Photoelectrochemical
(PEC) water splitting devices using semiconductors
and electrocatalysts rely on heterogeneous interfaces that drive charge
separation, thus determining potential gradients that dictate the
reaction efficiency. The PEC potential of the electrocatalyst depends
on the chemical oxidation state of forming elements, which may strongly
vary under the photoinduced charge flow. However, element-sensitive,
real-time measurements of the oxidation state of the electrocatalyst
are not generally possible using conventional X-ray absorption techniques.
Here, we show that fixed-energy X-ray absorption voltammetry and chronoamperometry,
which measure the X-ray absorption coefficient variations along with
photocurrent, can follow in real time the redox kinetics of electrocatalysts.
To demonstrate the validity, we investigate hematite (α-Fe2O3) photoanodes covered with a nickel hydroxide
electrocatalyst and show that it is fully oxidized by photogenerated
holes to nickel oxyhydroxide with Ni reaching a higher oxidation state
(NiIV) than that observed under electrocatalytic oxygen
evolution in dark conditions. Highly oxidized Ni results from charge
accumulation in the overlayer and can be observed only in the case
of thick layers (with low PEC performance). On the other hand, the
average oxidation state of Ni reaches lower values, under operative
conditions, for very thin layers, resulting in high PEC activity.
We complete our study by presenting PEC activity and impedance spectroscopy
analysis using different thicknesses of the electrocatalyst, thus
giving a detailed picture of the multiple and complex charge transfer
processes occurring at a semiconductor/electrocatalyst junction.