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Impedance spectroscopy (IS), intensity‐modulated photocurrent spectroscopy (IMPS), and intensity‐modulated photovoltage spectroscopy (IMVS) are well‐established powerful modulated techniques to characterize optoelectronic devices. Their combined use has proven to provide an understanding of the behavior and performance of these systems, far beyond the output obtained from their independent analysis. However, this combination is shown to be challenging when applied to complex systems. Herein, IS, IMPS, and IMVS are cooperatively used, for the first time, to study the distributed photogeneration, diffusion, and recombination processes in a photoanode of zircon‐doped bismuth vanadate. The use of this methodology reveals that the carriers that determine the response of the device are the electrons when the device is illuminated from the hole‐collector side (electrolyte) and the holes when the illumination reaches the device from the electron‐collector side. Detailed quantitative information is obtained for each carrier, including recombination lifetime, diffusion coefficient and collectrion and separation efficiencies, identifying the latter as the main limitation of this device. This methodology is a powerful tool that can be used for the characterization and understanding of the operating processes of other photoconversion devices.

We review how crystal facets, structural reconstructions and disorder impact the performance of electrodes for energy conversion.

Bismuth vanadate (BiVO4), which has attractive applicability as a photoactive material, presents applications that range from catalysis to water treatment upon visible light irradiation. In this study, we develop a simple synthesis of < 200 nm monoclinic BiVO4 nanoparticles, which were further deposited on transparent conductive substrates by spin coating and calcination, obtaining nanostructured films. The obtained nanostructured BiVO4 photoanodes were tested for water oxidation, leading to promising photocurrents exhibiting competitive onset potentials (~0.3 V vs. RHE). These nanoparticulate BiVO4 photoanodes represent a novel class of highly potential materials for the design of efficient photoelectrochemical devices.

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