Crystal Structure of β-Fe2O3 and Topotactic Phase Transformation to α-Fe2O3

beta-Fe2O3 is the scarce polymorph of Fe2O3 phases and is transformed easily into alpha-Fe2O3 at high temperature. However, its crystal structure and the transformation, mechanism to alpha-Fe2O3 are still unclear because of the difficulty in obtaining monophasic beta-Fe2O3 crystals. We established a synthesis method of the monophasic beta-Fe2O3. It was synthesized by a two-step reaction: heating a mixture of Na2SO4 and Fe-2(SO4)(3) in air at 250 degrees C to form NaFe(SO4)(2), and subsequent heating the resultant phase with NaCl in air at 500 degrees C. The crystal structure was refined to a bixbyite-type cubic structure (Ia (3) over bar) with alpha = 9.4039(1) angstrom by the Rietveld method. Single crystalline beta-Fe2O3 particles of approximately 1 mu m in size were topotactically transformed into single alpha-Fe2O3 crystals. Electron diffraction analysis revealed the crystallographic orientation relationships between beta-Fe2O3 and alpha-Fe2O3 to be [100](beta)//[0001](alpha), [010](beta)//[10 (1) over bar0](alpha), and [001](beta)//[(1) over bar2 (1) over bar0](alpha).