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Three types of heterogeneous Fenton catalysts based on Fe-silicalite-1 were synthesized: (1) microcrystals with an average size of 5 μm (m-FeZ); (2) a hierarchical porous sample consisting of 100–200 nm nanocrystals prepared using a dry polystyrene latex template (h-FeZ); and (3) three hierarchical porous samples consisting of 30–50 nm nanocrystals prepared by steam-assisted crystallization (n-FeZ-1,2,3). The synthesis procedure for n-FeZ-1 and n-FeZ-2 included gel pretreatment at 90°C for 72 h. This pretreatment specifically involved introducing Fe into the reaction mixture after (for n-FeZ-1) and before (for n-FeZ-2) the gel aging. The samples were tested as heterogeneous Fenton catalysts in H2O2-mediated total oxidation of ethanol. The performance of the heterogeneous catalysts was compared with a conventional homogeneous Fenton catalyst. [ABSTRACT FROM AUTHOR]