Spatially Separated Redox Centers in One‐Dimensional Sp ² ‐Carbon Covalent Organic Frameworks Enable Synergistic Photocatalytic Palladium Recovery and Bisphenol A Mineralization

ABSTRACT The simultaneous recovery of precious metal and pollutant degradation is often hindered by competing redox processes. Herein, we address this condition by designing a one‐dimensional covalent organic framework (COF), olefin‐linked iridium COF (Ole Ir‐COF ²⁺ ), featuring a donor–acceptor–acceptor cascade. Ir complexes and pyrene units form a dual photosensitizing system enabling broad‐spectrum absorption, while quaternized bipyridine groups precisely modify the framework edges to create a cationic interface that selectively anchors PdCl ₄ ²⁻ . The fully conjugated backbone establishes spatially separated oxidation (Ir/pyrene) and reduction (bipyridinium) centers, synergistically promoting efficient mass transfer and directional charge transport. Ole Ir‐COF ²⁺ exhibits a carrier lifetime of 5.06 ns (threefold longer than Ole COF ⁴⁺ ) and an ultralow exciton binding energy of 25.3 meV (half that of Ole COF ⁴⁺ ). Without sacrificial agents, it achieves a palladium [Pd(II)] extraction capacity of 1749 mg g ⁻¹ (twofold higher than that of Ole COF ⁴⁺ ) and a bisphenol A (BPA) degradation rate constant of 0.1710 min ⁻¹ .