Effect of Electrolyte Cations on Organic Electrosynthesis: The Case of Adiponitrile Electrochemical Production

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., <10%). However, the combined effect of alkali cations and selectivity-directing ions (i.e., TAA ions) is essential in the enhancement of ADN synthesis. The insights gained in this study provide guidelines for the design of aqueous electrolytes that improve selectivity and limit hydrogen evolution in organic electrosynthesis.