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FeOx/HZSM-5 catalyst with 8 wt.% Fe-loading (8-FeZ) exhibited significantly higher reactivity in the benzylation of benzene with benzyl chloride than FeOx/HZSM-5 catalyst with 2.5 wt.% Fe-loading (2.5-FeZ) because the synergistic catalysis between isolated Fe3+ and superfine Fe2O3 occurred on 8-FeZ in the reaction.