Surface‐Strongly Complexed <scp> BiVO ₄ </scp> Homojunction Photoanodes: Enabling Efficient Antibiotic Pollutant Degradation and Resource Upgrading

Photoelectrochemical (PEC) technology offers a promising approach for degrading antibiotic pollutants, yet it remains constrained by low efficiency and incomplete mineralization. Herein, a Co‐doped BiVO 4 /Mo‐doped BiVO 4 homojunction photoanode and kanamycin strongly complexed PEC system is constructed for efficient pollutant degradation and H 2 generation. Mo doping and homojunction formation enhance the electrical conductivity and charge separation of the photoanode, while the strong complexation between the photoanode and kanamycin facilitates interfacial charge transfer. Consequently, the optimized photoanode delivers a current density of 9.61 mA cm −2 at 1.00 V versus a reversible hydrogen electrode under simulated sunlight irradiation and maintains excellent stability. Near‐unity Faradaic efficiencies for both anodic CO 2 /N 2 generation and cathodic H 2 evolution confirm the complete mineralization and chemical energy recovery of kanamycin. To mitigate carbon emissions and valorize the generated CO 2 and H 2 , a photothermal CO 2 hydrogenation system is further integrated, demonstrating a superior CO yield of 122.65 mmol g −1 h −1 with nearly 100% selectivity. This synergistic PEC‐photothermal platform achieves simultaneous kanamycin remediation and resource valorization, providing a viable strategy to address energy and environmental concerns.