Efficient synthesis of bifeo3 by the microwave-assisted sol-gel method: "a" site influence on the photoelectrochemical activity of perovskites

Abstract

BiFeO3 (BF) and LaFeO3 (LF) perovskites were synthesized using a microwave-assisted (MW) and sol-gel (SG) methods. XRD, XPS, TEM, UV-DRS techniques were applied to study physicochemical properties of perovskites. In addition, Incident Photon-to-Current Efficiency (IPCE) measurements, Linear Sweep Voltammetry (LSV) and impedance spectroscopy were used to characterize electrochemical properties of the materials. The band gap energy increases in the following way: BF-MW (2.05 eV), LF-MW (2.18 eV), BF-SG (2.26 eV) and LF-SG (2.54 eV), demonstrating a remarkable influence of the synthesis method on the optical and electronic properties of the materials. Furthermore, XRD showed a significant impact of the synthesis methods on the crystal structure. Perovskites synthesized under MW irradiation showed a pure crystal structure compared to the perovskites prepared by SG method, which contained some admixtures. IPCE shows that LF-MW has a better charge separation ability compared to BF-MW. However, BF-SG showed the highest activity. Temperature programmed reduction tests (TPR) revealed a better ability of BF-MW to adsorb/desorb oxygen, compared to LF-MW. XPS measurements pointed at the presence of Fe4+. Finally, the photocatalytic activity of the perovskites was tested in solar water-splitting as a function of the synthesis method and presence of Bi and La in "A" sites of the ABO(3) perovskites. We postulate, that the Jahn-Teller distortion effect in LF-MW increases its catalytic activity by decreasing the binding energy compared to BF-MW.