Dorchies Florian, Grimaud Alexis
Chimie du Solide et de l'Energie, UMR 8260, Collège de France 75231 Paris Cedex 05 France
Réseau sur le Stockage Electrochimique de l'Energie (RS2E) CNRS FR3459 80039 Amiens Cedex France.
Chem Sci. 2023 May 23;14(26):7103-7113. doi: 10.1039/d3sc01889j. eCollection 2023 Jul 5.
Electrosynthesis is a method of choice for designing new synthetic routes owing to its ability to selectively conduct reactions at controlled potentials, high functional group tolerance, mild conditions and sustainability when powered by renewables. When designing an electrosynthetic route, the selection of the electrolyte, which is composed of a solvent, or a mixture of solvents, and a supporting salt, is a prerequisite. The electrolyte components, generally assumed to be passive, are chosen because of their adequate electrochemical stability windows and to ensure the solubilization of the substrates. However, very recent studies point towards an active role of the electrolyte in the outcome of electrosynthetic reactions, challenging its inert character. Particular structuring of the electrolyte at nano- and micro-scales can occur and impact the yield and selectivity of the reaction, which is often overlooked. In the present Perspective, we highlight how mastering the electrolyte structure, both in bulk and at electrochemical interfaces, introduces an additional level of control for the design of new electrosynthetic methods. For this purpose, we focus our attention on oxygen-atom transfer reactions using water as the sole oxygen source in hybrid organic solvent/water mixtures, these reactions being emblematic of this new paradigm.
由于电合成能够在可控电位下选择性地进行反应，对官能团具有高耐受性，反应条件温和且由可再生能源供电时具有可持续性，因此它是设计新合成路线的首选方法。在设计电合成路线时，选择由一种溶剂或多种溶剂的混合物以及一种支持盐组成的电解质是先决条件。电解质成分通常被认为是惰性的，选择它们是因为它们具有足够的电化学稳定窗口，并确保底物的溶解。然而，最近的研究表明电解质在电合成反应结果中起着积极作用，这对其惰性特征提出了挑战。电解质在纳米和微米尺度上可能会发生特殊的结构形成，并影响反应的产率和选择性，而这一点常常被忽视。在本综述中，我们强调了掌握本体和电化学界面处的电解质结构如何为设计新的电合成方法引入了额外的控制维度。为此，我们将注意力集中在以水作为唯一氧源的混合有机溶剂/水混合物中的氧原子转移反应上，这些反应是这一新范式的典型代表。
