ABSTRACT
A unique two-step co-doping strategy of in situ fluorine doping followed by ex situ titanium doping enhances the performance of the hematite photoanode in photoelectrochemical water splitting much more effectively than single-step co-doping strategies that are either all in situ or all ex situ. The optimized fluorine, titanium co-doped Fe2O3 photoanode without any cocatalyst achieves 1.61 mA cm-2 at 1.23 VRHE under 100 mW cm-2 solar irradiation, which is â¼2 and 3 times those of titanium or fluorine singly-doped Fe2O3 photoanodes, respectively. The promotional effect is attributed to the synergy of the two dopants, in which the doped fluorine anion substitutes oxygen of Fe2O3 to increase the positive charges of iron sites, while the doped titanium cation substitutes iron to increase free electrons. Moreover, excess titanium on the surface suppresses the drain of in situ doped fluorine and agglomeration of hematite during the high-temperature annealing process, and passivates the surface trap states to further promote the synergy effects of the two dopants.
ABSTRACT
An ultrathin (ca. 2â nm) amorphous FeOOH overlayer was deposited conformally on a hematite nanostructure by a simple solution-based precipitation method, to generate an oxygen evolution cocatalyst for efficient solar water splitting. This uniform and highly conformal coating of the ultrathin metal oxyhydroxide is rare and is distinguished from the layers prepared by other conventional methods. With the FeOOH overlayer as the cocatalyst, the water oxidation photocurrent of hematite increased by a factor of approximately two and the onset potential shifted in the cathodic direction by 0.12â V under 1â sun illumination. The enhanced performance was attributed to the improved water oxidation kinetics and the passivation of the surface states of the hematite.
