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Herein, we report, for the first time, a comparative study on the electrocatalytic reduction of chloroform on silver in different aqueous supporting electrolytes. Cyclic voltammetry measurements were performed at a wide range of scan rates and concentrations of CHCl 3  using 0.05 M NaClO 4 , NaH 2 PO4, and Na 2 HPO 4  as supporting electrolytes. We observed that a type of supporting electrolyte anion strongly influences both the potential as well as the current density of the chloroform reduction peak, mainly due to the presence of OH −  in an alkaline Na 2 HPO 4  solution, which is a specifically interacting anion. Moreover, the highest sensitivity of the Ag electrode toward CHCl 3  reduction was observed in a neutral NaClO 4  aqueous solution. It was found that the electroreduction of chloroform at the silver surface occurs via a concerted mechanism regardless of the type of the studied supporting electrolyte.

Effect of the Supporting Electrolyte on Chloroform Reduction at a Silver Electrode in Aqueous Solutions