Highly ordered TiO₂ nanotube arrays (TNTAs) and their heterostructure nanocomposites by structural engineering design were utilized as heterogeneous photocatalysts for highly efficient broadband photoinduced controlled radical polymerization (photoCRP), including photoATRP and PET-RAFT. Highly efficient broadband UV–visible light responsive photoCRP was achieved by combining the acceleration effects of electron transfer derived from the distinctive highly ordered nanotube structure of TNTAs and the localized surface plasmon resonance (LSPR) effect combined with the formation of the Schottky barrier via modification of Au nanoparticles. This polymerization system was capable to polymerize acrylate and methacrylate monomers with high conversion, “living” chain-ends, tightly regulated molecular weights, and outstanding temporal control properties. The heterogeneous nature of the photocatalysts enabled simple separation and effective reusability in subsequent polymerizations. These results highlight the modular design of highly efficient catalysts to optimize the controlled radical polymerization process.

中文翻译：

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分层结构的纳米管阵列作为高效宽带光致受控自由基聚合的异相光催化剂

高度有序的TiO ₂纳米管阵列 (TNTA) 及其通过结构工程设计的异质结构纳米复合材料被用作高效宽带光诱导受控自由基聚合 (photoCRP) 的异质光催化剂，包括 photoATRP 和 PET-RAFT。通过结合源自 TNTA 独特高度有序纳米管结构的电子转移加速效应和局域表面等离子共振 (LSPR) 效应以及通过修饰金纳米粒子。该聚合体系能够聚合具有高转化率、“活性”链端、严格调节的分子量和出色的时间控制性能的丙烯酸酯和甲基丙烯酸酯单体。光催化剂的异质性使其能够在随后的聚合反应中实现简单的分离和有效的重复使用。这些结果突出了高效催化剂的模块化设计，以优化受控自由基聚合过程。