Perfluorosulfonic acid polymer composites: Effect of the support and synthesis method on the acid and catalytic properties

[Display omitted] •Sulfated perfluorinated polymers were deposited on SiO2, carbon nanofibers and ZrO2.•The performance of the carbon nanofibers based composites surpassed that other samples.•Zirconia-based composites had increased resistance to the polymer desorption.•Polymers with low-equivalent weight and high acidity can be deposited on ZrO2. Several composite samples containing perfluorosulfonic acid polymer (PFSA; e.g. Nafion) over silica, carbon nanofibers or zirconia were synthesized to determine the effect of the support on the acid catalytic properties. The synthesized composites contained 5–25 wt.% of the perfluorosulfonic acid polymer with variable concentration of sulfonic groups (equivalent weight of PFSA). The acidity of the composites was investigated by titrimetric techniques, in a model catalytic reaction between resorcinol and ethyl acetoacetate, by EPR using spin probes and by temperature programmed desorption of propylene. It is shown that impregnation of silica with high surface area or mesoporous carbon nanomaterials yields samples with characteristics exceeding commercially available SAC (Nafion over silica) samples. A method for synthesis of zirconia-based catalytic composites was developed. It was shown that despite the relatively low catalytic activity (compared to PFSA/SBA-15 and PFSA/CNF samples) these samples have increased resistance to the PFSA desorption. So, polymers with low-equivalent weight characterized by higher acidity can be used.