Defect‐Engineered Inert Interfaces on Iron‐Rich Clay Minerals Boost Exclusive Electron Transfer Pathway in Fenton‐Like Reactions

Abstract The coexistence of electron donor/acceptor properties in oxidants leads to competing redox reactions at the interfacial active site in heterogeneous Fenton‐like systems, generating reactive oxygen species and posing persistent challenges for achieving complete electron transfer processes (ETP). Here, a mechanochemical strain‐induced defect engineering strategy is developed for chlorite inert silicate layers (BC/D─Chl) to enable a complete ETP pathway independent of oxidant adsorption mode modulation. Iron‐rich clay minerals inherently serve as electron sources and sinks, yet their inert silicate interfaces typically hinder oxidant activation. The constructed defect sites enhance the affinity of the silicate layer for peroxydisulfate (PDS), while the silicate lattice‐confined Fe(II)/Fe(III) redox cycle facilitates accelerated electron transfer across defects and reduces the interfacial charge‐transfer resistance. Additionally, silicate coordination confinement suppresses iron leaching, ensuring long‐term catalytic stability. As a result, BC/D─Chl achieves nearly 100% ETP‐dominated pollutant degradation, with 12.4‐ and 48.4‐fold improvements in reaction efficiency and kinetics, respectively, while maintaining 100% substrate removal over 192 h in a simulated continuous‐flow reactor. This work demonstrates the feasibility of inert interface defect engineering in natural layered silicates for sustainable Fenton‐like reactions via complete ETP pathways.