Nanometric Fe-Substituted ZrO2_Madkikar et al.

In this contribution, we demonstrate the presence of high-spin Fe3+ in Fe-substituted ZrO2 (FexZr1−xO2−δ), as deduced from X-ray photoelectron spectroscopy (XPS), near-edge X-ray absorption fine structure (NEXAFS), and 57Fe Mössbauer spectroscopy measurements. The activity of this carbon-supported FexZr1−xO2−δ catalyst towards the oxygen reduction reaction (ORR) was examined by both the rotating (ring) disk electrode (R(R)DE) method and in single-cell proton exchange membrane fuel cells (PEMFCs). DFT calculations suggest that the much higher ORR mass activity of FexZr1−xO2−δ compared to Fe-free ZrO2 is due to the enhanced formation of oxygen vacancies: their formation is favored after Zr4+ substitution with Fe3+ and the oxygen vacancies create potential adsorption sites, which act as active centers for the ORR. H2O and/or H2O2 production observed in RRDE measurements for the Fe0.07Zr0.93O1.97 is also in agreement with the most likely reaction paths from DFT calculations. In addition, Tafel and Arrhenius analyses are performed on Fe0.07Zr0.93O1.97 using both RRDE and PEMFC data at various temperatures.