Electron pump-shuttle cathode enables coupled directed-electron flows for resource-oriented treatment of radioactive wastewater.

Recovering uranium from radioactive wastewater is imperative for environmental sustainability and nuclear energy security, yet it is severely impeded by stable UO22+-organic complexes. Herein, we present a solar-driven self-sustaining photoelectrochemical system (SDSSPS) that achieves sustainable and resource-oriented treatment through coupled directed‑electron flows between a self‑biased photoanode and a copper nanowire/copper foam (CuNWs/CF) cathode. The photoanode efficiently degrades organics to disrupt complexes and drives photogenerated electrons toward the cathode. The dual-function CuNWs/CF cathode provides reductive Cu0 sites that pump electrons via a Cu-O-U bridge to spontaneously reduce adsorbed UO22+ into UO2 deposits even in the dark, while simultaneously shuttling incoming electrons to regenerate active Cu0 from Cu+, thereby maintaining a persistent redox cycle. This synergistic coupling enables efficient treatment, achieving 98.7% uranium recovery and 96.5% tetracycline hydrochloride (TCH) removal, corresponding to 2.25- and 2.17-fold kinetic enhancements over the CF-based SDSSPS. The system demonstrates strong anti-interference capability, broad applicability, and excellent stability over eight consecutive cycles (> 90.0% removal efficiency, > 95.0% uranium elution). Its practical viability is further validated using real uranium-containing wastewater, under natural sunlight, and in continuous-flow operation. This solar‑powered, self‑sustaining electron‑management design establishes a stable and sustainable strategy for resource‑oriented remediation of complex radioactive wastewater.