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[Display omitted] • Homogeneous mixed Mn 2-x Fe x O 3 were derived from bimetallic Metal-Organic Frameworks. • Mn 1.82 Fe 0.18 O 3 shows superb toluene conversion up to 90 % at 226 °C in 60000 h−1. • Fe doping makes the Mn 2 O 3 surface less acidic and weakens toluene adsorption. • Fe doping could elongate M = O bond and enhance nucleophilicity of active oxygen. • Mn 1.82 Fe 0.18 O 3 has excellent water resistance and recycling performance. Homogeneous mixed iron-manganese oxide nanoparticles prepared from bimetallic MOFs were examined for their catalytic performance to examine toluene degradation. Introducing Fe into Mn 2 O 3 to obtain Mn 2-x Fe x O showed significantly improved catalytic combustion of toluene compared to single manganese or iron oxide. Among these catalysts, Mn 1.82 Fe 0.18 O 3 exhibited optimal catalytic performance showing the lowest T 10 , T 50 and T 90 in weight hourly space velocity (WHSV) of 60000 mL·(g·h)-1. In high-water content atmosphere, catalytic activity was excellent even after four cycles and such a good catalytic performance of Mn 1.82 Fe 0.18 O 3 might be due to the high surface area (103 m2·g−1) and uniform doping of Fe caused by MOFs roasting. Fe doping enhanced the weak acid sites onto Mn 2 O 3 surface, thus promoting the activation of toluene. The doped Fe elongated M = O bond to enhance the nucleophilicity of the active sites, which increased the intrinsic activity of Mn 2 O 3 catalyst. This study could serve as a reference for active sites modification of metal oxide catalysts. [ABSTRACT FROM AUTHOR]