ISSN 1070-4272, Russian Journal of Applied Chemistry, 2007, Vol. 80, No. 12, pp. 2107!2110. + Pleiades Publishing, Ltd., 2007.
Original Russian Text + A.B. Shishmakov, Yu.V. Mikushina, M.S. Valova, O.V. Koryakova, L.A. Petrov, 2007, published in Zhurnal Prikladnoi Khimii,
2007, Vol. 80, No. 12, pp. 2029 !2032.
AND INDUSTRIAL ORGANIC CHEMISTRY
Titanium Dioxide Xerogel Modified with Powder Cellulose
in Oxidation of Trimethylhydroquinone
A. B. Shishmakov, Yu. V. Mikushina, M. S. Valova,
O. V. Koryakova, and L. A. Petrov
Institute of Organic Synthesis, Ural Division, Russian Academy of Sciences, Yekaterinburg, Russia
Received May 2, 2007
Abstract-A procedure was developed for modification of titanium dioxide xerogel by addition of powder
cellulose in the stage preceding hydrolysis of tetramethoxytitanium. The resulting catalytic systems based
on the new material were studied in a model liquid-phase catalytic process of oxidative dehydrogenation
of trimethylhydroquinone with atmospheric oxygen.
Titanium dioxide is widely used as a sorbent and
a catalyst support. The efficiency of its application is
mainly governed by the structural and texture charac-
teristics, development of the surface, and accessibility
of its active centers throughout the entire volume.
Synthesis of xerogels of element oxides by any
method is accompanied by their shrinkage and, as
a result, by a decrease in the specific surface area
on drying. There are several ways to eliminate this
phenomenon: variation of the composition of disper-
sion medium, drying for longer time, and the use of
special additives .
The aim of this study was modify titanium dioxide
with powder cellulose (PC) and to study the resulting
materials in a model catalytic process of oxidative
dehydrogenation of trimethylhydroquinone (TMHQ)
with atmospheric oxygen.
Powder cellulose was prepared by hydrolysis of
kraft cellulose produced at the Baikal Paper and Pulp
Plant (Technical Specification OP 13-027 94 88-083
91) in 2.5 N hydrochloric acid at 100oC. Hydrolysis
was performed for 2 h. The resulting product was
washed with distilled water on a filter until neutral
pH of the aqueous extract. The product was dried at
Three samples of titanium dioxide xerogels K1,
K2, and K3 were prepared as follows: 1.5, 3, and 9 ml
of tetrabutoxytitanium (TBT), respectively, was dis-
solved in 20 ml of methanol. Hydrolysis was per-
formed with 500 ml of water at 20oC. The precipitate
was washed on a filter until the absence of butanol
in the wash water and dried at 100oC.
To prepare modified xerogels (MXs) with the TiO
PC ratios of 0.45 : 0.55, 0.26 : 0.74, and 0.06 : 0.94,
9-, 3-, and 1.5-ml portions of TBT, respectively, were
dissolved in 20 ml of methanol. To each of these
solutions, 1 g of PC was added. Hydrolysis was per-
formed at 20oC in 500 ml of water with stirring.
The solutions were kept for 10 min and by this time
the major fraction of the precipitate settled. The aque-
ous phase was decanted from the modified TiO
The precipitate was treated as described above.
: PC gels of compositions
0.31 : 0.69, 0.62 : 0.38, and 0.81 : 019 were prepared
from a solution of 9 ml of TBT in 20 ml of methanol.
Modification was performed by addition of 2, 1, and
0.5 g of PC, respectively, to the solution. Hydro-
lysis was performed in 500 ml of water. The precip-
itate was separated on a filter without preliminary
decantation and washed. After completion of wash-
ing, the paste was placed in a flask filled with 50 ml
The IR spectra of the samples in the form of solid
powders were recorded on a Perkin-Elmer Spectrum
One IR Fourier spectrophotometer in the range 40003
using diffuse reflection attachment (DRA).
The sorption of 1,4-hydroquinone (HQ) was performed
by addition of a solution of HQ in methanol into MX
[weight ratio HQ : MX = 1 : (0.2538)], followed by