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Hollow α-Fe₂O₃ nanofibres for solar water oxidation: improving the photoelectrochemical performance by formation of α-Fe₂O₃/ITO-composite photoanodes

Einert, M., Ostermann, R., Weller, T., Zellmer, S., Garnweitner, G., Smarsly, B. M., Marschall, R.
Journal of materials chemistry A 2016 v.4 no.47 pp. 18444-18456
electric current, electrolytes, ferric chloride, ferric oxide, humidity, iron, mass transfer, nanocomposites, nanocrystals, nanofibers, nanoparticles, nanotubes, oxidation, semiconductors, surface area
We demonstrate the synthesis and photoelectrochemical performance of high-aspect ratio dense and hollow α-Fe₂O₃ nanofibres, and the formation of core–shell-like α-Fe₂O₃/indium-tin oxide (ITO) nanocomposites utilised as a photoanode for solar water splitting. α-Fe₂O₃ nanofibres were prepared via a single-nozzle electrospinning technique using iron chloride (FeCl₃) and poly(vinylpyrrolidone) (PVP) as precursors, followed by calcination. A new synthetic formation mechanism has been proposed taking into account the significance of three control parameters: (i) the iron precursor, (ii) the role of a co-solvent and (iii) the influence of the humidity on the tube evolution of α-Fe₂O₃ nanotubes. Hollow α-Fe₂O₃ fibres showed enhanced photocurrents and incident photon-to-current efficiency (IPCE) values compared to dense fibres, which are ascribed to the superior surface area of hollow fibres offering a good accessibility for the electrolyte and thus leading to improved mass transport. The photoelectrochemical properties of the α-Fe₂O₃ nanofibres could be further enhanced by the combination with highly crystalline, uniform ITO nanocrystals (Ø 10 nm), thus forming a core–shell-like α-Fe₂O₃/ITO fibre nanocomposite. The doubled photocurrent of the α-Fe₂O₃/ITO nanocomposite can most likely be attributed to the fast interfacial charge carrier exchange between the highly conductive ITO nanoparticles and α-Fe₂O₃, thus inhibiting the recombination of the electron–hole pairs in the semiconductor by spatial separation.