Document Type


Corresponding Author(s)

Wen-Hua Leng (


Photocatalytic splitting of water over p-type semiconductors is a promising strategy for production of hydrogen. However, reports on the determination of rate law are rare. To this end, CuO as a model photocathode in this study, the photogenerated surface charge density, interfacial charge transfer rate constant and their relation to the water reduction rate (in terms of photocurrent) were investigated by a combination of (photo)electrochemical techniques. The results show that the charge transfer rate constant is exponential-dependent on the surface charge density and that the photocurrent equals to the product of the charge transfer rate constant and surface charge density. The reaction is first-order in terms of surface charge density. Such an unconventional rate law contrasts with the reports in literature. The charge density-dependent rate constant results from the Fermi level pinning (Galvani potential is the main driving force for the reaction) due to accumulation of charge in the surface states and/or Frumkin behavior (chemical potential is the main driving force). This study therefore may be helpful for further investigation on the mechanism of hydrogen evolution over CuO photocathode and for designing more efficient CuO-based photocatalysts.

Graphical Abstract


CuO, Photoelectrochemical water splitting, Electrochemical impedance spectroscopy, Rate law, Kinetics of photogenerated carriers

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