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Recently, heterostructured photocatalysts have gained significant attention in the field of photocatalysis due to their superior properties compared to single photocatalysts. One of the key advantages of heterostructured photocatalysts is their ability to enhance charge separation and broaden the absorption spectrum, thereby improving photocatalytic efficiency. Zinc oxide is a widely used n-type semiconductor with a proper photoelectrochemical activity. In this study, zinc oxide nanorod arrays were synthesized, and then the surfaces of ZnO nanorods were modified with the p-type semiconductor Co3O4 to create a p–n junction heterostructure. A significant increase in the photocurrent for the ZnO/Co3O4 composite, of 4.3 times, was found compared to pure ZnO. The dependence of the photocurrent on the morphology of the ZnO/Co3O4 composite allows for optimization of the morphology of the ZnO nanorod array to achieve improved photoelectrochemical performance. The results showed that the ZnO/Co3O4 heterostructure exhibited a photocurrent density of 3.46 mA/cm2, while bare ZnO demonstrated a photocurrent density of 0.8 mA/cm2 at 1.23 V. The results of this study provide a better understanding of the mechanism of charge separation and transfer in the heterostructural ZnO/Co3O4 photocatalytic system. Furthermore, the results will be useful for the design and optimization of photocatalytic systems for water splitting and other applications. [ABSTRACT FROM AUTHOR]