Efficient Catalytic Elimination of Chlorobenzene Based on the Water Vapor-Promoting Effect within Mn-Based Catalysts: Activity Enhancement and Polychlorinated Byproduct Inhibition.

Achieving no or low polychlorinated byproduct selectivity is essential for the chlorinated volatile organic compounds (CVOCs) degradation, and the positive roles of water vapor may contribute to this goal. Herein, the oxidation behaviors of chlorobenzene over typical Mn-based catalysts (MnO 2 and acid-modified MnO 2 ) under dry and humid conditions were fully explored. The results showed that the presence of water vapor significantly facilitates the deep mineralization of chlorobenzene and restrains the formation of Cl 2 and dichlorobenzene. This remarkable water vapor-promoting effect was conferred by the MnO 2 substrate, which could suitably synergize with the postconstructed acidic sites, leading to good activity, stability, and desirable product distribution of acid-modified MnO 2 catalysts under humid conditions. A series of experiments including isotope-traced (D 2 O and H 2 18 O) CB-TPO provided complete insights into the direct involvement of water molecules in chlorobenzene oxidation reaction and attributed the root cause of the water vapor-promoting effect to the proton-rich environment and highly reactive water-source oxygen species rather than to the commonly assumed cleaning effect or hydrogen proton transfer processes (generation of active OOH). This work demonstrates the application potential of Mn-based catalysts in CVOCs elimination under practical application conditions (containing water vapor) and provides the guidance for the development of superior industrial catalysts.