Photoelectrochemical Oxygen Evolution Reaction Research Articles

New Insights into Water Splitting at Mesoporous α-Fe2O3 Films: A Study by Modulated Transmittance and Impedance Spectroscopies

Thin mesoporous films of α-Fe(2)O(3) have been prepared on conducting glass substrates using layer-by-layer self-assembly of ca. 4 nm hydrous oxide nanoparticles followed by calcining. The electrodes were used to study the oxygen evolution reaction (OER) in the dark and under illumination using in situ potential-modulated absorption spectroscopy (PMAS) and light-modulated absorption spectroscopy (LMAS) combined with impedance spectroscopy. Formation of surface-bound higher-valent iron species (or "surface trapped holes") was deduced from the PMAS spectra measured in the OER onset region. Similar LMAS spectra were obtained at more negative potentials in the onset region of photoelectrochemical OER, indicating involvement of the same intermediates. The impedance response of the mesoporous α-Fe(2)O(3) electrodes exhibits characteristic transmission line behavior that is attributed to slow hopping of holes, probably between surface iron species. Frequency-resolved PMAS and LMAS measurements revealed slow relaxation behavior that can be related to the impedance response and that indicates that the lifetime of the intermediates (or trapped holes) involved in the OER is remarkably long.

Photoproduction of hydrogen: Potential dependence of the quantum efficiency as a function of wavelength

The quantum efficiencies ( Q) of the photoelectrochemical oxygen evolution reaction on reduced TiO 2 in 0.1 N NaOH have been measured as a function of electrode potential and photon energy ( E) over the range 3.2–4.0 eV. Maxima in the Q- E relations over the potential range −0.4–+1.25 V NHE were observed and the maxima shifted towards lower photon energies as the potential became more positive. This trend can be interpreted in terms of the variation of the absorption coefficient with frequency.