Differentiating Defects and Their Influence on Hematite Photoanodes Using X‑ray Absorption Spectroscopy and Raman Microscopy

A high degree of variability in behavior and performance of hematite as photoanodes for the oxygen evolution reaction signifies a need to improve our understanding of the interplay between defects and photoelectrochemical performance. We approach this problem by applying structure–property analysis to a series of hematite samples synthesized under either O₂ or N₂ environments such that they exhibit highly variable performance for photoelectrocatalytic oxygen evolution. X-ray absorption fine-structure spectroscopy and Raman spectroscopy provide parameters describing the structure of samples across the series. Systematic comparisons of these parameters to those describing photoelectrochemical performance reveal different defects in samples prepared under N₂ or O₂. Distinct correlations between both the iron oxidation state and charge carrier density with photoelectrocatalytic performance lead to assignment of the primary defects as oxygen vacancies (N₂) and iron vacancies (O₂). Differences in the structural distortions caused by these defects are seen in correlations between short-range structural parameters and photoelectrochemical behavior. These distortions are readily observed by Raman spectroscopy, suggesting that it may be possible to calibrate the width, energy, and intensity of peaks in Raman spectra to enable direct analysis of defects in hematite photoanodes.