The novel class of inorganic nanoclusters, \{\[AlO\-4Al\-\{12\}(OH)\-\{24\}(H\-2O)\-\{12\}\]\}\{\[SiW\-\{11\}O\-\{39\}CoCl\]\}\511H\-2O, \{\[AlO\-4Al\-\{12\}(OH)\-\{24\}(H\-2O)\-\{12\}\]\}\{\[P\-2W\-\{18\}O\-\{62\}\]\}Cl\533H\-2O and \{\[AlO\-4Al\-\{12\}(OH)\-\{24\}(H\-2O)\-\{12\}\]\}\-2\[NaP\-5W\-\{30\}O\-\{110\}\]\524H\-2O, consisting of Keggin cations and heteropolyoxometalates, has been synthesized and characterized by ICP, IR and NMR. It is proved that the intrinsic identities of Keggin cation and heteropolyanions of the clusters are preserved within the gels.
Microporous heteropolyoxometalates Cs\-\%x\%H\-\{5-\%x\%\}PW\-\{10\}V\-2O\-\{40\}/SiO\-2 were synthesized by a sol\|gel technique and characterized by IR, UV\|Vis, BET adsorption/desorption isotherm. The structural frameworks of Cs\-\%x\%H\-\{5-\%x\%\}PW\-\{10\}V\-2O\-\{40\} are preserved within the silica networks. Cs\-\%x\%H\-\{5-\%x\%\}PW\-\{10\}V\-2O\-\{40\}/SiO\-2 are a kind of polyoxometalate\|silica gel hybrids with uniform micropores of ca. 0.65 nm. They show a high catalytic activity for oxidation reaction of benzyl alcohol by H\-2O\-2(30%) in liquid\|solid systems and product selectivity for benzaldehyde(>96%). The highest activity is observed at \%x\%=2.5 in Cs\-\%x\%H\-\{5-\%x\%\}PW\-\{10\}V\-2O\-\{40\}/SiO\-2 and little formation of benzoic acid and a more deeply oxidized product is observed.
