The discriminative activities and mechanisms for activation of O-O bond in peroxy compounds via single-atom catalysts (SACs) especially with a higher coordination number (M-N 5 ) are rarely explored. Herein, the atomic catalyst (Fe-SAC) with Fe-N 5 as the active center was constructed, which could simultaneously and effectively activate peroxymonosulfate (PMS), peroxydisulfate (PDS), and hydrogen peroxide (H 2 O 2 ). Density functional theory (DFT) calculations combined with experiments results demonstrated that the degradation efficiencies of acyclovir were corresponding to the changes of O-O bond length in various peroxy compounds. Meanwhile, the experiments exposed that the three oxidants all produced • OH, but the PMS also contained 1 O 2 and Fe(IV)=O, and PDS contained O 2 •- additively. The scale-up experiment showed Fe-SAC could operate steadily for nearly 7 d. Overall, this work unveils the discriminative mechanisms for activation of O-O band in different Fenton-like systems. Moreover, the Fe-SAC with high coordination numbers has excellent catalytic properties and practical performance.
Although a high-activity yield of hydrogen peroxide (H 2 O 2 ) can be achieved by direct synthesis from hydrogen and oxygen, developing an extreme catalyst with high activity and stability is still very challenging, which limits its industrial application. Here, we reported a catalyst Pd/SPE with polyelectrolyte membranes SPE as an electronic acceptor to anchor Pd, which achieves H 2 O 2 selectivity of 90.1% and productivity of 5764.4 mmol∙g Pd -1 ∙h −1 . The results of TEM, XRD and ICP-MS, XPS, CO-DRIFT, O 2 -TPD, synchrotron radiation and density functional theory (DFT) simulations reveal that the electrons of Pd are transferred into polyelectrolyte membranes and Pd clusters are strongly chemisorbed on SPE, which is beneficial for O 2 adsorption and inhibits the dissociation of O-O bond, leading to significantly enhanced H 2 O 2 productivity and selectivity.
A novel nanoconfinement-engineered hollow perovskite catalyst (Ca 1.1 MnO 3-δ @HCNS) has been proposed for efficient catalytic ozonation in this study. This catalyst was constructed using a two-step hard-templating approach to enhance O-O bond elongation (1.28→1.34 Å) and electron transfer (0.44 vs. 0.38 eV), reducing activation barrier by 86 % versus non-hollow Ca 1.1 MnO 3-δ @CN-SiO 2 . Ca 1.1 MnO 3-δ @HCNS exhibits exceptional resistance to environmental quenchers (e.g., SO 4 2- , Cl - , humic acid) and achieves complete bisphenol A elimination within 20 min in complex water matrices such as domestic sewage and industrial wastewater, while maintaining excellent degradation efficacy for endocrine disruptors, pharmaceuticals, and phenolic contaminants (>99.9 % removal within 20 min). The turnover frequency (TOF) of Ca 1.1 MnO 3-δ @HCNS is more than 6 times higher than that of catalysts reported in the literature. These results demonstrate that nanoconfinement engineering can overcome the key limitations of conventional ozonation catalysts. This work establishes a nanoarchitecture design principle for advanced oxidation processes and elucidates nanoconfinement-mediated reaction mechanisms.
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