Paired electrolysis methods are appealing for chemical synthesis because they generate valuable products at both electrodes; however, development of such reactions is complicated by the need for both half-reactions to proceed under mutually compatible conditions. Here, a modular electrochemical synthesis (ModES) strategy bypasses these constraints using a “redox reservoir” (RR) to pair electrochemical half-reactions across aqueous and nonaqueous solvents. Electrochemical oxidation reactions in organic solvents, the conversion of 4-t-butyltoluene to benzylic dimethyl acetal and aldehyde in methanol or the oxidative C–H amination of naphthalene in acetonitrile, and the reduction of oxygen to hydrogen peroxide in water were paired using nickel hexacyanoferrate as an RR that can selectively store and release protons (and electrons) while serving as the counter electrode for these reactions. Selective proton transport through the RR is optimized and confirmed to enable the ion balance, and thus the successful pairing, between redox half-reactions that proceed with different rates, on different scales, and in different solvents (methanol, acetonitrile, and water).

中文翻译：

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由氧化还原储层电极实现的水性和非水性电合成反应的配对

配对电解方法对化学合成很有吸引力，因为它们在两个电极上都能产生有价值的产品；然而，由于需要在相互兼容的条件下进行两个半反应，因此此类反应的发展变得复杂。在这里，模块化电化学合成 (ModES) 策略绕过这些限制，使用“氧化还原储层”(RR) 来配对水性和非水性溶剂中的电化学半反应。有机溶剂中的电化学氧化反应，4- t的转化-丁基甲苯在甲醇中生成苄基二甲基缩醛和醛或萘在乙腈中氧化 C-H 胺化，以及氧在水中还原成过氧化氢，使用六氰基铁酸镍作为 RR 配对，可以选择性地储存和释放质子（和电子） ) 同时作为这些反应的反电极。通过 RR 的选择性质子传输得到优化和确认，以实现离子平衡，从而成功配对以不同速率、不同规模和不同溶剂（甲醇、乙腈和水）进行的氧化还原半反应。