Incorporation of Decavanadate Ions into Silica Gels and Mesostructured Silica Walls

Abstract

Decavanadate (V10O286-) polyoxometalate (POM) ions in water decompose into smaller POM ions or monomeric H2VO4- when the pH is raised to higher than 6. In this report, however, we have found that silicate ions can kinetically stabilize decavanadate ions for up to 8 h at pH 12 conditions. Gelation of these solutions by lowering the pH to 4−5 followed by aging produced monolithic vanadia−silica composite gels with a wide range of vanadium contents (V/(V + Si) up to 48%). Solid state 51V NMR and infrared spectroscopic data show that the vanadium species is predominantly V10O286- when the vanadium content is 2.3% ≤ V/(V + Si) ≤ 32% and another V(V) species in distorted octahedral coordination starts to appear in addition to V10O286- for high vanadium content of V/(V + Si) = 48%. The kinetic stabilization of decavanadate by silicate ions suggests that the silicate ions condense around the decavanadate ions to form a core−shell like structure that may behave as pure silica in some chemical reactions. Thus, upon...