Leibniz Institute for Catalysis, Albert-Einstein-Str. 29a, 18059, Rostock, Germany.
Institute of Chemistry, Rostock University, Albert-Einstein-Str. 3a, 18059, Rostock, Germany.
Chemistry. 2023 Feb 21;29(11):e202202730. doi: 10.1002/chem.202202730. Epub 2023 Jan 24.
Homogeneous catalysts ("mediators") are frequently employed in organic electrosynthesis to control selectivity. Despite their advantages, they can have a negative influence on the overall energy and mass balance if used only once or recycled inefficiently. Polymediators are soluble redox-active polymers applicable as electrocatalysts, enabling recovery by dialysis or membrane filtration. Using anodic alcohol oxidation as an example, we have demonstrated that TEMPO-modified polymethacrylates (TPMA) can act as efficient and recyclable catalysts. In the present work, the influence of the molecular size on the redox properties and the catalytic activity was carefully elaborated using a series of TPMAs with well-defined molecular weight distributions. Cyclic voltammetry studies show that the polymer chain length has a pronounced impact on the key-properties. Together with preparative-scale electrolysis experiments, an optimum size range was identified for polymediator-guided sustainable reaction control.
均相催化剂（“介体”）常用于有机电合成中以控制选择性。尽管它们具有优势，但如果仅使用一次或回收效率低下，它们可能会对整体能源和质量平衡产生负面影响。多介体是可溶的氧化还原活性聚合物，可用作电催化剂，可通过透析或膜过滤回收。我们以阳极醇氧化为例，证明了 TEMPO 修饰的聚甲基丙烯酸酯（TPMA）可以作为高效且可回收的催化剂。在本工作中，使用一系列具有明确分子量分布的 TPMAs 仔细阐述了分子大小对氧化还原性质和催化活性的影响。循环伏安法研究表明，聚合物链长对关键性质有显著影响。结合制备规模的电解实验，确定了适用于介体指导可持续反应控制的最佳聚合物尺寸范围。
