Crystalline‐Amorphous Heterointerfaces Enable Elastic Peracetic Acid Activation for Resilient Remediation of Hypersaline Wastewater

ABSTRACT Hypersaline organic wastewater treatment is chronically impeded by mechanistic inhibition and rigid lattice inelasticity. Herein, we design a MnBiCoO x catalyst featuring crystalline‐amorphous (C‐A) heterointerfaces and propose a synergistic “remote electron pump‐localized electronic depot” mechanism for peracetic acid (PAA) activation. This architecture leverages interfacial symmetry breaking and spin polarization to modulate e g orbital occupancy and d‐d hybridization, establishing a resilient electronic structure with intrinsic charge‐buffering capacity that ensures robust catalytic stability against hypersaline environments. Intriguingly, the presence of chloride ions (Cl − ) induces a counterintuitive 2.58‐fold kinetic acceleration, reframing halides as coordination‐driven modulatory hubs that promote spin‐polarized electron injection into PAA σ* antibonding orbitals. Quantitative contribution analysis identifies singlet oxygen ( 1 O 2 ) as the dominant matrix‐tolerant species (65.47%), underscoring a mechanistic shift toward non‐radical‐mediated pathways. Density functional theory (DFT) calculations reveal that the d z 2 ‐mediated σ‐bonding overlap, coupled with an upward shift of the d‐band center, substantially reduces the activation barrier. Crucially, the MnBiCoO x /PAA system exhibits operational stability for 912 h in hypersaline wastewater, and life cycle assessment (LCA) confirms its exceptional environmental sustainability. This work provides mechanistic insights into rationally designing catalysts with structural resilience and electronic responsiveness for adaptive environmental remediation.