Halogen Coordination Modulates Silver Immobilization Pathways on Cu(I)‐MOFs for Selective Silver Recovery From Complex Wastewaters

ABSTRACT Regulating the electronic structure is critically important for direct recovering elemental valuable metals from wastewater streams. Here, a series of electronegative halogens (Cl, Br, I) are incorporated to regulate the electronic structure of Cu(I)‐based metal–organic frameworks (MOFs), enabling efficient and selective Ag(I) recovery from complex wastewater. Among them, the chlorine‐coordinated CuClMOF, featuring Cu 2 (µ 2 ‐Cl) motifs, exhibits excellent performance by precisely tuning the electron density of low‐valent Cu(I) sites. This electronic regulation accelerates the rate‐limiting steps of Ag(I) recovery process, shifting from conventional Ag‐halide precipitation toward a controllable and efficient reduction‐nucleation pathway. As a result, CuClMOF achieves a record‐high Ag(I) recovery capacity (1279 mg g −1 ) and rapid kinetics ( k f ≈ 8.9 × 10 −5 m s −1 ), while maintaining exceptional selectivity against competing ions (exceeding state‐of‐the‐art adsorbents by 1‐4 orders of magnitude). Importantly, CuClMOF maintains > 99.4% recovery in real mining wastewater and electronic waste leachates, highlighting its robustness under environmentally relevant and chemically complex conditions. The recovered silver, with a purity of 99.8%, enables direct reuse, reducing the need for primary resource extraction. By coupling high‐efficiency silver enrichment with robust adsorbent reusability, this work establishes a halogen‐mediated electronic modulation strategy for designing redox‐active adsorbents, providing a material‐level solution for silver resource recovery from complex wastewaters.