• Energy Research

The photoelectrochemical behavior of a planar 1 cm2 thick Ti-doped hematite film deposited on F:SnO2 coated glass was studied with both front and back illumination. Despite low quantum efficiency, photocurrent was observed upon back illumination with low wavelengths, indicating that some photogenerated holes are able to traverse at least 700 nm across the hematite film and effectively oxidize water. This cannot be accounted for using the commonly accepted hole collection length of hematite based on fitting to the Gartner model. Furthermore, under back illumination, 450 nm excitation resulted in increased photocurrent as compared to 530 nm excitation despite most of the light being absorbed further away from the surface. These results demonstrate that the photocurrent is strongly dependent on the optical excitation wavelength, and related to both delocalized holes with long lifetime and localized excitations rather than only being dependent on the proximity of the absorption to the surface.

Heteroepitaxial hematite thin film photoanodes were fabricated, characterized, and shown to be a model system for fundamental studies into solar water splitting.

Doping with Ti enhances the electron conductivity and photoelectrochemical properties in hematite (α-Fe2O3) photoanodes with respect to those of undoped hematite photoanodes. However, the optimal doping level is unknown. This work examined the influence of the Ti doping level on the photoelectrochemical properties of thin-film (∼50-nm) hematite photoanodes. The films were deposited by pulsed laser deposition (PLD) on glass substrates coated with transparent electrodes (fluorinated tin oxide, FTO) from Ti-doped Fe2O3 targets with different Ti concentrations: 0 (undoped), 0.25, 0.8, 1, and 7 cation %. The film thicknesses, morphologies, microstructures, and optical properties were nearly the same for all of the photoanodes, thereby enabling systematic comparison of the effect of the doping level without spurious side effects related to morphological variations. The photoelectrochemical performances of all of the Ti-doped photoanodes were considerably higher than that of the undoped photoanode. Among the dop...

The spin states at the surface of epitaxial thin films of hematite, both undoped and doped with 1% Ti, Sn or Zn, respectively, were probed with x-ray magnetic linear dichroism (XMLD) spectroscopy. Morin transitions were observed for the undoped (T_M~200 K) and Sn-doped (T_M~300 K) cases, while Zn and Ti-doped samples were always in the high and low temperature phases, respectively. In contrast to what has been reported for bulk hematite doped with the tetravalent ions Sn4+ and Ti4+, for which T_M dramatically decreases, these dopants substantially increase T_M in thin films, far exceeding the bulk values. The normalized Fe LII-edge dichroism for TT_M state was achieved. The temperature dependence of the critical field for the Sn-doped sample was characterized in detail. It was demonstrated the sample-to-sample variations of the Fe LIII-edge spectra were, for the most part, determined solely by the spin orientation state. Calculations of the polarization-depedent spectra based on a spin-multiplet model were in reasonable agreement with the experiment and showed a mixed excitation character of the peak structures. 8 pages, 8 figures

Reference EPFL-ARTICLE-216288doi:10.1002/aenm.201500817View record in Web of Science Record created on 2016-02-16, modified on 2017-12-03

Electrolytic hydrogen production faces technological challenges to improve its efficiency, economic value and potential for global integration. In conventional water electrolysis, the water oxidation and reduction reactions are coupled in both time and space, as they occur simultaneously at an anode and a cathode in the same cell. This introduces challenges, such as product separation, and sets strict constraints on material selection and process conditions. Here, we decouple these reactions by dividing the process into two steps: an electrochemical step that reduces water at the cathode and oxidizes the anode, followed by a spontaneous chemical step that is driven faster at higher temperature, which reduces the anode back to its initial state by oxidizing water. This enables overall water splitting at average cell voltages of 1.44–1.60 V with nominal current densities of 10–200 mA cm−2 in a membrane-free, two-electrode cell. This allows us to produce hydrogen at low voltages in a simple, cyclic process with high efficiency, robustness, safety and scale-up potential. Conventionally, the two half reactions involved in water electrolysis occur simultaneously, presenting materials and process challenges. Here, the authors decouple these to split water efficiently in two steps: electrochemical hydrogen evolution, followed by spontaneous oxygen evolution at elevated temperature.

Abstract

Thin (~50 nm) film hematite photoanodes doped with different dopants at a concentration of 1 cation% display internal solar to chemical (ISTC) conversion efficiency in the following order: Sn > Nb > Si > Pt > Zr > Ti > Zn > Ni > Mn.