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The study considers the effect of fluorine doping of the alumina matrix used for the synthesis of supported sulfated zirconia catalysts. Hydrofluoric acid served as a fluorinating agent. The addition of fluorine was shown to affect the textural characteristics of the Al2O3 matrix and hence the surface area of sulfated zirconia catalysts based on the doped systems. It was found that the introduction of fluorine into the catalysts increases their activity (the conversion of hexane) and the yield of high-octane isomer 2,2-dimethylbutane.