Understanding charge transport in non-doped pristine and surface passivated hematite (Fe2O3) nanorods under front and backside illumination in the context of light induced water splitting.

Hematite (Fe2O3) nanorods on FTO substrates have been proven to be promising photoanodes for solar fuel production but only with high temperature thermal activation which allows diffusion of tin (Sn) ions from FTO, eventually enhancing their conductivity. Hence, there is a trade-off between the conductivity of Fe2O3, and the degradation of FTO occurring at high annealing temperatures (>750 °C). Here, we present a comprehensive study on undoped Fe2O3 nanorods under front and back illumination to find the optimum annealing temperature. Bulk/surface charge transport efficiency analysis demonstrates minimum bulk recombination indicating overall high quality crystalline Fe2O3 and the preservation of FTO conductivity. Surface recombination is further improved by growing a TiOx overlayer, which improves the photocurrent density from 0.2 mA cm-2 (backside) to 1.2 mA cm-2 under front side and 0.8 mA cm-2 under backside illumination. It is evident from this study that the performance of undoped and unpassivated hematite nanorods is limited by electron transport, whereas that of doped/passivated hematite nanorods is limited by hole transport.

Improved Charge Separation in WO3/CuWO4 Composite Photoanodes for Photoelectrochemical Water Oxidation.

Porous tungsten oxide/copper tungstate (WO3/CuWO4) composite thin films were fabricated via a facile in situ conversion method, with a polymer templating strategy. Copper nitrate (Cu(NO3)2) solution with the copolymer surfactant Pluronic®F-127 (Sigma-Aldrich, St. Louis, MO, USA, generic name, poloxamer 407) was loaded onto WO3 substrates by programmed dip coating, followed by heat treatment in air at 550 °C. The Cu2+ reacted with the WO3 substrate to form the CuWO4 compound. The composite WO3/CuWO4 thin films demonstrated improved photoelectrochemical (PEC) performance over WO3 and CuWO4 single phase photoanodes. The factors of light absorption and charge separation efficiency of the composite and two single phase films were investigated to understand the reasons for the PEC enhancement of WO3/CuWO4 composite thin films. The photocurrent was generated from water splitting as confirmed by hydrogen and oxygen gas evolution, and Faradic efficiency was calculated based on the amount of H2 produced. This work provides a low-cost and controllable method to prepare WO3-metal tungstate composite thin films, and also helps to deepen the understanding of charge transfer in WO3/CuWO4 heterojunction.

Revealing the Role of TiO2 Surface Treatment of Hematite Nanorods Photoanodes for Solar Water Splitting.

Ultrathin TiO2 is deposited on conventional hydrothermal grown hematite nanorod arrays by atomic layer deposition (ALD). Significant photoelectrochemical water oxidation performance improvement is observed when the ALD TiO2-treated samples are annealed at 650 °C or higher temperatures. The electrochemical impedance spectroscopy (EIS) study shows a surface trap-mediated charge transfer process exists at the hematite-electrolyte interface. Thus, one possible reason for the improvement could be the increased surface states at the hematite surface, which leads to better charge separation, less electron-hole recombination, and hence, greater improvement of photocurrent. Our Raman study shows the increase in surface defects on the ALD TiO2-coated hematite sample after being annealed at 650 °C or higher temperatures. A photocurrent of 1.9 mA cm(-2) at 1.23 V (vs RHE) with a maximum of 2.5 mA cm(-2) at 1.8 V (vs RHE) in 1 M NaOH under AM 1.5 simulated solar illumination is achieved in optimized deposition and annealing conditions.

Hydrothermal grown nanoporous iron based titanate, Fe2TiO5 for light driven water splitting.

We report the synthesis of iron based titanate (Fe2TiO5) thin films using a simple low cost hydrothermal technique. We show that this Fe2TiO5 works well as a photoanode for the photoelectrochemical splitting of water due to favorable band energetic. Further characterization of thin films including band positions with respect to water redox levels has been investigated. We conclude that Fe2TiO5 is a promising material comparable to hematite for constructing PEC cells.

Improving the efficiency of hematite nanorods for photoelectrochemical water splitting by doping with manganese.

Here, we report a significant improvement of the photoelectrochemical (PEC) properties of hematite (α-Fe2O3) to oxidize water by doping with manganese. Hematite nanorods were grown on a fluorine-treated tin oxide (FTO) substrate by a hydrothermal method in the presence on Mn. Systematic physical analyses were performed to investigate the presence of Mn in the samples. Fe2O3 nanorods with 5 mol % Mn treatment showed a photocurrent density of 1.6 mA cm(-2) (75% higher than that of pristine Fe2O3) at 1.23 V versus RHE and a plateau photocurrent density of 3.2 mA cm(-2) at 1.8 V versus RHE in a 1 M NaOH electrolyte solution (pH 13.6). We attribute the increase in the photocurrent density, and thus in the oxygen evolving capacity, to the increased donor density resulting from Mn doping of the Fe2O3 nanorods, as confirmed by Mott-Schottky measurement, as well as the suppression of electron-hole recombination and enhancement in hole transport, as detected by chronoamperometry measurements.

Iron based photoanodes for solar fuel production.

In natural photosynthesis, the water splitting reaction of photosystem II is the source of the electrons/reducing equivalents for the reduction of carbon dioxide to carbohydrate while oxygen is formed as the by-product. Similarly, for artificial photosynthesis where the end product is a solar fuel such as hydrogen, a water splitting-oxygen evolving system is required to supply high energy electrons to drive the reductive reactions. Very attractive candidates for this purpose are iron based semiconductors which have band gaps corresponding to visible light and valence band energies sufficient to oxidise water. The most studied system is hematite (Fe2O3) which is highly abundant with many attributes for incorporation into photoelectrochemical (PEC) cells. We review the recent progress in manipulating hematite for this purpose through nanostructuring, doping and surface modifications. We also consider several hybrid iron-based semiconducting systems like ferrites and iron titanates as alternatives to hematite for light driven water splitting emphasizing their advantages with respect to their band levels and charge transport properties.

Surface treatment of hematite photoanodes with zinc acetate for water oxidation.

A simple and inexpensive method to form a hematite photoanode for efficient water oxidation is reported. A very thin ZnO overlayer was deposited on top of a thin film of hematite and found, compared with non-treated hematite, to increase the photocurrent and reduce the onset potential for generating oxygen from water. After 3 cycles of ZnAc treatment, the photocurrent increased more than 40% to 1.08 mA cm(-2) at 0.23 V vs. Ag/AgCl and onset potential for water oxidation shifted by -170 mV. It is proposed that the ZnO overlayer changes the flat band potential of hematite and reduces the surface defects.