Self‐Driven and Self‐Cleaning Electrochemical System for Energy‐Efficient and High‐Selectivity Uranium Extraction

Abstract Extracting U(VI) from water is significant for the sustainability of nuclear energy and environmental remediation. An electrochemical route with rapid kinetics and high extraction capacity is a promising option. However, conventional electrochemical methods suffer from intrinsic trade‐offs among efficiency, selectivity, and energy consumption. Herein, a self‐driven and self‐cleaning electrochemical (SDCE) system is constructed for the synergistic U(VI) extraction and electricity generation by spatially decoupling redox reactions and the design of self‐cleaning electrode. By coupling Fe oxidation with the 2e − oxygen reduction reaction, electricity generation and the spontaneous production of H 2 O 2 are achieved, which selectively precipitates U(VI) as (UO 2 )O 2 ·4H 2 O(s). The precisely constructed hydrophobic microenvironment of the self‐cleaning electrode blocks competitive ions and uranium products from adhesion, while boosting H 2 O 2 generation and its subsequent reaction with U(VI). Consequently, the system demonstrates both exceptional extraction efficiency and selectivity for U(VI) in various complex water samples. Notably, the U(VI)/V(V) separation factor of the system reaches 720, much higher than that of conventional electrochemical methods. Besides, the system operates with zero energy consumption and a low operating cost of 32.22 USD kg −1 U, making it one of the most economical U(VI) extraction systems. Overall, this work establishes a new paradigm for the cost‐effective and selective extraction of U(VI).