Highly efficient photocatalysis by BiFeO3/α(γ)-Fe2O3 ferromagnetic nano p/n junctions formed by dopant-induced phase separation

A series of Bi1−x Ca x FeO3 (BCFO) nanoparticles (with x = 0.0, 0.03, 0.07, 0.10, 0.15, and 0.20) have been synthesized by sol–gel reaction. X-ray diffraction patterns establish the formation of hexagonal bismuth ferrite as the prominent phase, with a small contribution of the Bi2Fe4O9 phase (as reported by others as well) which diminishes rapidly with the increase in Ca concentration. Interestingly, above a calcium dopant concentration of about 10 % peaks of Fe2O3 (both α and γ components) are observed with a concomitant enhancement of ferromagnetism. Small contribution of the Bi6Ca4O13 phase is also noted in these samples. This phase evolution is driven by dopant-induced strain energy and increasing oxygen vacancy concentration for local charge balance. Transmission electron microscopy (with elemental scanning) and Mossbauer spectroscopy techniques bring out the evolution of nanoparticle morphology (and elemental distribution) and phase configuration, respectively. Measurements of photocatalytic activity (and photo-Fenton activity with H2O2) reveal that Ca doping at the Bi site in BFO enhances the activity significantly in the concentration regime where BFO/α(γ)-Fe2O3 phases coexist in the form of a nanocomposite. The enhancement can thus be attributed to the carrier transfer between BFO and α(γ)-Fe2O3 across nano p/n junctions leading to enhanced carrier lifetime. Importantly, the magnetization of the nanocomposite (about 16 emu gm−1 at x = 0.20) provides a convenient way to collect the photocatalyst with the help of an external magnet for reuse.