Synergistic Photoelectrocatalytic Degradation of Tetracycline Using Phosphate-Grafted Mo:BiVO4 Photoanode Coupled with Pd/CMK-3 Cathode for Dual-Functional Activation of Water and Molecular Oxygen

This research introduces a synergistic photoelectrocatalytic (PEC) system designed for the effective degradation of tetracycline (TC), integrating a PO43−-grafted Mo-doped BiVO4 (PO43−-Mo:BiVO4) photoanode with a Pd-loaded ordered mesoporous carbon (Pd/CMK-3) cathode. The incorporation of Mo doping and PO43− modification significantly improved the photoanode’s charge separation efficiency, achieving a photocurrent density of 2.9 mA cm−2, and fine-tuned its band structure to enhance hydroxyl radical (·OH) generation. Meanwhile, the Pd/CMK-3 cathode promoted a two-electron oxygen reduction reaction pathway, producing hydrogen peroxide (H2O2) and facilitating molecular oxygen activation via atomic hydrogen (H*) intermediates. Under optimized conditions—1.0 V vs. Ag/AgCl of anodic potential, pH 6.58, and oxygen saturation—the combined system accomplished 80% TC degradation within 60 min, markedly surpassing the performance of the photoanode (72%) or cathode (71%) alone. Notably, this synergistic approach also reduced energy consumption to 0.0065 kWh m−3, outperforming individual components. Radical quenching experiments and liquid chromatography–mass spectrometry (LC-MS) analysis revealed that the photogenerated holes (h+) and ·OH were the key reactive species responsible for TC mineralization. The system demonstrated remarkable stability, with only a 2.96% decline in activity, and effectively degraded other contaminants, such as phenol, 4-chlorophenol, and ciprofloxacin. This study highlights an energy-efficient PEC strategy that harnesses the combined strengths of anodic oxidation and cathodic molecular oxygen activation to significantly enhance the removal of organic pollutants.