Impact of Alkali Metal Cations and Iron Impurities on the Evolution of Hydrogen on Cu Electrodes in Alkaline Electrolytes

Electrocatalytic Cu is key to the development of processes that can convert CO and CO₂ to hydrocarbons, and nitrate to ammonia. The hydrogen evolution reaction (HER) often competes with these processes. Few studies studied this reaction on Cu under alkaline conditions. Herein, we examined the HER on Cu electrodes under alkaline conditions in Na⁺-and Cs⁺-containing electrolytes. We found that in 0.1 M solutions of NaOH and CsOH of the highest commercially available purity grades, trace impurities of iron deposit on the Cu electrode during electrolysis. As a result, the rate of the HER is enhanced by up to a factor of ≈5 over the course of eleven cyclic voltammograms (CV) from 0.15 to-0.65 V vs the reversible hydrogen electrode. After removal of the iron impurities, the CVs are stable as a function of cycle number. Comparison of the CVs in pre-electrolyzed 0.1 M NaOH and CsOH reveals that changing the cation from Na⁺ to Cs⁺ has no measurable effect on the HER. With density functional theory (DFT), we further rationalized our experimental findings. We discuss the implications of our results for electrocatalytic processes on Cu electrodes.