Unraveling chlorine poisoning and partial reversibility over Mn-based oxide catalysts during chlorobenzene oxidation

Chlorine species represent a major challenge for the catalytic oxidation of chlorine-containing volatile organic compounds (CVOCs) such as chlorobenzene (CB) because they readily deactivate catalysts. However, the underlying deactivation pathway remains incompletely understood, leaving a clear knowledge gap. Elucidating this pathway is therefore crucial for the rational optimization of CVOCs oxidation technologies. In this work, the structure-activity relationships of fresh MnO₂, chlorine-poisoned MnO₂-Cl, and regenerated MnO₂-Cl-R were systematically investigated by integrating catalytic performance tests and kinetic analysis with comprehensive physicochemical characterization. The results show that chlorine species deteriorate the structural integrity of MnO₂ and disrupt the uniformity of elemental distribution through physical aggregation and chemical interactions, thereby reducing the accessibility and exposure of active sites. Mechanistically, during CB oxidation, chlorine poisoning decreases Mn dispersion and the ordering of oxygen species and lowers the fraction of high-valence Mn, collectively weakening the intrinsic oxidative capability of the active sites and causing performance loss. Regeneration removes a portion of surface chlorine deposits, alleviates manganese aggregation, and partially restores lattice‑oxygen participation, leading to an activity level between those of the fresh and poisoned catalysts. Nevertheless, complete recovery is not achieved: the stability of MnCl bonding, coupled with limitations arising from side reactions during regeneration, prevents full removal of chemically bound chlorine and leaves residual poisoning. Overall, this study clarifies the chlorine-poisoning pathway on MnO₂ and provides guidance for designing chlorine-tolerant catalysts and optimizing CVOCs catalytic oxidation processes.