Constructing Cooperative Dual-Sites on α-MnO ₂ : Effective Catalytic Ozonation of Toluene at Ambient Temperature

Manganese-based catalysts have been widely employed in catalytic ozonation for the elimination of volatile organic compounds (VOCs), yet the cooperative mechanism among multiple active sites remains unclear, impeding rational catalyst design. Here, a multivalent manganese oxide catalyst was synthesized using a manganese nitrate precursor, which achieved nearly complete synchronous conversion of toluene and ozone at ambient temperature. Detailed characterizations and DFT calculations revealed that dual active sites, consisting of surface acid sites and oxygen vacancies (OVs), worked in synergistic coupling. The acid sites preferentially adsorbed and activated toluene, while the OVs facilitated ozone decomposition, generating active oxygen species to further oxidize intermediate products. This dynamic redox coupling ensured the complete oxidation of toluene and maintained excellent long-term stability. This study unveils the synergistic mechanism of dual active sites in catalytic ozonation and provides design insights for developing efficient manganese-based catalysts for VOCs removal.