In Situ Charge Transfer at the Ag@ZnO Photoelectrochemical Interface toward the High Photocatalytic Performance of H₂ Evolution and RhB Degradation

Designing an efficient hybrid structure photocatalyst for photocatalytic decomposition and hydrogen (H₂) evolution has been considered a great choice to develop renewable technologies for clean energy production and environmental remediation. Enhanced charge transfer (CT) based on the interaction between a noble metal and a semiconductor is a crucial factor influencing the movement of photogenerated electron-hole pairs. Herein, we focus on the recent advances related to plasmon-enhanced noble metals and the semiconductor nature to drive the photocatalytic H₂ production and photodegradation of the organic dye rhodamine B (RhB) under UV and visible light irradiation. Specifically, the combination of concerted catalysis and green nanoengineering strategies to design ZnO-based composite photocatalysts and their decoration with metallic Ag have been realized by the radio frequency (RF) sputtering technique at room temperature. This simultaneity enhances the interface coupling between Ag and ZnO and reduces the energy threshold. The creation of charge transfer in the heterojunction and Schottky barrier changes the photoelectronic properties of the as-synthesized Al-doped ZnO (AZO); afterward, these effects promote the migration, transportation, and separation of photoinduced charge carriers and enhance the light-harvesting efficiency. As a result, the as-synthesized AZO-20 hybrid nanostructure exhibits a photocurrent density of 2.5 mA/cm² vs Ag/AgCl, which is improved by almost 12 times compared with that of bare ZnO (0.2 mA/cm²). The hydrogen evolution rates of AZO-20 were ∼38 and ∼24 μmol/h under UV and visible light exposure, which are almost five- and tenfold higher than those of pristine ZnO, respectively. Additionally, the RhB degradation efficacies of the obtained AZO-20 were greater than almost 97 and 82% under UV and visible light illumination, respectively. The achieved apparent rate constant for the photocatalytic RhB decomposition was 0.014 min^-1, indicating that it is 14-fold than that in pristine ZnO (0.001 min^-1). Heterostructure AZO photocatalysts possess excellent practical stability in the water-splitting reaction and photocatalytic RhB decomposition, posing as promising candidates in practical works for pollution and energy challenges.