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Tubular hematite with high-concentration, uniform doping is regarded as a promising material for photoelectrochemical water oxidation. However, the high-temperature annealing commonly used for activating doped hematite inevitably causes deformation of the tubular structure and an increase in the trap states. In the present work, Sn-doped tubular hematite on fluorine-doped tin oxide (FTO) is successfully obtained at 750 °C from a Sn-coated FeOOH tube precursor. Sn/P codoping, which is rarely considered for hematite, is also achieved via a gas phase reaction in phosphide atmosphere. The tubular morphology allows the dopant to diffuse from both the inner and outer surfaces, thus decreasing the doping profile in the radial direction. The even distribution of Sn and P synergetically increases the carrier density of hematite by one order of magnitude, which shortens the width of the depletion layer to ca. 2.3 nm (compared with 19.3 nm for the pristine sample) and leads to prolonged carrier lifetime and efficient charge separation. In addition, this codoping protocol does not introduce additional surface trap states, as evidenced by the increased charge injection efficiency and surface kinetic analysis using intensity modulated photocurrent spectroscopy (IMPS). As a result, the morphology- and doping-engineered hematite exhibits photocurrents of 0.9 mA cm−2 at 1.23 V and 3.8 mA cm−2 at 2.0 V vs. RHE under AM 1.5 G illumination (100 mW cm−2) in 1.0 M NaOH, representing 4.5-fold and 4.8-fold enhancements, respectively, compared with the photocurrents of undoped hematite. The present method is shown to be effective for preparing multi-element-doped hematite nanotubes and may find broad application in the development of other nanotubular photoelectrodes with or without doping for efficient and robust water oxidation. [ABSTRACT FROM AUTHOR]

To overcome tough conditions currently used for the preparation of nanostructured hematite films on a conducting substrate, a rational and easy method of chemical etching involving Fe3+ release and material growth in the presence of OH− has been developed. By carefully tuning the parameters influencing the morphologies of hematite, including the synthetic procedure, the concentration of etching solution, temperature, etching time and the morphology controlling surfactant, hematite films grown on iron foil with various morphologies (e.g. nanorod, nanowire, ultrathin nanoflake and cauliflower-like shape) have been achieved. In particular, it is found that F− is an effective surfactant to control the morphology as well as the crystallization process of hematite. Ultrathin nanoflakes having a minimized feature size exhibit the best photocurrent of 0.5 mA cm−2 (1.23 V vs. RHE, RHE is reversible hydrogen electrode) among the samples tested as a result of facilitated hole diffusion to the electrolyte and thus lowered carrier recombination. Compared with pristine hematite, a nearly tripled photocurrent is observed when H2O2 is added in the electrolyte as a hole scavenger, suggesting the presence of a charge injection barrier in the surface of samples. According to this, the strategy of Co2+ treatment is utilized and the improved photocurrent is seen, likely due to the improved water oxidation kinetics and surface state passivation. We believe that this convenient and economical method can be extended to the synthesis of other alkaline metal oxide nanomaterials as long as the redox potential of S2O82−/SO42− is higher than Mn+/M (M refers to metal). [ABSTRACT FROM AUTHOR]