Charge-Carrier Dynamics at the CuWO₄/Electrocatalyst Interface for Photoelectrochemical Water Oxidation

Unraveling the charge-carrier dynamics at electrocatalyst/electrode interfaces is critical for the development of efficient photoelectrochemical (PEC) water oxidation. Unlike the majority of photoanodes investigated for PEC water oxidation, the integration of electrocatalysts with CuWO₄ electrodes generally results in comparable or worse performance compared to the bare electrode. This is despite the fact that the surface state recombination limits the water oxidation efficiency with CuWO₄ electrodes, and an electrocatalyst ought to bypass this reaction and improve performance. Here, we present results that deepen the understanding of the energetics and electron-transfer processes at the CuWO₄/electrocatalyst interface, which controls the performance of such systems. Ni_0.75Fe_0.25O (denoted as Ni75) was chosen as a model electrocatalyst, and through dual-working electrode experiments, we have been able to provide significant insight into the role of the electrocatalyst on the charge-transfer process at the CuWO₄/Ni75 interface. We have shown a lack of performance improvement for CuWO₄/Ni75 relative to the bare electrode to water oxidation. We attribute this surprising result to water oxidation on the CuWO₄ surface kinetically outcompeting hole transfer to the Ni75 electrocatalyst interface.