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The removal of persistent organic pollutants through catalytic ozonation remains a significant challenge, particularly in developing catalysts that combine high efficiency with robust stability. To address this, we present an innovative strategy for synthesizing a series of energetic metal-organic framework (EMOF)-derived porous carbon spheres doped with various transition metals (denoted as EMS, EMFeS, EMCuS, EMNiS, and EMMnS). This approach combines a phase transfer pathway with controlled expansion of energy-containing MOFs during high-temperature pyrolysis, resulting in hierarchically porous structures. When applied to tetracycline (TTCH) degradation, EMFeS exhibited remarkable catalytic activity with ozone and the reaction rate constant is 0.131 min−1, which is superior to individual ozone system (0.088 min−1). The superior catalytic performance is attributed to two aspects: (i) The three-dimensional hierarchical porous architecture facilitates efficient mass transfer and improves reaction kinetics, while (ii) the well-dispersed metal active sites (including Mn, Fe, Cu, and Ni) significantly enhance ozonolysis efficiency. Comprehensive mechanistic studies through quenching experiments and LC-MS analysis elucidated the degradation pathways, while continuous flow catalytic tests and biotoxicity assessments confirmed the practical applicability of these catalysts. This work not only advances the development of high-performance ozonation catalysts but also provides new insights into the design of water treatment materials.

This is an open access article under the terms of the Creative Commons Attribution 4.0 International License (CC BY 4.0, https://creativecommons.org/licenses/by/4.0/).
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