Isoprene synthesis from formaldehyde and isobutene over Keggin-type heteropolyacids supported on silica † V. L. Sushkevich, * a V. V. Ordomsky ab and I. I. Ivanova ac Gas phase Prins condensation of isobutene with formaldehyde has been studied over different Keggin-type heteropolyacids supported on amorphous silica. The catalysts were characterized by elemental analysis, X-ray diffraction, low temperature nitrogen adsorption, TPD of ammonia, FTIR of adsorbed pyridine and NMR spectroscopy. The activity of the supported heteropoly compounds was found to increase in the following order: H 4 SiMo 12 O 40 < H 3 PMo 12 O 40 < H 4 SiW 12 O 40 ≈ H 3 PW 12 O 40 . The lower activity of the supported molybdenum heteropolyacids was attributed to their low thermal stability and partial decomposition during catalyst activation, which resulted in lower acidity. The variation of HPA content from 5 to 33 wt% was also shown to increase catalyst activity. Based on the relationship between the content of weak Brønsted sites, the amount and type of carbonaceous deposits and the catalytic activity, it was concluded that the generation of "working" active sites over HPA catalysts involves the formation of unsaturated branched surface species over weak Brønsted sites. These active carbonaceous species are responsible for selective isoprene synthesis. The best catalyst performance is observed over the catalyst with 20 wt% of H 3 PW 12 O 40 , which shows an isoprene yield of 48% with a selectivity of 63%.Catal. Sci. Technol. This journal is Scheme 1 Two-step process for on-purpose isoprene synthesis from isobutene and formaldehyde.