Mixed iron-nickel-based systems with tuned microstructure have recently emerged as promising non-noble electrocatalysts for alkaline water splitting. The understanding of interfacial reaction induced charge-transfer mechanisms and active phases, however, is still limited in overall water splitting. Herein, we report a detailed investigation of active surface phases and mechanisms during both the oxygen evolution (OER) and hydrogen evolution (HER) reactions in an alkaline electrolyte through in-situ Raman and impedance spectroscopy. The frequency response of electrical behavior is interpreted by a full theoretical equivalent circuit model and is related to the Raman spectra.
The results show that the reaction resistance exhibits a strong dependence on applied bias and electrode materials in natural correlation with the reaction rate under both OER and HER process. The presence of iron (Fe) results in a less inductive feature observed in HER impedance spectroscopy, which is associated with the coverage relaxation of involved adsorbed intermediates. By in-situ Raman spectroscopy, it is clear to see that the main function of Ni and Fe sites are dependent on the applied energy. When the Femi level shifts to more negative potentials, the hydroxyl groups are prone to adsorb on Fe3+ sites to form Fe oxyhydroxides, whereas the hydrogen groups show the tendency to adsorb (or migrate) to Ni sites, which accelerates water reduction and thus enhances HER activity. Moreover, the presence of Fe promotes the formation of high Ni valency (γ-NiOOH), leading to an improved OER catalytic performance. Our findings provide insights into the active phases formed in-situ under both the HER and OER reactions and are expected to be valuable for design strategies for efficient and earth-abundant Ni-Fe based catalytic systems.