Direct Observation of the Chemical Transformations in BiVO4 Photoanodes upon Prolonged Light‐Aging Treatments

Exposing BiVO4 photoanodes to light‐aging treatments is known to produce a significant photocurrent enhancement. Until now, the interpretation given to this phenomenon is associated to the formation of oxygen vacancies and little is reported about chemical changes in the material. Herein, the chemical segregation of Bi species toward the surface upon light‐aging treatment is demonstrated, which takes place with the concomitant formation of intra‐bandgap states associated to the oxygen vacancies. It is further demonstrated that these intra‐bandgap states are photoactive and generate photocurrent under infrared excitation. These results highlight the importance of understanding light‐induced effects while employing multinary metal oxide photoelectrodes. Prolonged light treatments over BiVO4 photoanodes under air conditions induce Bi segregation in the surface, new intra‐bandgap states, as well as the formation of oxygen vacancies.