Engineering Charge Transfer Characteristics in ZnO NRs/Ag₂O NPs p–n Heterojunctions: Toward Highly Efficient and Recyclable Photocatalysts

Staggered gap p-n heterojunction ZnO nanorods/Ag₂O nanoparticles, a paradigm of photocatalysts, were developed via engineering the hydrothermal and coprecipitation method. Under simulated sunlight, the photocatalytic characteristics of ZnO/Ag₂O(Zn/A) heterojunctions with varying mole ratios (from 8:1 to 8:4, named Zn/A-1-Zn/A-4) were systematically evaluated through the degradation of methylene blue (MB). The influence of key experimental variables, including photocatalyst concentration, MB concentration, and solution pH, on the photocatalyst performance was further analyzed. The incorporation of Ag₂O enhanced visible-light absorption, improved electron-hole separation efficiency, and significantly improved the photocatalytic recyclability of the Zn/A heterojunctions. Additionally, metallic Ag generated during photodegradation was found to enhance the photocatalytic activity further. Kinetic studies indicated that the photocatalytic degradation of MB followed pseudo-first-order kinetics, with the Zn/A-3 heterojunction showing the highest photocatalytic activity, achieving a degradation rate constant (<i>k</i>) of 0.028 min^-1. Scavenger experiments confirmed that •OH radicals, holes (h⁺), and superoxide radicals (•O₂^-) were the primary reactive species involved in the degradation process. The photocatalytic mechanism was identified as a Z-scheme charge transfer system, facilitating efficient charge separation. Moreover, the Zn/A-3 heterojunction exhibited remarkable recyclability, retaining >91% of the photocatalytic activity after five cycles. This study demonstrates the potential of Zn/A heterojunctions for practical applications in industrial wastewater treatment using solar energy.