Studies of the formation of homogeneous mixed silicon-titanium/zirconium oxides by the sol-gel route

Abstract

This thesis is concerned with the preparation of mixed silicon-titanium oxides (Ti02=4.1-21.9wt%) and silicon-zirconium oxides (Zr02=4.1-22.Iwt%) by the sol-gel route. Methods of preparing homogeneous Si02-TiO2 gels and SiO2-Zr02 gels have been explored.

In this work bis(acetylacetonato)titanium diisopropoxide or bis(acetylacetonato)zirconium dipropoxide and tetraethyl orthosilicate (TEOS) have been hydrolysed simultaneously in iso-propanol to form homogeneous gels. Using these systems, the effects of the reaction conditions, amount of titania/zirconia present in the gel, drying conditions and thermal treatment of the dry gels on the bulk and structural properties have been investigated by a variety of experimental methods including X-ray diffraction, mid- and near-infrared spectroscopy and gas adsorption techniques.

For SiO2-TiO2 powders and monoliths, and SiO2-ZrO3 monoliths, thermal treatment has been found to significantly reduce the surface area (from 750-1.0m2g-1), pore volume (from 0.56-0.001cm3g-1') and relative number of silanol groups on the surface of the sample above 700°C. Average pore diameters remain constant at temperatures below 900°C (ca 54-21Å for monoliths), although the micropore volume does decrease (0.04-0.0cm3g-1) suggesting that smaller pores are destroyed by the heating process. For SiO2-TiO2 powders, the average pore diameter was ca IOÅ larger than for the corresponding monolith suggesting that small pores are destroyed during powdering. At 1100°C, gas adsorption data indicate that the samples are fully densified. This is supported by NIR spectra which detect no silanol groups on the surface of the sample.

Structural changes arising from compositional changes and differing thermal treatment regimes have been monitored using mid-infrared spectroscopy and X-ray diffraction. With increasing temperature the silica matrix strengthens and titanium/zirconium are incorporated into the matrix. Monolithic SiO2-TiO2 gels (Ti02=6.34 weight%) remained amorphous at 1100°C, whereas powders began to exhibit diffraction patterns predominantly from anatase at 700°C. Anatase crystallite sizes have been calculated using the Scherrer equation and have been found to be between 16.3 and 5.4nm. Monolithic SiO2-ZrO2 gels containing 4.1 and 4.9 weight% zirconia were found to be amorphous after treatment at 1100°C. Increasing the zirconia content to 6.4 and 22.1 weight% resulted in gels that were amorphous up to 900°C. Further treatment at 1100°C, resulted in tetragonal zirconia and some cristobalite being formed. Crystallite sizes have been calculated as being between 2.7 and 1.6nm for tetragonal zirconia and from 4.1 to 2.8nm for cristobalite.

Increasing the levels of titania/zirconia in the sample resulted in higher relative levels of hydrogen-bonded silanol groups. On hydration, the increased levels of titania/zirconia resulted in no observable free silanol groups on the surface suggesting that the surface becomes more hydrophilic as the amount of titania/zirconia present in the sample increases. This suggests that water becomes more tightly bound to Ti-OH /Zr-OH groups on the surface and within the pores, resulting in fewer free silanol type groups.

A double alkoxide bis(acetylacetonato)titanium di(triethoxysilane) [Ti(acac)2(OSi(OC2H5)3)2] has also been synthesised and characterised. Mixed Si02-TiO2 gels have also been prepared by the simultaneous hydrolysis of Ti(acac)2(OSi(OC2H5)3)2 and TEOS under acidic conditions in ethanol. The effects of reaction conditions and thermal treatment of the dry gels have been investigated.

Increasing the treatment temperature of the samples resulted in the progressive decrease in surface area (533-3.0m2g-1), pore volume (0.18-0.003cm3g-1), micropore volume (0.06-0.00cm3g-1) and relative number of silanol groups on the surface. However, the average pore diameter remained constant at temperatures up to 700°C. Changes in pore volume (0.07-0.005cm3g-1), surface area (300-3.0m2g-1) and average pore diameter (26.9-91.9Å) were largest at 900°C, and the samples were found to be almost completely dense. This was confirmed by the absence of observable silanol groups by NIR spectroscopy.

After heating at temperatures up to 900°C, the samples were found to be amorphous by XRD. However increasing the temperature to 1100°C resulted in the formation of some crystalline anatase. The anatase crystal sizes have been calculated as being from 16.3 to 10.8nm in diameter.

NIR studies of silica-zirconia and silica-titania gels (prepared by both methods), indicate that decreasing the amount of acid used in the hydrolysis reaction resulted in higher relative levels of hydrogen bonded silanol species. Similarly, decreasing the amount of acid increased the micropore volume and decreased the mesoporosity of the resulting samples.

Generally, decreasing the amount of acid used for the hydrolysis for silica-zirconia and silica-titania gels (prepared by both methods), results in a decrease in the overall surface area and pore volume of the resulting material. The resulting isotherms indicate that the samples became less mesoporous as the amount of acid used in the hydrolysis reaction decreased. This was accompanied by an increase in the micropore volume.

For SiO2-TiO2 monoliths prepared from a double alkoxide and Si02-ZrO2 monoliths the resulting pore structure is more rigid and composed of smaller pores than that of SiO2-TiO2 powders and monoliths prepared from bis(acetylacetonato)titanium diisopropoxide.