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Relations between the catalyst structure, redox function, acid and catalytic properties of two types of silica (silica gel and layer silica) modified by -ferric oxide nanoparticles of a different size (3-4 and 8-10 nm) were studied in the benzene alkylation by benzyl chloride. The catalysts were tested by means of Mossbauer spectroscopy, temperature-programmed NH3 desorption, temperature-programmed H2 reduction and diffuse-reflectance IR-spectroscopy using CO and CD3CN as test molecules. It was found that the particle size and the silica structure affect the catalytic behavior.