Understanding the oxygen evolution reaction (OER) activity and stability of the NiFe-based materials is important for achieving low-cost and highly efficient electrocatalysts for practical water splitting. Here, we report the roles of Ni and Fe on the OER activity and stability of metallic NiFe and pure Ni thin films in alkaline media. Our results support that Ni(OH) 2 /NiOOH does not contribute to the OER directly, but it serves as an ideal host for Fe incorporation, which is essential for obtaining high OER activity. Furthermore, the availability of Fe in the electrolyte is found to be important and necessary for both NiFe and pure Ni thin films to maintain an enhanced OER performance, while the presence of Ni is detrimental to the OER kinetics. The impacts of Fe and Ni species present in KOH on the OER activity are consistent with the dissolution/re-deposition mechanism we proposed. Stability studies show that the OER activity will degrade under prolonged continuous operation. Satisfactory stability can, however, be achieved with intermittent OER operation, in which the electrocatalyst is cycled between degraded and recovered states. Accordingly, two important ranges, that is, the recovery range and the degradation range, are proposed. Compared to the intermittent OER operation, prolonged continuous OER operation (i.e., in the degradation range) generates a higher NiOOH content in the electrocatalyst, which is likely related to the OER deactivation. If the electrode works in the recovery range for a certain period, that is, at a sufficiently low reduction potential, where Ni 3+ is reduced to Ni 2+ , the OER activity can be maintained and even improved if Fe is also present in the electrolyte.
Direct solar hydrogen generation via a combination of photovoltaics (PV) and water electrolysis can potentially ensure a sustainable energy supply while minimizing greenhouse emissions. The PECSYS project aims at demonstrating a solar‐driven electrochemical hydrogen generation system with an area >10 m2 with high efficiency and at reasonable cost. Thermally integrated PV electrolyzers (ECs) using thin‐film silicon, undoped, and silver‐doped Cu(In,Ga)Se2 and silicon heterojunction PV combined with alkaline electrolysis to form one unit are developed on a prototype level with solar collection areas in the range from 64 to 2600 cm2 with the solar‐to‐hydrogen (StH) efficiency ranging from ≈4 to 13%. Electrical direct coupling of PV modules to a proton exchange membrane EC to test the effects of bifaciality (730 cm2 solar collection area) and to study the long‐term operation under outdoor conditions (10 m2 collection area) is also investigated. In both cases, StH efficiencies exceeding 10% can be maintained over the test periods used. All the StH efficiencies reported are based on measured gas outflow using mass flow meters.
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