Here we investigated the photoelectrodeposition of oxygen-evolving catalysts (OECs) based on oxy-hydroxides-phosphates of Co, Fe, or Ni (CoPi, FePi, and NiPi) on the WO3/BiVO4 heterojunction and their activity in water oxidation. The OECs were deposited by cycles of (i) open-circuit potential (OCP) and (ii) applying a potential positive enough to oxidize the metallic precursor on the WO3/BiVO4. The crystalline and optical properties of the photoanodes were not significantly affected by the OECs deposition. However, there was a remarkable increase in the photocurrent densities (jpc) to water oxidation, where the modification with FePi showed the best result, achieving 2.12 mA cm-2, which corresponds to 2.83 times higher than the heterojunction without the OECs. Furthermore, the OECs deposition changed the morphology of the heterojunction with the deposition of a thin film on its surface. In addition, during the FePi deposition, the BiVO4 layer seems to partially dissolve. Our study shows a facile methodology to boost the activity of photoanodes to the water oxidation by photoelectrodeposition of OECs.

The well-known electrochemical probe Fe(CN)63-/Fe(CN)64- is widely used for estimating the electrochemically active area of electrodes modified with carbon nanotubes, conductive polymers, enzymes, etc. In this study, we used the platinum electrode, smooth or platinized with different roughness factors, to demonstrate that such a redox couple fails to respond to a surface roughness variation. We determined the roughness factors of the Pt surfaces by atomic force microscopy (AFM) images, which yielded values between 2.72 and 25.91. Almost the same values were found by using the charge of the hydrogen monolayer desorption obtained from steady-state cyclic voltammetry experiments performed in an acid medium. They were then compared with those provided by peak current in voltammetry or chronoamperometry with Fe(CN)63-/Fe(CN)64- which all yielded values nearly to one. Such comparison demonstrates that the electrochemical behavior of the redox probe is an outer sphere reaction with a quite small interaction with the electrode surface, thus not being suitable to be related with active areas.