Combining impedance and hydrodynamic methods in electrocatalysis. Characterization of Pt(pc), Pt₅Gd, and nanostructured Pd for the hydrogen evolution reaction

Electrochemical hydrodynamic techniques typically involve electrodes that move relative to the solution. Historically, approaches involving rotating disc electrode (RDE) configurations have become very popular, as one can easily control the electroactive species’ mass transport in those cases. The combination of cyclic voltammetry and RDE is nowadays one of the standard characterization protocols in electrocatalysis. On the other hand, impedance spectroscopy is one of the most informative electrochemistry techniques, enabling the acquisition of information on the processes taking place simultaneously at the electrode/electrolyte interface. In this work, we investigated the hydrogen evolution reaction (HER) catalyzed by polycrystalline Pt (Pt(pc)) and Pt₅Gd disc electrodes and characterized them using RDE and electrochemical impedance spectroscopy techniques simultaneously. Pt₅Gd shows higher HER activities than Pt in acidic and alkaline media due to strain and ligand effects. The mechanistic study of the reaction showed that the rotation rates in acidic media do not affect the contribution of the Volmer-Heyrovsky and Volmer-Tafel pathways. However, the Volmer-Heyrovsky pathway dominates at lower rotation rates in alkaline media. Besides, the HER in acidic solutions depends more strongly on mass diffusion than in alkaline media. In addition to simple and clearly defined systems, the combined method of both techniques is applicable for systems with greater complexity, such as Pd/C nanostructured catalysts. Applying the above-presented approach, we found that the Volmer-Tafel pathway is the dominating mechanism of the HER for this catalytic system.