Applied Surface Science 252 (2005) 828–832

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Acetone gas phase condensation on alkaline metals doped

TiO2 sol–gel catalysts
Marcial Zamora a,c, Tessy López a,*, Ricardo Gómez a,b,
Maximiliano Asomoza a, Ruth Meléndrez c
a
Depto. de Quı́mica, Universidad A. Metropolitana-I, Av. San Rafael Atlixco No. 186, A.P. 55-534, México 09340, DF, Mexico
b
Instituto Mexicano del Petróleo, Programa de Ing. Molecular, México 07300, DF, Mexico
c
Benemérita Universidad Autónoma de Puebla, Fac. De Quı́mica, C.U. Puebla Pue, Mexico

Available online 8 April 2005

Abstract

The vapor-phase condensation of acetone was studied over sol–gel prepared TiO2 and TiO2-doped with 1 wt.% of Li+ or Rb+.
The acetone condensation was catalyzed by basic sites and the obtained products were mesityl oxide (MO), isomesityl oxide
(ISMO), mesitylene (M) as well as isophorone (IP) and phorone (P). The TiO2 crystalline structure was characterized by XRD
and the basicity of catalysts by means of CO2 chemisorption. The number of basic sites was 0.057 mmol CO2/g for TiO2 and Rb/
TiO2 and 0.676 mmol CO2/g for Li/TiO2 catalyst. CO2-TPD showed that the strongest of the basic sites follows the order Rb/
TiO2 > TiO2 > Li/TiO2. Activity was found of the same order in the three catalysts. Selectivity patterns shown that MO (70%)
was the main product in Li/TiO2 while for TiO2 and Rb/TiO2 comparable amounts of MO (41 and 44%) and M (39 and 39%)
were obtained.
# 2005 Elsevier B.V. All rights reserved.

Keywords: Titania; Sol–gel titania; Lithium–titania; Rubidium–titania; Acetone oligomerisation; Sol–gel basic catalysts

1. Introduccion of its importance, few reports related to gas phase

Basic solid catalysts conventionally are used in
process carried out in liquid phase catalytic reactors.
A great number of organic reactions like alquene
isomerization, Cannizzaro and Tischenko reactions,
Michael, Witting and Knoevenagel condensation have
been achieved with basic catalysts. However, in spite
* Corresponding author.
E-mail address: tesy@xanum.uam.mx (T. López).
reactions over basic catalysts have been published
[1,2]. Basic zeolites, as well magnesium oxide or
alkaline metals supported over MgO are the basic
catalysts reported recently [3]. Heterogeneous basic
catalysis requirse supports having important basic
properties. However, the use of supports showing
weak acid–basic properties but modified by the
addition of strong bases like alkaline oxides could
be an alternative via to control the formation of
dimmers or trimmers during the acetone condensation.

0169-4332/$ – see front matter # 2005 Elsevier B.V. All rights reserved.
doi:10.1016/j.apsusc.2005.02.061
 M. Zamora et al. / Applied Surface Science 252 (2005) 828–832
It seems then interesting to study supports like titania
which is a solid showing weak acid–basic properties
[4–6]. The acid–basic character of TiO2 has been
observed during the isopropanol decomposition in
which propene (acid sites) and acetone (basic and acid
sites) were the main products [7,8].
When titania was prepared by the hydrolysis of
titanium alkoxides (sol–gel method) the textural,
structural and acid–basic properties can be modified in
depending of the preparation conditions [9,10].
Moreover, alkaline metals can be added during the
gelling of the TiO2 producing solids in which the
alkaline ion can be inserted in to the TiO2 network
[11].
To improve the basic character of TiO2 in the
present work we prepare titania doped with lithium
and rubidium by the sol–gel method. The catalysts
were studied in the gas phase acetone condensation
reaction which is a reaction depending of the basicity
of the catalysts. The products are a,b-insaturate
cetones, like the mesityl oxide (MO) and isophorone.
Acetone gas phase condensation is an interesting
organic reaction since the products obtained from the
reaction have important applications in the fine
chemical industry. Acetone condensation initially
produces diacetone alcohol, which by dehydration
forms the mesityl oxide. However, the reaction is not
very selective, since it is dependent of the catalyst used
and work conditions. Numerous products can be
obtained by the effect of complex reactions mainly
those which involves the cross reaction between the
diacetone alcohol and the acetone. The addition of a
third acetone molecule also occurs and isophorone
(IP), phorone (P) or mesitylene oxide are obtained.
2. Experimental
2.1. Catalysts preparation
Reference TiO2: In a flask were mixed 3.2 mol of
deionized water, 1.2 mol of ethanol (Baker 99.9%)
and 0.2 ml of nitric oxide (Baker 65% volume in
water) to adjust the pH of the solution to a value of 3.
The solution was then put under reflux at 70 8C and
dropwise were added 0.2 mol of titanium n-butoxide
(Ti(Obut)4, Aldrich 99.9%) and 16 mol of water to
accomplish hydrolysis, then the solution was main-
829
tained for 2 h until gelling. Total water/alcohol ratio
16. For doped TiO2 catalysts, the synthesis process
was the same described about, but in the hydrolysis
water was added the corresponding amount lithium or
rubidium chlorides (Baker 99%) to obtain 1 wt.% of
the alkaline metal. The gelled samples were dried
overnight and the calcined at 400 8C in air for 12 h.
2.2. X-ray diffraction
The crystalline structures of the TiO2 were
determined by X-ray diffraction with a Advance
Bruker D-8 Difractometer using Cu Ka radiation. The
structures were refined via the Ritveld method using
the DBWS-941 code [12].
2.3. Specific surface area
The specific surface areas were calculated form the
nitrogen adsorption isotherms by the BET method
using a Quantasorb automatic equipment. To calculate
the mean pore size diameter the BJH equation was
used.
2.4. Thermal programmed desorption
Basicity was determined by CO2-TPD with
Micromerictis TPD/TPR 2900 equipped with a
thermal conductivity detector. The samples were
reactivated in situ with nitrogen flow (1 ml/s) in a glass
quartz reactor at 400 8C. After, the temperature was
down to room temperature and a gas flow Ar–CO2
(90:10) was passed in the reactor and then fluxed with
He flow (1 ml/min) with a rate temperature program of
10 8C/min. De amount of CO2 was calculated from de
desorption TPD curves.
2.5. Catalytic activity
Acetone aldol condensation was determined in gas
phase at atmospheric pressure and at a temperature of
300 8C. Catalyst sample (50 mg) were put in a glass
reactor (volume 3 ml) and then reactivated at 400 8C
with nitrogen flow (1 ml/s). Acetone was passed with
nitrogen flow, trough a glass saturator immersed in
water contained at a temperature of 0 8C (66 Torr).
The reactor was coupled on line with a gas
chromatograph Perkin Elmer equipped with a capil-
830 M. Zamora et al. / Applied Surface Science 252 (2005) 828–832

lary colonna PE-1100% phenylsilicone. The main Table 1

Composition (wt.%) of crystalline TiO2 phases and crystallite size
products detected in the reaction were mesityl
(nm)
oxide,isomesityl oxide (ISMO), mesitylene (M) and
Catalyst Brookita Anatase
minor quantities isophorone (IP) and phorone (P).
Some deactivation is observed in function of time and TiO2 6 (26) 94 (13)
Li–TiO2 8 (13) 12 (65)
the values for activity and selectivity were calculated
Rb–TiO2 6 (12) 94 (14)
in the first 60 min.

3. Results and discussion
The crystalline phases its relative abundance as
well as the crystallite size of the catalysts were
determined form the XRD patterns and refined using
the Rietveld method. XRD patterns are shown in Fig. 1
for the samples annealed at 400 8C. Anatase was the
main crystalline phase and brookite was also observed
in minor quantity. The calculation of the relative
amounts of each TiO2 phase and the corresponding
crystallite size are reported in Table 1. Anatase is
present at values higher than 90% in all the samples.
The catalysts are nano structured and the crystallite
size for brookite phase was comprised between 12 and
26 nm. For anatse phase the crystallite was 13–14 nm
for TiO2 and Rb/TiO2, respectively, while for Li/TiO2
it was four times larger (65 nm).
The BET specific surface areas can be affected by
the nature (cation radi) of the alkaline metal. In
Table 2, BET specific surface areas of 132–125 m2/g
for TiO2 and Rb/TiO2 are reported, while for the Li/
TiO2 catalyst small specific surface area was obtained
(90 m2/g). These results are in agreement with the
Table 2
Specific surface area and CO2 chemisorption for titania and doped
titania sol–gel catalysts
Catalyst Surface area (m2/g) CO2 (mmol/g) CO2 (mmol/m2)  103
TiO2 132 0.057 0.42
Li–TiO2 90 0.676 7.5
Rb–TiO2 125 0.057 0.46
calculated crystallite size, since the sample showing
the large crystallite size (Li/TiO2) corresponds to the
catalyst with the small specific surface area.
Basicity of the samples obtained from the CO2-
TPD varies in depending of the TiO2 catalyst. In
Table 2, the CO2 (mmol/g) obtained for each catalyst
are reported. In TiO2 and Rb/TiO2 they were 0.057
CO2 mmol/g for both catalysts, while for the Li/TiO2
catalyst the amount of CO2 desorbed is ten times
bigger (0.676). We have then the TiO2 and Rb/TiO2
pair with low number of basic sites and on the other
hand the Li/TiO2 catalyst with a high number of basic
sites. However, the results of Table 2, are related to the
number of basic sites, but the information about their

Fig. 1. XRD spectra of TiO2, Li/TiO2 and Rb/TiO2 sol–gel catalysts

calcined at 400 8C. Fig. 2. CO2-TPD of TiO2, Li/TiO2 and Rb/TiO2 sol–gel catalysts.
 M. Zamora et al. / Applied Surface Science 252 (2005) 828–832 831

Table 3
Activity and selectivity for the acetone condensation at 300 8C on titania and doped titania sol–gel catalysts
Catalyst ISMO MO M P IP Activity (mol/g s)  105 Activity (mol/m2 s)  107
TiO2 18 41 36 2 2 4.40 3.72
Li–TiO2 13.4 70.3 12.3 2.4 1.6 2.70 1.90
Rb–TiO2 11.7 44.1 39.2 0.5 4.5 3.91 31.2

strongest can be obtained from the CO2-TPD
thermograms. In Fig. 2, it can be seen that the
desorption peak for Li/TiO2 is around 85 8C while for
TiO2 and Rb/TiO2 the peaks are at 135 and 150 8C,
respectively. Usually the strongest of surface sites
determined by TPD are related to desorption
temperature. From Fig. 2, then we have in Li/TiO2
a high number of basic sites but with low strongest,
meanwhile in TiO2 and Rb/TiO2 we have small
quantity of basic sites but with stronger basicity. The
catalytic activity as well as the selectivity patterns
must be more sensible to the strongest that to the total
number of basic sites.
The results obtained in the evaluation of the
catalysts for the acetone condensation reaction are
reported in Table 3. The reaction rate for the three
samples was comprised between 4.4 and 2.7
(10 5 mol/g s) and we can considered them of the
same order. Currently, differences of at least of five
times are recommended to speculate in activity
behavior and that is not our case. On the other hand,
in Table 3, the selectivity patterns for the three

Fig. 3. Proposed mechanism for the acetone condensation at 300 8C.

832 M. Zamora et al. / Applied Surface Science 252 (2005) 828–832
catalysts are tabulated. The main products were the
ISMO, MO and M. In Fig. 3 the probable mechanism
for the acetone condensation is represented. Similar
mechanisms were used to explain the synthesis of
organic products using cetones or aldehides [14–18].
First we can look the proposed mechanism for the
formation of ISMO and MO in Fig. 3. Acetone
condensation is a complex reaction in which the
selectivity is very sensitive to the nature of the basic
sites and support [3]. At low temperature de aldol is
stable and being a important product [13], while at
high temperature the aldol initially formed is faster
dehydrated to form the ISMO and the MO. In that
concerning the formation of MO we can see that the
selectivity is higher in a big proportion in the Li/TiO2
catalyst, since we have 70% of MO on Li/TiO2 while
42 and 44% correspond to the TiO2 and Rb/TiO2
catalysts, respectively. The high selectivity to MO
showed by the Li/TiO2 catalyst is a consequence of the
fast desorption of MO adsorbed on weak basic sites,
the addition of third acetone molecule is highly
avoided and then only small amounts of isophorone
are obtained. On the other hand, on TiO2 and Rb/TiO2
catalysts showing stronger basic sites the isomesityl
oxide is strongly adsorbed and with out desorption
from de catalyst surface a third molecule of acetone
was added forming mesitylene in important propor-
tion. Such results showed that the selectivity of the
reaction depends of the strongest of the basic sites,
the formation acetone oligomerization only can be
achieved over strong basic sites.
4. Conclusions
The synthesis of TiO2, and doped Li/TiO2 and Rb/
TiO2 was accomplished gelling titanium alkoxide with
the alkaline chloride. XRD identified anatase and
brookite in nanocrystalline structures. High specific
surface areas were obtained on the three catalysts
(90–132 m2/g). The basicity determined by CO2-TPD
indicates that in Li/TiO2 a high number of weak basic
were formed, meanwhile in TiO2 and Rb/TiO2 the
number of basic sites was smaller but with strong
basicity than the former catalyst. During the acetone
condensation reaction similar activity was observed in
the three catalysts. Meanwhile, important differences
in selectivity were observed. For Li/TiO2 catalyst due
to the weakness of their basic sites the formation of
mesityl oxide was favored. In TiO2 and Rb/TiO2
important formation of mesitylene was obtained, since
the stronger basicity of these catalysts permit the
addition of third molecule of acetone.
Acknowledgement
To CONACYT for the financial support given to
the Heterogeneous Basic Reactions grant M.Z. to
PROMEP-SEP program.
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