Facile Fabrication of a Highly Crystalline and Well-Interconnected Hematite Nanoparticle Photoanode for Efficient Visible-Light-Driven Water Oxidation

Facile and scalable fabrication of α-Fe₂O₃ photoanodes using a precursor solution containing Fe^III ions and 1-ethylimidazole (EIm) in methanol was demonstrated to afford a rigidly adhered α-Fe₂O₃ film with a controllable thickness on a fluorine-doped tin oxide (FTO) substrate. EIm ligation to Fe^III ions in the precursor solution brought about high crystallinity of three-dimensionally well-interconnected nanoparticles of α-Fe₂O₃ upon sintering. This is responsible for the 13.6 times higher photocurrent density (at 1.23 V vs reference hydrogen electrode (RHE)) for photoelectrochemical (PEC) water oxidation on the α-Fe₂O₃ (w-α-Fe₂O₃) photoanode prepared with EIm compared with that (w/o-α-Fe₂O₃) prepared without EIm. The w-α-Fe₂O₃ photoanode provided the highest charge separation efficiency (η_sep) value of 27% among the state-of-the-art pristine α-Fe₂O₃ photoanodes, providing incident photon-to-current conversion efficiency (IPCE) of 13% at 420 nm and 1.23 V vs RHE. The superior η_sep for the w-α-Fe₂O₃ photoanode is attributed to the decreased recombination of the photogenerated charge carriers at the grain boundary between nanoparticles, in addition to the higher number of the catalytically active sites and the efficient bulk charge transport in the film, compared with w/o-α-Fe₂O₃.