Understanding Cation Trends for Hydrogen Evolution on Platinum and Gold Electrodes in Alkaline Media

In this work, we study how the cation identity and concentration alter the kinetics of the hydrogen evolution reaction (HER) on platinum and gold electrodes. A previous work suggested an inverted activity trend as a function of alkali metal cation when comparing the performance of platinum and gold catalysts in alkaline media. We show that weakly hydrated cations (K⁺) favor HER on gold only at low overpotentials (or lower alkalinity), whereas in more alkaline pH (or high overpotentials), a higher activity is observed using electrolytes containing strongly hydrated cations (Li⁺). We find a similar trend for platinum; however, the inhibition of HER by weakly hydrated cations on platinum is observed already at lower alkalinity and lower cation concentrations, suggesting that platinum interacts more strongly with metal cations than gold. We propose that weakly hydrated cations stabilize the transition state of the water dissociation step more favorably due to their higher near-surface concentration in comparison to a strongly hydrated cation such as Li⁺. However, at high pH and consequently higher near-surface cation concentrations, the accumulation of these species at the outer Helmholtz plane inhibits HER. This is especially pronounced on platinum, where a change in the rate-determining step is observed at pH 13 when using a Li⁺- or K⁺-containing electrolyte.