Defect‐Engineered Solid Frustrated Lewis Pairs Direct Dual Nonradical Oxidation in Single‐Atom Catalysis via Push‐Push Electron Transfer

ABSTRACT Achieving controlled nonradical oxidation remains challenging because catalytic interfaces rarely provide decoupled yet electronically communicating pathways for directional electron transfer. Here, we demonstrate that defect‐engineered solid frustrated Lewis pair (FLP) coupled with Cu single atom establish a “push‐push” electron relay that orchestrates cooperative formation of high‐valent metal‐oxo and singlet oxygen ( 1 O 2 ) for a predominantly dual nonradical oxidation. The Cu single‐atom catalyst (D‐Cu‐N/C) integrates Cu n+ Lewis‐acid sites and defect‐anchored pyridinic‐N Lewis‐base sites, forming spatially separated yet electronically coupled FLP ensembles that polarize periodate. This concerted electron relay enables cooperative activation along two distinct channels, synchronizing Cu(III) = O formation with delocalized spin‐conserved oxygen evolution. Benefiting from this FLP‐directed dual nonradical pathway, D‐Cu‐N/C achieves a 1.7‐fold higher apparent rate constant for fluoxetine (FLU) removal and robustness against complex water matrices than Cu‐N/C. Mechanistic analyses reveal that defect engineering upshifts the Cu 3d band and strengthens dual‐site charge polarization that stabilize high‐valent Cu‐oxo species and accelerate spin‐conserved 1 O 2 evolution. This solid‐FLP concept provides a broadly applicable platform for programming interfacial electron transfer and enabling selective, sustainable oxidation in single‐atom catalysis.