Effect of Electrolyte Cations on Organic Electrosynthesis: The Case of Adiponitrile Electrochemical Production
Effect of Electrolyte Cations on Organic Electrosynthesis: The Case of Adiponitrile Electrochemical Production
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DOI：
10.1149/1945-7111/abc766
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发表时间：
2020-12-01
影响因子：
3.9
通讯作者：
Modestino, Miguel A.
中科院分区：
文献类型：
--
作者：
Blanco, Daniela E.;Atwi, Rasha;Modestino, Miguel A.
电解液离子对电化学体系的反应环境有着深远的影响，是决定电化学反应的反应速率和选择性的关键驱动因素。我们结合实验和计算方法来了解支持碱性阳离子的大小和浓度的单独影响，以及它们与其他电解质离子在己二腈(ADN)电合成中的协同作用。载体碱性阳离子的大小影响表面电荷密度、水分子的利用率和反应中间体的稳定性。较大的碱性阳离子可以通过降低近电极区的水分子的可用性来帮助限制氢气的释放和中间体的早期质子化。在-20 mA cm(-2)的磷酸铯盐、乙二胺四乙酸和四烷基铵离子(TAA离子)电解液中，ADN的选择性达到93%。只含有支持的磷酸盐的电解质促进中间物种的早期加氢，从而导致低的ADN选择性(即，
Electrolyte ions have a profound impact on the reaction environment of electrochemical systems and can be key drivers in determining the reaction rate and selectivity of electro-organic reactions. We combine experimental and computational approaches to understand the individual effect of the size and concentration of supporting alkali cations, as well as their synergies with other electrolyte ions on the electrosynthesis of adiponitrile (ADN). The size of supporting alkali cations influences the surface charge density, availability of water molecules, and stability of reaction intermediates. Larger alkali cations can help limit hydrogen evolution and the early protonation of intermediates by lowering the availability of water molecules in the near electrode region. A selectivity of 93% towards ADN was achieved at -20 mA cm(-2) in electrolytes containing cesium phosphate salts, ethylenediaminetetraacetic acid, and tetraalkylammonium ions (TAA ions). Electrolytes containing only supporting phosphate salts promote the early hydrogenation of intermediate species leading to low ADN selectivities (i.e.,