Photocatalytic Oxygen Reduction Pathway Modulating on Cadmium Sulfide via Surface Doping Engineering for In‐Situ Synthesis of Hydrogen Peroxide Coupled With Organic Valorization

ABSTRACT

Tuning the oxygen reduction reaction (ORR) pathway is essential for steering the selective generation of reactive oxygen species (ROS) in targeted applications. Here, Fe‐doped cadmium sulfide (Fe‐CdS) nanorods were rationally designed to modulate surface ORR pathways, enabling efficient hydrogen peroxide (H ₂ O ₂ ) production via optimized electron transfer dynamics. By precisely controlling the content of Fe doping, we have achieved customized generation of photocatalytic reactive oxygen species. Under irradiation, low Fe doping (1%) favored a 2‐electron ORR pathway, yielding H ₂ O ₂ at a rate of 483.5 µM h ⁻¹ , surpassing that of CdS and 2%–5% Fe‐CdS. In contrast, 5% Fe doping induced a shift toward H ₂ O ₂ production and decomposition‐mediated the generation of hydroxyl at 110.2 µM h ⁻¹ . Strong metal–support interactions facilitated efficient charge separation, while excess Fe sites catalyzed H ₂ O ₂ decomposition. The photocatalytic H ₂ O ₂ production platform was further integrated with in situ organic synthesis, demonstrating dual‐functional photoredox transformations, including arylboronic acid oxidation and amide coupling. This work establishes structure‐activity relationships governing ROS‐selectivity in doped photocatalysts, while pioneering a light‐driven synthetic paradigm that concurrently addresses green oxidant production and selective organic synthesis.