Mixed oxide semiconductors based on bismuth for photoelectrochemical applications

The structural and photoelectrochemical properties of mixed oxide semiconductor films of Bi-Nb-M-O (M = Al, Fe, Ga, In) were studied in order to explore their use as photoanodes in photoelectrochemical cells. These films were prepared on AISI/SAE 304 stainless steel plates by sol–gel dip-coating. The films were characterized by scanning electron microscopy—energy dispersive spectroscopy (SEM-EDS), X-ray diffraction (XRD), and X-ray photoelectron spectroscopy (XPS), and their photoelectrochemical properties were studied by open circuit potential (OCP) measurements, linear sweep voltammetry (LSV), and cyclic voltammetry (CV). SEM micrographs show homogeneous and rough films with agglomerates on the surface. EDS analyses show that the films are composed of Bi, Nb, and M, and the agglomerates are mainly composed of Bi. XRD analyses show a predominant crystalline phase of bismuth(III) oxide (Bi₂O₃) and a secondary phase composed of Bi-M mixed oxides. It is noteworthy that there was no identified niobium-based crystalline phase. XPS results reveal that the films are composed by Bi(III), Nb(V), and M(III). CV results show that the electrochemical behavior is attributed only to the semiconductor films which indicate a good coating of the stainless steel support. OCP measurements show that all the films have n-type semiconductor properties and exhibited photoresponse to the visible light irradiation. LSV results show that the application of a potential higher than +0.1 V enhances the photocurrent which can be attributed to an improved charge carrier separation. The results indicate that these materials can be used in photoelectrochemical cells.