Russian Journal of Applied Chemistry, 2013, Vol. 86, No. 2, pp. 151−155.
Pleiades Publishing, Ltd., 2013.
Original Russian Text © A.B. Shishmakov, O.V. Koryakova, A.S. Seleznev, L.A. Petrov, S.A. Melkozerov, 2013, published in Zhurnal Prikladnoi Khimii,
2013, Vol. 86, No. 2, pp. 166−170.
AND INDUSTRIAL INORGANIC CHEMISTRY
Synthesis of Double Oxides TiO
Titanium Content by Hydrolysis
of Tetrabutoxytitanium–Tetraethoxysilane Mixture
in an Atmosphere of Water Vapor and Ammonia
A. B. Shishmakov
, O. V. Koryakova
, A. S. Seleznev
, L. A. Petrov
, and S. A. Melkozerov
Postovskii Institute of Organic Synthesis, Ural Branch, Russian Academy of Sciences, Yekaterinburg, Russia
Ural State University of Forestry Engineering, Yekaterinburg, Russia
Received March 20, 2012
Abstract—A series of TiO
binary xerogels with the titanium content lower than 7 mol % were prepared by
joint hydrolysis of tetrabutoxytitanium and tetraethoxysilane in a desiccator in the atmosphere of vapor over 5%
solution under static conditions. The physicochemical properties of the material were examined by
IR spectroscopy and by the kinetic method with hydrogen peroxide decomposition as model reaction.
Double oxides TiO
are widely used as thin-
ﬁ lm coatings, catalyst supports, selective sorbents, and
photocatalysts [1, 2]. Of particular interest is the binary
with low titanium content (<7 mol %),
which is characterized by homogeneous distribution of
titanium dioxide with predominant formation of Ti–O–Si
The functional characteristics (catalytic activity, pho-
toactivity, reactivity) of double oxides TiO
mined by the surface and bulk properties of this material,
largely depend on the preparation procedure. The tradi-
tional sol–gel synthesis of TiO
hydrolysis of a mixture of titanium and silicon alkoxides
in aqueous-alcoholic solutions in the presence of cata-
lysts (acids or alkalis), followed by controllable drying.
However, when organometallic compounds that strongly
differ in hydrolysis rates, e.g., tetrabutoxytitanium (TBT)
and tetraethoxysilane (TES), are used as precursors, it
is difﬁ cult to perform simultaneous hydrolysis ensuring
homogeneous distribution of titanium in the silica matrix.
Therefore, it seemed appropriate to abandon the use of
aqueous-alcoholic solutions and perform the hydrolysis of
the alkoxide mixture in an NH
O atmosphere. The
use of such atmosphere favors simultaneous hydrolysis
of the components. TBT undergoes hydrolysis already
under the action of atmospheric moisture, and ammonia
is the traditional catalyst of TES hydrolysis.
The goal of this study was to prepare a series of
binary xerogels containing 1–6 mol % Ti by
hydrolysis of a mixture of TBT and TES in an atmosphere
of water vapor and ammonia and to examine the physi-
cochemical properties of the material obtained.
Hydrolysis was performed at 22°С in a 3000 cm
iccator containing a beaker with 100 ml of 5% aqueous
ammonia solution. TES, TBT, and their mixtures were
poured into 30-ml round-bottomed porcelain cups 60 mm
in diameter and placed in the desiccator.
To prepare double oxides TiO
(sample no. 1), 5.1 (no. 2), 3.9 (no. 3), 2.6 (no. 4), and
1.3 mol % TiO
(no. 5), 10 ml of TES was mixed with 1,