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Ruthenium-doped (5 wt%) acidic heteropoly salt Cs2.5H0.5[PW12O40] (CsPW) is an active bifunctional catalyst for the one-pot hydrogenolysis of glycerol to 1,2-propanediol (1,2-PDO) in liquid phase, providing 96% selectivity to 1,2-PDO at 21% glycerol conversion at 150 °C and an unprecedented low hydrogen pressure of 5 bar. Rhodium catalyst, 5%Rh/CsPW, although less active, shows considerable selectivity to 1,3-PDO (7.1%), with 1,2-PDO being the main product (65%).

The coking during propene oligomerisation and subsequent regeneration of both silica-supported heteropoly acid H3PW12O40 (PW) and its palladium-modified form (1.6–2.5 wt% Pd) have been studied. 31P MAS NMR studies have revealed that the Keggin structure of the catalyst was unaffected by coke deposition in both unmodified PW/SiO2 and Pd-modified form. As shown by 13C MAS NMR and TGA/TPO, the Pd modification affects the nature of the coke formed: for the standard catalyst (PW/SiO2) both soft coke, comprising mainly high molecular weight aliphatic oligomers, and hard coke, comprising polynuclear aromatics, are formed whilst on the Pd-modified catalyst only the soft coke is observed. Coke formation causes strong deactivation of the catalyst in the oligomerisation of propene. The aerobic burning of coke on the unmodified PW/SiO2 occurs in the temperature range of 470–520°C. Doping the catalyst with Pd significantly decreases this temperature to allow catalyst regeneration at temperatures as low as 350°C without loss of catalytic activity.

17O MAS NMR spectra for17O enriched solid heteropoly acid H3PMo12O40 are reported. The oxygen exchange between solid H3PMo1217O40 and H216O vapor at 200–250°C is shown to be accompanied by fast mixing of terminal Mo=O and bridging Mo-O-Mo oxygens in the Keggin unit. The oxygen exchange in H3PMo1217O40 is much faster than in H3PW1217O40 in solution as well as in the gas phase.

The structure of the bulk proton sites in dehydrated solid Keggin-type heteropoly acids (HPA) H3PW12O40 and H4SiW12O40 was determined by17O NMR. The terminal W=O oxygen atoms in Keggin heteropolyanions were found to be the predominant protonation sites. The protonation of HP As in solution is also discussed on the basis of17O NMR data.

New solid acid catalysts, consisting of heteropoly acid (HPA) H3PW12O40 (PW) supported on a mesoporous pure-silica molecular sieve MCM-41, have been prepared and characterized by nitrogen physisorption, X-ray diffraction, FT-IR, and31P magic angle spinning NMR. The PW/MCM-41 compositions with PW loadings from 10 to 50 wt% have ∼ 30 A uniformly-sized mesopores. HPA retains the Keggin structure on the MCM-41 surface and forms finely dispersed HPA species. No HPA crystal phase is developed even at HPA loadings as high as 50 wt%. PW/MCM-41 exhibits higher catalytic activity than H2SO4 or bulk PW in liquid-phase alkylation of 4-t-butylphenol (TBP) by isobutene and styrene. In the alkylation of TBP by styrene, PW/MCM-41 shows a size selectivity compared to bulk PW and PW/SiO2, providing higher yields of a 2-(1-phenylethyl)-4-t-butylphenol, at the expense of the more bulky 2,6-bis-(1-phenylethyl)-4-t-butylphenol. The PW/MCM-41 compositions, having strong acid sites and a regular mesoporous system, are promising catalysts for the acid-type conversion and formation of organic compounds of large molecular size.

17O MAS NMR spectra for solid heteropoly acid (HPA) H3PW12O40 are reported. Comparison of solid-state and solution17O resonances shows that in the solid dehydrated H3PW12O40 terminal W=O oxygen atoms are the predominant protonation sites. H3PW12O40 and H4SiW12O40 supported on chemically activated carbon have been studied by means of NMR, FT-IR and XRD. The carbon-supported HPA's retain their Keggin structure and form finely dispersed HPA species. No HPA crystal phase is developed even at an HPA loading as high as 45 wt%.31P,29Si and17O MAS NMR spectra for bulk and carbon-supported HPA's indicate interaction of the HPA Keggin units with the carbon surface, causing large line broadening in the NMR spectra.

Tungstophosphoric acid supported on silica gel has been shown to catalyze Diels-Alder reactions of quinones. The catalyst is active under mild conditions and can be easily recovered and re- used.