Mechanistic insights into lepidocrocite conversion to hematite from variable temperature Raman microscopy

Abstract The consistent fabrication of high performance α -Fe ₂ O ₃ photoanodes for the oxygen evolution reaction remains a challenge. We work towards resolving this issue by developing in situ variable temperature Raman spectroscopy as a means to better understand the formation of α -Fe ₂ O ₃ , using the conversion of γ -FeOOH to α -Fe ₂ O ₃ under varied gaseous environments as a model case. The sensitivity of Raman spectroscopy to structural changes provides mechanistic insights that are not readily available in more conventional approaches, such as thermal gravimetric analysis and differential scanning calorimetry. The Raman spectra are combined with conventional thermal analyses to interpret the photoelectrocatalytic performance of a series of α -Fe ₂ O ₃ photoanodes prepared by systematic variation of a three-stage annealing protocol. The combined results suggest that protohematite, a form of α -Fe ₂ O ₃ where trapped hydroxyl ligands are balanced by Fe(III) vacancies, forms between 200 °C and 400 °C in a reaction environment-dependent fashion. This protohematite is shown to be remarkably persistent once formed, degrading photoelectrocatalytic performance. This research advances understanding of the γ -FeOOH to α -Fe ₂ O ₃ structural transformation, illustrates a powerful method to study solid state phase transitions, and provides guidance for the synthesis of high quality α -Fe ₂ O ₃ from a convenient precursor.