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Abstract: Ammonia-catalyzed sol–gel process of polyvinylpyrrolidone/tetraethoxysilane (PVP/TEOS) system in methanol was studied by in situ liquid 29Si nuclear magnetic resonance (NMR), dynamic light scattering (DLS), small angle X-ray scattering (SAXS) and rheology. A scientific connection was established between the reaction composition and the microstructures of sol particles. It was found that the concentration of PVP played an important role in the hydrolysis kinetics of TEOS and the SiO2 sol–gel process. The results of in situ 29Si NMR showed that PVP addition reduced both hydrolysis rate and condensation rate of TEOS, and the condensation rate decreased more seriously than the hydrolysis rate. The particle size distributions obtained from DLS and SAXS indicated that PVP held back the growth of SiO2 clusters by hydrogen-bonding the silanol groups on particle surface with the electronegative inner amide of PVP side chain. Thus, gelation was retarded and the rheology of sol was largely modified by PVP. Rheology study showed typical Newtonian fluid behavior before gelation and shear thinning fluid behavior after gelation point, respectively. The changes in fractal dimensions of PVP/SiO2 sols, obtained by SAXS, explained the different microstructures of SiO2 sol particles in the presence of PVP. The changes of microstructure and macroscopic properties should be pre-determined by the very early stages of sol–gel process. [Copyright &y& Elsevier]

Abstract: Titania–silica composite nanoparticles were prepared by sol–gel-hydrothermal and sol–gel routes, respectively, and their physico-chemical and photocatalytic properties were compared. The results of XRD, TEM and BET surface areas showed that sol–gel-hydrothermal route led to anatase titania–silica composite nanoparticles with large specific surface area, but the sol–gel route tended to form mixture of anatase and rutile. The composite nanoparticles prepared by sol–gel-hydrothermal route had better thermal stability against phase transformation from anatase to rutile, agglomeration and particle growth than those prepared by sol–gel route. On the basis of XRD, FT-IR, XPS and 29Si MAS-NMR, a strong interaction was found between SiO2 and TiO2, and Ti–O–Si bonds formed during both the two routes. But more Ti–O–Si bonds formed in the composite nanoparticles prepared by sol–gel-hydrothermal route than those prepared by sol–gel route. As a result, the titania–silica composite nanoparticles prepared by sol–gel-hydrothermal route exhibited higher photocatalytic activity in decomposition of methylene blue than that prepared by sol–gel route, and it had excellent photocatalytic activity even after calcined at 1000°C. [Copyright &y& Elsevier]