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We report on the fabrication and characterization of a novel $Cu_2O/CuO$ heterojunction structure with CuO nanorods embedded in $Cu_2O$ thin film as an efficient photocathode for photoelectrochemical (PEC) solar water splitting. A CuO nanorod array was first prepared on an indium-tin-oxide-coated glass substrate via a seed-mediated hydrothermal synthesis method; then, a $Cu_2O$ thin film was electrodeposited onto the CuO nanorod array to form an oxide semiconductor heterostructure. The crystalline phases and morphologies of the heterojunction materials were examined using X-ray diffraction and scanning electron microscopy, as well as Raman scattering. The PEC properties of the fabricated $Cu_2O/CuO$ heterojunction photocathode were evaluated by photocurrent conversion efficiency measurements under white light illumination. From the observed PEC current density versus voltage (J-V) behavior, the $Cu_2O/CuO$ photocathode was found to exhibit negligible dark current and high photocurrent density, e.g. $-1.05mA/cm^2$ at -0.6 V vs. $Hg/HgCl_2$ in $1mM\;Na_2SO_4$ electrolyte, revealing the effective operation of the oxide heterostructure. The photocurrent conversion efficiency of the $Cu_2O/CuO$ photocathode was estimated to be 1.27% at -0.6 V vs. $Hg/HgCl_2$. Moreover, the PEC current density versus time (J-T) profile measured at -0.5 V vs. $Hg/HgCl_2$ on the $Cu_2O/CuO$ photocathode indicated a 3-fold increase in the photocurrent density compared to that of a simple $Cu_2O$ thin film photocathode. The improved PEC performance was attributed to a certain synergistic effect of the bilayer heterostructure on the light absorption and electron-hole recombination processes.
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