化性能。分子量范围为 20 kDa 至 300 kDa 且分散度低的聚合物的合成控制良好证实了这一点。此外，CM-EY 在 ATRP 的多个循环中表现出优异的光稳定性和可回收性。光 ATRP 的非均相催化提供了高时间控制，并为合成蛋白质-聚合物杂交 （PPH） 提供了良性条件。当与引发剂改性的 CM （CM-BIB） 结合使用时，CM-EY 促进了均聚物和具有可回收性能的嵌段共聚物的固相合成。然而，由于回收过程中活性物质的浸出，配位结合的Ir@CM显示出对光氧化还原脱卤的催化活性和效率降低。 本研究强调了催化剂与固体载体的共价键相对于非共价相互作用的优势，强调了功能化聚合物树脂作为一种有前途的支架的潜力。这种方法提供了定制和可调性，为绿色化学的创新提供了机会。