Visible-light driven generation of reactive radicals over BiFeO<inf>3</inf>/TiO<inf>2</inf> nanotube array: experimental evidence and energetic mechanism
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© 2015, Springer Science+Business Media Dordrecht. BiFeO<inf>3</inf>-based materials have attracted broad interests due to their multiferric and photoactive properties, but there remains some controversial uncertainty about the electronic structures of various nanoparticles of BiFeO<inf>3</inf>. In this work, BiFeO<inf>3</inf> nanoparticles smaller than 100 nm have grown into TiO<inf>2</inf> nanotube array by an ultrasonic-immersion method. Some evidences on the energy band position of BiFeO<inf>3</inf> nanoparticles in BiFeO<inf>3</inf>/TiO<inf>2</inf> nanotube array were from the visible-light driven photo responses. Positive surface photovoltage polarity of the composite is the same as that of the pure TiO<inf>2</inf> nanotube array, which reveals the photo-induced electron transfer from BiFeO<inf>3</inf> nanoparticles to TiO<inf>2</inf> nanotubes. Furthermore, both ·OH and ·O<inf>2</inf> <sup>-</sup> radicals could be detected by the electron paramagnetic resonance (EPR) spin-trapping method. According to the EPR result, the valence band edge of BiFeO<inf>3</inf> nanoparticles could be deduced as more positive than the potential at which ·OH radical could be generated. A scheme on the energy band alignment and photo-induced charges transfer processes is then proposed based on the observed visible-light photo activity of BiFeO<inf>3</inf>/TiO<inf>2</inf> nanotube array.
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