Alternating current (AC) and pulsed electrolysis are gaining traction in electro(organic) synthesis due to their advantageous characteristics. We employed AC electrolysis in electrochemically mediated Atom Transfer Radical Polymerization (eATRP) to facilitate the regeneration of the activator CuI complex on Cu0 electrodes. Additionally, Cu0 served as a slow supplemental activator and reducing agent (SARA ATRP), enabling the activation of alkyl halides and the regeneration of the CuI activator through a comproportionation reaction. We harnessed the distinct properties of Cu0 dual regeneration, both chemical and electrochemical, by employing sinusoidal, triangular, and square‐wave AC electrolysis alongside some of the most active ATRP catalysts available. Compared to linear waveform (DC electrolysis) or SARA ATRP (without electrolysis), pulsed and AC electrolysis facilitated slightly faster and more controlled polymerizations of acrylates. The same AC electrolysis conditions could successfully polymerize eleven different monomers across different mediums, from water to bulk. Moreover, it proved effective across a spectrum of catalyst activity, from low‐activity Cu/2,2‐bipyridine to highly active Cu complexes with substituted tripodal amine ligands. Chain extension experiments confirmed the high chain‐end fidelity of the produced polymers, yielding functional and high molecular‐weight block copolymers. SEM analysis indicated the robustness of the Cu0 electrodes, sustaining at least 15 consecutive polymerizations.

中文翻译：

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交流电驱动的电化学介导原子转移自由基聚合

交流电 (AC) 和脉冲电解由于其有利的特性而在电（有机）合成中受到关注。我们在电化学介导的原子转移自由基聚合 (eATRP) 中采用交流电解来促进 Cu0 电极上活化剂 CuI 络合物的再生。此外，CuO 作为缓慢的补充活化剂和还原剂 (SARA ATRP)，能够通过歧化反应活化烷基卤化物并再生 CuI 活化剂。我们通过采用正弦波、三角波和方波交流电解以及一些可用的最活跃的 ATRP 催化剂，利用了 Cu0 双重再生的独特特性（化学和电化学）。与线性波形（直流电解）或 SARA ATRP（无电解）相比，脉冲和交流电解促进丙烯酸酯的聚合速度稍快且更受控制。相同的交流电解条件可以成功地在不同介质（从水到本体）中聚合十一种不同的单体。此外，它被证明在一系列催化剂活性中都是有效的，从低活性的 Cu/2,2-联吡啶到具有取代的三足胺配体的高活性 Cu 络合物。扩链实验证实了所生产的聚合物具有高链端保真度，从而产生了功能性高分子量嵌段共聚物。 SEM 分析表明 Cu0 电极的坚固性，可维持至少 15 次连续聚合。