Catalysis Today xxx (xxxx) xxx–xxx

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Catalysis Today
journal homepage: www.elsevier.com/locate/cattod

Acidic properties of Si- and Al- promoted TiO2 catalysts: Effect on 2-

propanol dehydration activity
⁎
Gustavo Pérez-Lópeza, , Román Ramírez-Lópeza, Tomás Viverosb
a
Departamento de Ingenieria Química Industrial, Escuela Superior de Ingeniería Química e Industrias Extractivas, Instituto Politécnico Nacional, Mexico
b
Area de Ingeniería Química, Universidad Autónoma Metropolitana-Iztapalapa, Av. San Rafael Atlixco 186, Col. Vicentina, Iztapalapa, Mexico

A R T I C L E I N F O A B S T R A C T

Keywords: The effect of Si and Al promoted in TiO2 catalysts on both acid-base properties and 2-propanol dehydration was
Titania mixed oxides studied. The sol-gel method was used to prepare pure TiO2 and TiO2-Al2O3 and TiO2-SiO2 mixed oxides with 1%,
Promoting silica 3% and 10% of Al2O3 or SiO2. The structure and surface characterization (XRD, TG-DTA, N2 sorption, 27Al and
Promoting alumina 19
Si MAS NMR) revealed that the promoted cations were dispersed in the TiO2 lattice. The acid and basic sites
Acid-base molar ratio
density was measured by NH3-TPD and CO2-TPD. FTIR-pyridine-TPD revealed predominantly Lewis-type acidity
2-Propanol dehydration
for all these catalysts and a low presence Brønsted-type acidity was detect only for 10% SiO2 promoted catalyst.
The change in the activity of 2-propanol decomposition was useful to detect the effect of type and content of
cation in the acid-base properties of promoted catalysts. The acid-base molar ratio of the catalytic surface was
increased as a function of content of Al and Si and it was related to the increase in the alcohols decomposition
activity. Dehydration activity was more sensitive for the Si-promoted catalysts than the Al-promoted ones,
showing an important role of cation coordination in the acidic and catalytic properties of these mixed oxides.

1. Introduction
It has been demonstrated that the formulation of mixed oxides by
different synthesis methods allows making materials with differences
on their surface acid-base properties, even with low content of pro-
moting cations [1–8]. The TiO2-SiO2 mixed oxides are catalysts applied
in reactions requiring the action of Brønsted acid sites [1,2,4], which
are promoted by the combination of TiO2 and SiO2. On the other hand,
TiO2-Al2O3 mixed oxides have been employed as supports in different
metal supported catalysts, especially in hydrotreating [5,9,10] due to
their improved thermal stability and acidic properties. Several synthesis
techniques have been developed to prepare mixed oxides, and sol-gel
method has been useful to promote an atomic scale mixing, demon-
strating that the mixing of components is an important fact to control
textural and acidic properties of catalytic materials [1,2,11–13]. The
surface acidity of titania-silica and titania-alumina mixed oxides has
been related to the composition and the development of atomic het-
erolinkages [1,14,15]. Metallic alkoxides are the most widely used
precursors in sol-gel preparation; hydrolysis and condensation of me-
tallic alkoxides are the initial steps in the synthesis, and the relative
reactivity of precursors can modify the distribution at the atomic level
[11–13]. The differences in hydrolysis and condensation rates of Al-,
Si-, and Ti- alkoxides hinder the ability to form M-O-M’ bonds, where M
and M’ denote two different cations (in other words, Al-O-Ti, Si-O-Ti)
[11]. Two-stage hydrolysis procedure seems to have overcome this
difficulty, although there are limits in the Si/Ti and Al/Ti ratios to
promote component oxide mixing [4]. Then, it is important to evaluate
the evolution of acid-base properties of mixed oxides as a function of
cation content.
The conversion of alcohols is a test profusely used to evaluate the
effect of the synthesis parameters on surface acidity for mixed oxides
[15–23] and the increase in alcohol dehydration activity has been re-
lated to the increase in the acid site density [15,24,25]. Thus, it has
been possible to evaluate the acid-base surface properties as a function
of the mixed oxides contents by alcohol conversion activity. The con-
version of alcohols proceeds by three pathways: E1, E2, and E1cB
[23,26–29]. It is generally accepted that there is not a pure elimination
route on each type of surface. However, the selective reaction product is
an indicative of the acid-base sites distribution. Then, 2-propanol con-
version produces propene in E1 route (large number of acid sites) or
propene and acetone in E1cB (acid-base surface) [18,29,30]. Subse-
quently, 2-propanol dehydration can be enhanced not only by increase
in acidity but also by changes in acid-base properties. It has been re-
ported improved acidity (acid site density) for both TiO2-Al2O3 and

⁎
Corresponding author at: Edificio-6, ESIQIE-Instituto Politécnico Nacional, Unidad Profesional Adolfo López Mateos, Zacatenco, Delegación Gustavo A. Madero, Ciudad de México,
Mexico.
E-mail addresses: gus.perezlopez@gmail.com, gmperez@ipn.mx (G. Pérez-López).

http://dx.doi.org/10.1016/j.cattod.2017.07.005
Received 12 April 2017; Received in revised form 28 June 2017; Accepted 4 July 2017
0920-5861/ © 2017 Published by Elsevier B.V.

Please cite this article as: Pérez-López, G., Catalysis Today (2017), http://dx.doi.org/10.1016/j.cattod.2017.07.005
G. Pérez-López et al.
TiO2-SiO2 mixed oxides as a function of Al2O3 and SiO2 content
[1,17,30], however, it is important to establish the difference in acidic
catalytic activity according to the type of promoter. Additionally, it is
significant to observe the relevance not only on acidic properties but
also the effect of both acid site density and acid-base molar ratio in the
alcohol dehydration activity.
The purpose of this work is to study the effect of the content of Al-
and Si-promoted cations in the catalytic dehydration of 2-propanol over
TiO2 and TiO2-Al2O3 and TiO2-SiO2 catalysts to correlate the acid-base
properties of these materials with the catalytic activity in dehydration
of 2-propanol. The TiO2-Al2O3 and TiO2-SiO2 mixed oxides were syn-
thesized by one-stage hydrolysis sol-gel method. The structural char-
acterization of catalysts includes TG-DTA, N2 physisorption, XRD and
27
Al, and 19Si MAS NMR. The surface acid-base characterization in-
cludes temperature programmed desorption of ammonia and carbon
dioxide (NH3-TPD, CO2-TPD), FTIR-pyridine-TPD. The main objective
is to correlate the changes in acidic properties of promoted catalysts
with the 2-propanol dehydration activity.
2. Experimental
2.1. Preparation of catalysts
The preparation of pure TiO2 and Al- and Si- promoted TiO2 was
carried out using aluminum tri-sec-butoxide (Aldrich), tetra-ethyl-
ortho-silicate (Aldrich) and titanium isopropoxide (Aldrich) diluted in
2-propanol (Baker) in amounts necessary to formulate 1, 3 and 10%
mol Al2O3 and 1%, 3% and 10% mol SiO2 in TiO2. The hydrolysis agent
was a 0.05 M HNO3 solution (deionized water, HNO3 Baker). Molar
ratios were H+/alkoxide = 0.01, alcohol/alkoxide = 65, water/alk-
oxide = 20. The sol-gel method did not include pre-hydrolysis proce-
dure. The gels were dried at room temperature, and the dry solids were
calcined at 500 °C for 4 h. At the same time, samples of catalysts were
calcined at 700 °C to observed the effect of both cation content thermal
treatment in crystalline structure and surface area.
2.2. Characterization methods
The crystallization and phase transitions, which occurred as a result
of thermal treatment of the xerogels, were observed by XRD (D-500,
Siemens, monochromatic CuKα radiation). Surface areas were analyzed
by N2 physisorption (Autosorb-1, Quantachrome). Thermal gravimetric
(TG) and differential thermal analysis (DTA) were conducted on a
Netzsch system using 100 mg of dried sample with a heating rate of
10 °C/min.
Magic-angle spinning nuclear magnetic resonance (MAS NMR)
analysis was carried out on a Bruker ASX 300. A standard bore Bruker
MAS probe was used. 27Al MAS NMR spectra were obtained at
78.21 MHz with spectral range of 12 kHz. Aluminum nitrate
(δ = 0 ppm) was used as reference. 29Si MAS NMR spectra were ob-
tained at 59.62 MHz with spectral range of 3.5 kHz, referenced to tet-
ramethylsilane (δ = 0 ppm).
Ammonia programmed temperature desorption (NH3-TPD) for
samples calcined at 500 °C was performed in an analyzer set-up with
flow and temperature control. Helium and 5% ammonia-helium gases
were used (PraxAir). Calcined samples (400 mg) were dried in-situ at
400 °C in helium flow. The NH3 adsorption was made by contact of the
dried sample with ammonia-helium flow at 100 °C, followed by He
flushing at the same temperature. The desorption was carried out be-
tween 100 and 500 °C with a heating rate of 10 °C/min and helium flow
of 100 mL min−1. The ammonia desorption was measured by TCD
(Gow-Mac). Carbon dioxide programmed desorption (CO2-TPD) was
performed in the same analyzer set-up, using a 5% carbon dioxide-he-
lium mixture (PraxAir). The CO2 adsorption for catalysts calcined at
500 °C was made by contact of the dried sample (400 mg) with carbon
dioxide-helium flow at 25 °C, followed by He flushing at the same
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Catalysis Today xxx (xxxx) xxx–xxx
temperature. The CO2 desorption was carried out between 25 and
500 °C with a heating rate of 10 °C/min and helium flow of
100 mL min−1 and measured by TCD.
FTIR-pyridine-TPD analysis for catalysts calcined at 500 °C was
carried out in a Nicolet 560 Magna spectrophotometer. Samples
(30 mg) of catalysts were dried in-situ at 400 °C at vacuum (10−6 Torr).
Pretreated sample was cooled at 50 °C to proceed to pyridine adsorp-
tion. Excess of pyridine was eliminated by vacuum at 50 °C. Lewis and
Brønsted acidic type was analyzed by FTIR-pyridine spectra at different
desorption temperatures (50, 100, 200, 300 and 400 °C). Lewis acidity
was analyzed at 1450 cm−1, 1575 cm−1, and 1605 cm−1 wave num-
bers, and Brønsted acidity was identified at 1545 cm−1 and 1636 cm−1
wave numbers.
2.3. Catalytic testing reactions
The catalytic acid-base properties of materials were studied with 2-
propanol dehydration as a model reaction. The dehydration of 2-pro-
panol (Aldrich) was carried out on catalysts calcined at 500 °C. Pyrex
tubular reactor was heated inside a furnace with a temperature control
device for adjusting to within 1 °C. The catalytic bed was prepared with
an in-situ thermal treatment at 400 °C in nitrogen flow for 1 h. The feed
was a nitrogen flow saturated with alcohol. Table 1 shows the partial
pressure of each alcohol in the reactor feed and the reaction conditions.
The composition of reaction products was analyzed by a Gow-Mac
series 750 gas chromatograph with a 2 m Porapak Q packed column,
using FID detector. The absence of external and internal diffusion under
the reaction conditions used was checked.
3. Results
3.1. Thermal gravimetric and differential thermal analysis
Fig. 1 shows the thermal evolution of TiO2, 3% Si- and 3% Al-pro-
moted TiO2 dried samples by TG and DTA. The positive or negative
values of DTA indicate endothermic or exothermic phenomena. All the
samples stabilize their weight loss approximately at 400 °C. For the
TiO2 precursor two exothermic signals are observed. The first one, at ca.
280 °C, attributed to the combustion of the organic components in the
precursor; the second, at ca. 400 °C, associated with the crystalline
conformation of anatase. The addition of Al and Si modifies the thermal
evolution in agreement with published results [31]. The differences in
the nature of the alkoxides used in the formulation of mixed oxides
generate changes in the combustion of precursors and the crystal-
lization to anatase occurs at higher temperatures. The conformation of
anatase in the TiO2-Al2O3 samples is at ca. 500 °C, and the signal is
wider than on pure TiO2. There is an exothermic signal at ca. 960 °C
which would correspond to the crystallization of Al2O3. The con-
formation of anatase in the TiO2-SiO2 mixed oxides is at ca. 500 °C, and
the DTA base line above 500 °C does not show another transformation
above 500 °C.
3.2. X-ray diffraction
The X-ray diffraction patterns for samples treated at 500 °C and
Table 1
Reaction Conditions.
Catalysts calcined at 500 °C
Catalyst weight, mg 80
Partial pressure, Torr 33
Volumetric flow, L h−1 1.2
Mesh 80–100
Temperature of reaction 200 °C
G. Pérez-López et al. Catalysis Today xxx (xxxx) xxx–xxx

Fig. 1. TG and DTA of xerogel precursors of (a) TiO2, (b) 3% Si- and (c) 3%
Al-promoted TiO2.

Fig. 2. X-ray diffraction of TiO2-SiO2 treated at 500 °C, (○) anatase, (●)
rutile: (a) TiO2, (b) 1% SiO2, (c) 3% SiO2, (d) 10% SiO2.

Fig. 3. X-ray diffraction of TiO2-Al2O3 treated at 500 °C, (○) anatase, (●)
rutile: (a) TiO2, (b) 1% Al2O3, (c) 3% Al2O3, (d) 10% Al2O3.

700 °C show the increased thermal stability of anatase by the addition estimated by measuring the X-ray line broadening at 2θ = 25.3° and
of the promoter (Figs. 2–5). Al2O3 or SiO2 phases were not detected. using the Scherrer equation. Anatase-rutile transition is modified by
The crystal phase evolution of TiO2 and its mean crystallite size are different contents of Al- and Si- in the TiO2. Pure TiO2 treated at 700 °C
sensitive to the composition (Table 2). The crystallite size was shows the well-known transition from anatase to rutile phases. The

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Fig. 4. X-ray diffraction of TiO2-SiO2 treated at 700 °C, (○) anatase, (●)
rutile: (a) TiO2, (b) 1% SiO2, (c) 3% SiO2, (d) 10% SiO2.

Fig. 5. X-ray diffraction of TiO2-Al2O3 treated at 700 °C, (○) anatase, (●)
rutile: (a) TiO2, (b) 1% Al2O3, (c) 3% Al2O3, (d) 10% Al2O3..

Table 2 3.3. Surface area and pore volume

Effect of contents and thermal treatment in mean crystallite size.
Fig. 6 shows the nitrogen sorption isotherm on TiO2 and 3% Al- and
Catalysts % Crystallite Size, Å
3% Si- promoted samples, calcined at 500 °C. All the samples treated at
500 °C 700° 500 °C and 700 °C have the type IV isotherm, characteristic of meso-
porous solids, and type H2 hysteresis, for solids made by aggregates or
TiO2 – 114 Anatase, 262
agglomerates of spherical particles and non-uniform shape of pores
Rutile, 290
TiO2-Al2O3 1 92 160
[33,34]. These characteristics can be related to the acidic hydrolysis of
TiO2-Al2O3 3 82 151 alkoxides and the condensation mechanism of xerogel particles [35]. As
TiO2-Al2O3 10 43 96 observed in Table 3, the BET surface area and pore volume are sensitive
TiO2-SiO2 1 101 134 to the cations contents and to the thermal treatment. The loss of surface
TiO2-SiO2 3 94 99
area and pore volume for mixed oxides calcined at 700 °C is lower than
TiO2-SiO2 10 55 78
for TiO2. Then, the texture properties of the promoted oxides have an
enhanced thermal stability as a function of Si and Al content. The
mixed oxides at the same temperature present only the anatase phase average pore size is almost the same for all the samples treated at
pattern, and a lower diffraction signal as the cation content is increased. 500 °C and 700 °C, except for TiO2. These effects in textural properties
The promotion of TiO2 by Al and Si delays the thermal evolution of of TiO2 base mixed oxides (increase of both surface area and thermal
anatase into rutile [5–7] by the action of the ion solution into the stability) by addition of cations can be explained as a result of cation
crystal lattice. This is in agreement with published results for TiO2-base dispersion into the solid, by the hand of results of crystalline char-
mixed oxides [31,32], as an effect of cations distribution into the solid. acterization [5,7,12]. Additionally, it is interesting to observe the ef-
fects of cations precursors in the sol-gel synthesis of mixed oxides [11]
that can promote to changes in the microstructural distribution of Al

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Fig. 6. Nitrogen sorption isotherm of (a) TiO2 and (b) 3% Al- and (b) 3%
Si- promoted catalysts, calcined at 500 °C.

and Si, related directly to the textural and chemical properties of the
mixed oxides.

3.4. Ammonia temperature-programmed desorption

Figs. 7 and 8 illustrate the deconvolution of ammonia TPD profiles

for TiO2 and TiO2-Al2O3 3% and TiO2-SiO2 3% catalysts, showing
Gaussian peaks associated to different acid strengths according to the
desorption temperature. The ammonia adsorption capacities of TiO2
and Al and Si promoted samples treated at 500 °C are listed in Figs. 9
and 10. It is known that the ammonia uptake per gram of catalyst is
enhanced by the promotion of Al and Si, and it has been related to the
generation of new acid sites [1,2,16,29]. On the contrary, it is inter-
esting to observe that the specific ammonia uptake (μmol NH3/m2) is
not enhanced by the promotion of cations. In fact, the specific ammonia
uptake shows a decrease as the cation content is increased, due to the
simultaneous increase of both ammonia uptake per gram and BET
surface area (m2/g). The enhancement of BET surface area is more
sensitive to the content of cations than the enhancement of ammonia
uptake per gram, diminishing the value of specific ammonia uptake. It
means that although the total number of acid sites is increase as a
function of Al2O3 and SiO2 content, the specific number of acid sites
decreases.
Also, it is known that ammonia has different sorption strengths Fig. 7. NH3-TPD profiles of (A) TiO2, (B) TiO2-Al2O3 1%, (C) TiO2-Al2O3 3% and (D)
depending on the surface conditions [36–38]. It is possible to classify TiO2-Al2O3 10%, calcined at 500 °C.
the deconvolution peaks in ammonia TPD associated to acid strength of
the catalytic surface, considering both peak area magnitude and central 3.5. Carbon dioxide temperature-programmed desorption
temperature of each peak. Then, four types of acid strengths is proposed
for these solids: weak (centered in the range 145–230 °C), intermediate The deconvolution of the CO2-TPD profiles is shown in Figs. 11 and
(280–300 °C), strong (360–400 °C) and very-strong (440–500 °C). The 12. The Gaussian peaks are associated to different basic strengths ac-
distribution of the specific ammonia sorption shows that the decrease in cording to the desorption temperature. The classification of the de-
the specific number of acid sites is more sensitive to the Al2O3 content convolution peaks is related to basic strength of the catalytic surface,
than SiO2 content, intermediate and strong acid strengths mainly.

Table 3
Effect of contents and thermal treatment in surface area and pore volume.

Catalysts % Surface Area m2g−1 Pore Volume cm3g−1 Average Pore Size, Å

500 °C 700 °C 500 °C 700 °C 500 °C 700 °C

TiO2 – 112 5 0.12 0.03 43 240

TiO2-Al2O3 1 154 34 0.12 0.03 31 35
TiO2-Al2O3 3 216 73 0.21 0.07 39 38
TiO2-Al2O3 10 287 89 0.42 0.12 59 54
TiO2-SiO2 1 163 35 0.22 0.07 54 80
TiO2-SiO2 3 217 97 0.23 0.10 42 41
TiO2-SiO2 10 290 131 0.28 0.12 38 37

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Fig. 8. NH3-TPD profiles of (a) TiO2, (B) TiO2-SiO2 1%, (C) TiO2-SiO2 3% and (D) TiO2- Fig. 11. CO2-TPD profiles of (A) TiO2, (B) TiO2-Al2O3 1%, (C) TiO2-Al2O3 3% and (D)
SiO2 10%, calcined at 500 °C. TiO2-Al2O3 10%, calcined at 500 °C.

Fig. 9. Specific ammonia uptake (μmol NH3 m−2): acid sites strength distribution for
TiO2-Al2O3 catalysts.

Fig. 12. CO2-TPD profiles of (a) TiO2, (B) TiO2-SiO2 1%, (C) TiO2-SiO2 3% and (D) TiO2-
SiO2 10%, calcined at 500 °C.

considering both peak area magnitude and central temperature of each

Fig. 10. Specific ammonia uptake (μmol NH3 m−2): acid sites strength distribution for
TiO2-SiO2 catalysts.
peak. Four types of basic strengths is proposed: weak (centered in the
range 100–180 °C), intermediate (240–250 °C), strong (310–330 °C)
and very-strong (400–500 °C). The distributions of the CO2 uptake and
per m2 as a function of desorption temperature are listed in Figs. 13 and
14, showing that the specific number of basic sites (μmol CO2/m2) is
more sensitive to the Al and Si promotion than de number of basic sites
per gram of catalyst. This decrease in the specific CO2 uptake is related
to the enhancement of BET surface area as a function of cation content.
The distribution of the specific CO2 uptake shows a noticeable decrease
in the specific number of basic sites for both Al and Si promoted TiO2,

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Fig. 13. Specific CO2-uptake (μmol CO2 m−2): basic sites strength distribution for TiO2-
Al2O3 catalysts.

Fig. 15. FTIR-pyridine-TPD profiles for TiO2 catalyst calcined at 500 °C.

Fig. 14. Specific CO2 uptake (μmol CO2 m−2): basic sites strength distribution for TiO2-
SiO2 catalysts.

practically in all the types of basic strength, except for the very-strong
strength.
The change of both the specific number of basic sites (CO2-TPD) and
the specific number of acid sites (NH3-TPD) by the Al and Si promotion
shows that the acid-base balance in the surface of these catalysts is
modified as a function of cation content. The molar ratio of acid sites
and basic sites is listed in Table 4. Although both specific numbers of
acid sites and basic sites decrease with the content of Al2O3 and SiO2,
the acid-base molar ratio is increased by both Al and Si promotion. It is
indicative of the effect of cation promotion in the acid-base balance on Fig. 16. FTIR-pyridine-TPD profiles for TiO2-Al2O3 10% catalyst calcined at 500 °C.

Table 4 the surface of these mixed oxides, generating a shift in the balance of
Reaction rates and TOF for 2-propanol dehydration at 200 °C. acidic and basic sites to improve the acidity of the catalytic surface.
Catalysts Cation Acid-base Reaction Rate TOF x104
Content molar ratio x1010 3.6. FTIR-pyridine-TPD
mmol g−1 NH3/CO2 mol m−2 s−1 s−1

TiO2 0.0 1.81 21.8 7.0 Figs. 15–17 show the FTIR-pyridine desorption spectra for TiO2,
TiO2-Al2O3 0.196 2.04 20.4 7.5 TiO2-Al2O3 10% and TiO2-SiO2 10% catalysts. Specific band for pyr-
1% idine sorption [15,17,29,39–43] are observed, identifying the interac-
TiO2-Al2O3 0.589 2.16 26.0 12.4
3%
tion of pyridine molecule according to the type of acidity: 1450 cm−1,
TiO2-Al2O3 1.962 2.78 55.1 33.0 1575 cm−1 and 1605 cm−1 for Lewis acid sites; 1545 cm−1 and
10% 1635 cm−1 for Brønsted acid sites. All these catalysts have pre-
TiO2-SiO2 1% 0.166 2.74 55.2 21.6 dominantly Lewis acidity, and a low presence of Brønsted acidity is
TiO2-SiO2 3% 0.499 2.50 72.9 30.4
detected only for the TiO2-SiO2 10% catalyst. These results reveal that
TiO2-SiO2 1.664 2.84 232.9 109.3
10% TiO2 and TiO2-Al2O3 catalysts perform at Lewis acidity and the addition
of Al as promoter generates Lewis-type TiO2-Al2O3 catalysts, according

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G. Pérez-López et al.
Fig. 17. FTIR-pyridine-TPD profiles for TiO2-SiO2 10% catalyst calcined at 500 °C.
to results reporting by several researches [14,29,43]. The band at
1620 cm−1 has been associated with pyridine sorption on Al+3 sites
with incomplete tetrahedral and octahedral coordination [40]. The
detection of Lewis and Brønsted acidity for TiO2-SiO2 catalysts is in
agreement with results reporting for this type of mixed oxides
[1,15,17,44,45]. However, it is important to indicate that Lewis acidity
is predominantly for both Al- and Si-promoted catalysts. The presence
of 1545 cm−1 band at 200–300 °C is an indicative of the relative force
of the Brønsted acidity for TiO2-SiO2 10% catalyst.
27 19
3.7. Al and Si MAS NMR
The 27Al MAS NMR spectra of 10% Al-promoted TiO2 and 19Si MAS
NMR of 10% Si-promoted TiO2 are shown in Fig. 18. Six-coordinated Al
species (at about −3 ppm) are related to non-framework aluminum,
and lattice aluminum in four- and five-coordinated environments is
detected with peaks at about 50 and 26 ppm [46]. The relative intensity
of the signal at −3 ppm indicates that non-framework aluminum sites
(octahedral Al species) are more abundant than framework aluminum
sites (tetrahedral Al species). This is an evidence of the formation of
micro-domains of six-coordinated Al atoms for 10% Al- promoted TiO2,
and it can be related to a low number of heterolinkages (Ti-O-Al). There
are peaks at −81, −90, −99 and −109 ppm in the 19Si MAS NMR
spectra, associated with Q1 = Si(OSi)1(OX)3, Q2 = Si(OSi)2(OX)2,
Q3 = Si(OSi)3(OX) and Q4 = Si(OSi)4 sites, where X = H or Ti. It has
been demonstrated that Q2 and Q3 peaks are related to the presence of
Ti in the second coordination sphere of silica [44,47,48]. However, Q2
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Catalysis Today xxx (xxxx) xxx–xxx
and Q3 signals just provide qualitative information about the Ti-O-Si
linkages because the 29Si resonances from SieOeH and SieOeTi bonds
are not distinguishable [15]. The relative intensity of Q4 signal in-
dicates the aggregation of non-framework silica.
3.8. Dehydration of 2-propanol
The 2-propanol dehydration reaction rates at 200 °C on catalysts
calcined at 500 °C are shown in Table 4. Turnover frequency (TOF) is
calculated by the relation of the 2-propanol decomposition reaction rate
and the total ammonia uptake in the NH3-TPD experiments. Propene
was the only product for all catalysts. Si-promoted catalysts present
higher reaction rates and TOF than the Al-promoted catalysts, in a same
range of values of molar cation content (mmol of cation per gram of
catalyst). In others words, the 2-propanol decomposition is more sen-
sitive to the Si promotion than the Al promotion. The increase in the 2-
propanol dehydration activity as a function of Al2O3 and SiO2 content
can be related to the generation of acid sites by differences in the co-
ordination of the cations in the surface of mixed oxides [30]. According
to the acid-base characterization by NH3-TPD and CO2-TPD experi-
ments, the increase of concentration of acid sites (μmol NH3 g−1) by Al
and Si promotion predicts that the increase in alcohol decomposition
would be more sensitive for Si-promoted catalysts. These differences of
the effect of Al and Si promotion in the 2-propanol dehydration activity
is an important fact related to the type of promoted cation and its effect
in the generation of acid sites: promoting cation allows the formation of
effective charge imbalance on the catalyst surface [29] and it generates
acid sites. This charge imbalance is related to the coordination number
of each cation in the mixed oxide. On the other hand, it is interesting to
observe that the specific number of acid sites decrease as the Al and Si
content increase, showing an inverse relationship of 2-propanol dehy-
dration activity with the specific NH3 uptake.
4. Discussion
For the catalysts studied in this work, XRD and TG-DTA analysis
reveal that Al and Si cations were dispersed in the TiO2 lattice, chan-
ging the thermal evolution of mixed oxides and the mean crystallite
size. The effect in the crystal phase evolution is similar for Al- and Si-
promoted samples; both Al and Si hinder the growth of the anatase
phase. Also, the shift of the temperature of anatase phase conformation
indicates the interaction of promoted cation in the thermal evolution of
TiO2. Nitrogen sorption showed that the thermal evolution of BET
surface areas is modified by the presence of cations. These results in-
dicate that the promotion of Al and Si in TiO2 at contents lower than
10% was enough to modify its structure and textural properties.
However, it was necessary to study the promotion effects in the cata-
lytic performance by acid-base and reaction characterization. The acid-
base properties of mixed oxides has been related to the production of
heterolinkages M-O-M’, where M and M’ are two different types of ca-
tions [29,30,46,47]. Tanabe’s hypothesis [29] predicts what type of
mixed oxides will show acidic properties. The generation of acid sites is
Fig. 18. 27Al MAS NMR spectra of (a) TiO2-Al2O3 10% and 19Si MAS NMR
spectra of (b) TiO2-SiO2 10%.
G. Pérez-López et al.
caused by an excess of charge (positive or negative) in the interaction of
the cations coordinated in the mixed oxide. This hypothesis postulates
that the coordination number of cations is maintained upon mixing; and
the coordination number of oxygen atoms bond to the higher content
cation (major component) are retained for all the oxygen atoms in the
mixed oxides. The application of this hypothesis for Ti-O-Si, where Ti is
the higher content cation (six-coordinated Ti, three-coordinated O)
predicts a positive charge difference, and Lewis acidity is assumed to
appear. For Si-O-Ti, where Si is the higher content cation (four-co-
ordinated Si, two-coordinated O) predicts a negative charge difference
which is compensated with protons to keep the electronic neutrality,
and Brønsted acidity is assumed to appear. Then, it is possible to gen-
erate Lewis and Brønsted acidity for TiO2-SiO2 mixed oxides in two
types of interactions. The application of the same hypothesis for Ti-O-
Al, where Ti is the higher content cation (six-coordinated Ti, three-
coordinated O), predicts a negative charge difference for six-co-
ordinated Al (Brønsted acidity), and predicts a positive charge differ-
ence for four-coordinated Al (Lewis acidity). For Al-O-Ti, where Al is
the higher content cation, six-coordinated Al is the most likely co-
ordination and the hypothesis predicts a zero charge difference (no
generation of acid sites by interaction of cations). In the catalyst surface
the presence of four-coordinated Al is possible and it predicts a negative
charge difference for Al-O-Ti, and the presence of some Brønsted
acidity. Then, it is possible to generate Lewis or Brønsted acidity for
TiO2-Al2O3 in several types of interactions. However, the six-co-
ordinated Al atoms are related to non-framework aluminum. In other
words, the presence of the six-coordinated Al is evidence of aggregates
of aluminum atoms with a low Ti-O-Al interaction (low production of
Brønsted acidity). Then, the generation of Lewis acidity by the inter-
action of six-coordinated Ti and four-coordinated Al is the most likely
interaction for TiO2-Al2O3.
Sol-gel method allows the synthesis of mixed oxides with high
number of heterolinkages. The rates of hydrolysis and condensation
steps are important to achieve a better dispersion of cations. However,
the generation of heterolinkages is modified by the content of the ca-
tions and thermal treatment. It has been demonstrated that the pro-
duction of heterolinkages in TiO2-SiO2 and TiO2-Al2O3 mixed oxides is
limited [49,50]. In this case, the 27Al and 19Si MAS NMR reveal a low
number of heterolinkages for TiO2-Al2O3 samples (high content of non-
framework Al) and higher for TiO2-SiO2 (presence of Ti in the second
coordination sphere of silica, Q2 and Q3). It is evident that the dis-
tribution of cations in the TiO2 lattice is different for Al and Si, mod-
ifying the interaction of promoted cations in the bulk and surface of
catalysts. In agreement with the hypothesis of Tanabe, the 27Al MAS
NMR result shows the possibility of increase in the Lewis acidity for
TiO2-Al2O3 samples by the interaction with four-coordinated Al; and
the 19Si MAS NMR result indicates the possibility of increase in both
Brønsted and Lewis acidity for TiO2-SiO2. Then, the noticeable differ-
ences in 2-propanol reaction rate between Al- or Si-promoted catalysts
could be related with the presence of Brønsted acidity, it in agreement
with the FTIR-pyridine-TPD results.
The ammonia uptake reveals the generation of acid sites by the
promotion of Al and Si, and the specific number of acid sites decrease as
the content cation increase for both Al- and Si-promoted samples. The
increase in the number of acid sites by promotion of cations is notice-
able for intermediate and strong acid strengths, centered at 280–300 °C
and 360–400 °C, respectively. This fact is important for reacting sys-
tems with adsorption, reaction and desorption like the conversion of
alcohols. Upon promotion, the acid-base properties of these oxides are
modified and the conversion of alcohols could be enhanced by the
production of acid sites. However, the results indicate an inverse re-
lationship between the specific number of acid sites and the reaction
rate for the dehydration of 2-propanol: while the alcohol dehydration
TOF is increased as a function of content of cations, the specific number
of acid sites decreases as the content of cations increases. The carbon
dioxide TPD analysis reveals that the increase of basic sites density of
9
Catalysis Today xxx (xxxx) xxx–xxx
mixed oxides catalysts is less sensitive to the content of promoted cation
than the increase of acid sites density (ammonia TPD). Then, it is im-
portant to observe that the molar ratio between acid-basic sites is in-
creased as a function to the content of cations, shifting the acid-base
balance of the catalytic surface to enhance the acidity of catalysts.
The dehydration of 2-propanol has been used to study the acid-base
properties of catalysts and reaction rate has been related to the number
of acid sites. The products distribution of the catalytic alcohol conver-
sion is useful to identify the predominant reaction mechanism on the
surface [51,52]. The E1 is a two-step pathway, the rate-determining
step of which is the ionization of the alcohol molecule to a carbenium
ion that rapidly loses a β proton. In the E2, both the OH group and the
proton depart simultaneously. This pathway takes place in a single step,
with the proton being pulled off by a base. In the E1cB mechanism, the
first step of dehydration is the formation of a carbanion by the elim-
ination of proton and the OH group elimination takes place in the
second step. The carbanion is the conjugate base of the surface acid site.
The elimination of the proton in the E1cB mechanism can also take
place from the oxygen atom, forming C]O bond. Catalysts with a large
number of acid sites lead predominantly to dehydration (E1 route), and
dehydrogenation takes place on basic surfaces (E1cB route). The 2-
propanol dehydration over TiO2-base mixed oxides at 200 °C indicates
that the alcohol dehydration is performed in the E1 route.
However, increase in the number of acid sites (measured by am-
monia-TPD) and the increase in acid-base molar ratio (NH3/CO2) does
not necessary mean an increase in the alcohols decomposition activity,
because there are several collateral effects in the adsorption of the al-
cohol molecule. Then, the alcohols decomposition results must be
carefully analyzed. Ammonia sorption takes place in absence of water
and other molecules. On the other hand, the conversion of alcohols
produces water, and the catalytic surface can modify its acid-base
performance by the presence of H2O. There are other effects, like the
differences in the adsorption strength of ammonia and alcohols. Studies
related to the kinetics of the 2-propanol conversion over TiO2 [53,54]
indicate the dependence of the dehydration-dehydrogenation se-
lectivity with the reaction conditions. The presence of water or oxygen
in the reactor feed and the thermal pretreatment of the catalyst modify
the selectivity in the alcohol conversion. The generation of acid sites by
edge crystal defects is another fact that modifies the catalytic perfor-
mance [55]. Both Al- and Si-promotion decrease the crystallite size of
anatase as a function of cation content, and simultaneously increase the
number of acid sites detected by NH3-TPD. However, the effect of
crystallite size in the reaction rate of alcohols conversion is more re-
levant for the Si-promoted catalysts than the Al-promoted ones. Then,
the generation of active sites for alcohols conversion depends not only
on the crystallite size but also the type of promoted cation. It could be
possible that the coordination of promoted cation acts in the charge
balance of crystal defect. The differences in the catalytic performance of
alcohols conversion can be related to a more effective difference in the
charge balance of crystal defect by Si-promotion than the Al promotion.
Moreover, it is important to point out that ammonia and alcohols
are adsorbed with different strengths on the same surfaces [1]. In others
words, the differences in the sorption strength of ammonia and 2-pro-
panol on the same catalytic surface is an important fact in the re-
lationship between alcohols decomposition activity and number of acid
sites. The differences in the 2-propanol reaction rate would be related to
changes in the alcohol adsorption strength on each catalytic surface due
to the modification of the number and strength of acid sites by pro-
motion of cations [49,56–58]. Then, it is not advisable to correlate the
total number of acid sites determined by NH3-TPD with the reaction
rate of alcohols decomposition. The enhancement in the reaction rate
and TOF of alcohols decomposition by cation promotion would be re-
lated to changes in the alcohol sorption affinity of sites. The promotion
of cations modifies both the number and sorption strength distribution
of acid sites, and NH3-TPD is useful to measure the acidic properties of
the promoted catalysts. At same time, the CO2-TPD is useful to measure
G. Pérez-López et al.
the effect of cation promotion in the acid-base sites balance. However,
the catalytic performance of these acid sites in the alcohol decom-
position depends on the interaction between the alcohol and surface
[59,60]. It is important to observe that the presence of Brønsted sites
(1545 cm−1 band) by the addition of Si in contrast with absence of this
type of acid sites Al-promoted catalysts, detected by FTIR-pyridine
spectra, indicating that the Brønsted acidity in TiO2-SiO2 promotes the
dehydration reaction rate acting in the determining step of E1 me-
chanism, mainly in the attraction of β proton of carbenium ion.
5. Conclusions
The molar ratio of acid-base sites densities of TiO2-base catalysts is
increased by the promotion of Al and Si into TiO2, and it this fact can be
related to the increase in the alcohols decomposition activity. However,
the specific number of acid sites decreased by the cations promotion,
generating an inverse relationship between the acid sites density and
the catalytic alcohol dehydration activity. On the other hand, the spe-
cific number of basic sites noticeably decreased by both Al and Si
promotion. Consequently, the balance between acid and basic sites
(acid-base molar ratio) on the catalytic surface is increased as a func-
tion of content of cations. The 27Al and 19Si MAS NMR results revealed
a low number of heterolinkages for TiO2-Al2O3 samples (high content of
non-framework Al) and higher for TiO2-SiO2 (presence of Ti in the
second coordination sphere of silica). Therefore, the generation of acid
sites in the Al-promoted materials could be not related to the generation
of heterolinkages. Additionally, the effect of Brønsted acidity in the
alcohol dehydration activity was more relevant for Si promoted cata-
lysts than Al promoted ones, showing that the type of promoted cation
has an important role in the catalytic performance for the conversion of
alcohols. It is possible to detect the effect in the 2-propanol conversion
by the promotion of cations in TiO2, indicating that the interaction of
the alcohol on the catalytic surface can be noticeable modified ac-
cording to the type of promoted cation. FTIR-pyridine-TPD analysis
reveals predominantly Lewis-type acidity for both, Si- and Al-promoted
catalysts, showing a presence of Brønsted acid sites for 10% SiO2 cat-
alysts. These results indicate that the noticeable increase of alcohol
dehydration activity can be related to the type of coordination of pro-
moted cation and according to the acidity type (Lewis or Brønsted).
References
[1] Z. Liu, J. Tabora, R.J. Davis, J. Catal. 149 (1994) 117.
[2] J.R. Sohn, H.J. Jang, J. Catal. 132 (1991) 563.
[3] F. Trejo, M.S. Rana, J. Ancheyta, A. Rueda, Fuel 100 (2012) 163–172.
[4] J.R. Sohn, D.C. Shin, App. Catal. B 77 (2008) 386–394.
[5] J. Escobar, J.A. De Los Reyes, T. Viveros, Ind. Eng. Chem. Res. 39 (3) (2000) 666.
[6] J. Escobar, J.A. De Los Reyes, T. Viveros, Stud. Surf. Sci. Cat. 143 (2002) 547.
[7] J.A. Montoya, T. Viveros, D. Chadwick, J.M. Domínguez, J. Navarrete, I. Schifter, J.
Sol Gel Sci. Technol. 2 (1994) 431.
[8] T. Onfroy, G. Clet, M. Houalla, J. Phys. Chem. B 109 (2005) 14588.
[9] V. Harlé, M. Vrinat, J.P. Scharff, B. Durnad, J.P. Deloume, App. Catal. A 196 (2000)
261.
[10] E.Y. Kaneko, S.H. Pulcinelli, V. Teixeira da Silva, C.V. Santilli, App. Catal. A 235
10
Catalysis Today xxx (xxxx) xxx–xxx
(2002) 71.
[11] J.B. Miller, E.I. Ko, Catal. Today 35 (1997) 269–292.
[12] H.P. Pastenes, A. Ochoa-Tapia, T. Viveros, A. Montoya, J. Sol-Gel Sci. Technol. 37
(2008) 49–56.
[13] A. Vazquez, T. López, R. Gómez, A. Morales, J. Solid State Chem. 128 (2) (1997)
161–168.
[14] E. Rodenas, T. Yamaguchi, H. Hattori, K. Tanabe, J. Catal. 69 (1981) 434.
[15] X. Gao, I.E. Wachs, Catal. Today 51 (1999) 233.
[16] C. Odenbrand, J. Brandin, G. Busca, J. Catal. 135 (1992) 505.
[17] H. Nakabayashi, Bull. Chem. Soc. Jpn. 65 (1992) 914.
[18] P. Berteau, B. Delmon, App. Catal. 70 (1991) 307.
[19] X. Chen, G. Clet, K. Thomas, M. Houalla, J. Catal. 273 (2010) 236–244.
[20] S. Hu, R.J. Willey, B. Notari, J. Catal. 220 (2003) 240.
[21] B. Notari, R.J. Willey, M. Panizza, G. Busca, Catal. Today 116 (2006) 99.
[22] A. Gil, M.A. Vicente, S.A. Korili, J. Catal. 229 (2005) 119.
[23] V.K. Diez, C.R. Apesteguia, J.I. DiCosimo, J. Catal. 215 (2003) 220.
[24] P.K. Doolin, S. Alerasool, D.J. Zalewski, J.F. Hoffman, Catal. Lett. 25 (1994) 209.
[25] T. Kataoka, J.A. Dumesic, J. Catal. 112 (1988) 66.
[26] M.A. Aramendia, V. Boráu, I.M. Garcia, C. Jiménez, A. Marinas, J.M. Marinas,
A. Porras, F.J. Urbano, Appl. Catal. A 184 (1999) 115.
[27] S. Delsarte, P. Grange, Appl. Catal. A 259 (2004) 269.
[28] C.D. Baertsch, K.T. Komala, Y.H. Chua, E. Iglesia, J. Catal. 205 (2002) 44.
[29] K. Tanabe, M. Misono, Y. Ono, H. Hattori, New Solids Acids and Bases, Elsevier,
1989.
[30] J.B. Miller, E.I. Ko, J. Catal. 159 (1996) 58.
[31] J.-J. Cheng, D.-W. Wang, J. Non-Cryst. Solids 100 (1988) 288.
[32] H. Nakabayashi, K. Tokuhiro, Bull. Kochi Nat. Coll. Technol. 33 (1990) 63.
[33] G. Leofanti, M. Padovan, G. Tozzola, V. Venturelli, Catal. Today 41 (1998) 207.
[34] S. Stork, H. Bretinger, W.F. Maier, Appl. Catal. A 174 (1998) 137.
[35] Q. Xu, M.A. Anderson, J. Am. Ceram. Soc. 77 (1994) 1939.
[36] M.V. Juskelis, J.P. Slanga, T.G. Roberi, A.W. Peters, J. Catal. 138 (1992) 391.
[37] G. Bagnasco, J. Catal. 159 (1996) 249.
[38] R. Valdez, B. Pawelec, J.M. Quintana, A. Olivas, Fuel 105 (2013) 688–694.
[39] T. López, P. Bosch, F. Tzompantzi, R. Gómez, J. Navarrete, E. López-Salinas,
M.E. Llanos, App. Catal. A 197 (2000) 107–117.
[40] C. Lahousse, F. Maugé, J. Bachellier, J.-C. Lavalley, J. Chem. Soc. Faraday Trans. 91
(1995) 2907–2912.
[41] G. Busca, Catal. Today 41 (1998) 191–206.
[42] M.C. Kung, H.H. Kung, Catal. Rev. Sci. Eng. 27 (1985) 425–460.
[43] A. Gutierrez-Alejandre, M. González-Cruz, M. Trombetta, G. Busca, J. Ramírez,
Microporous Mesoporous Mater. 23 (1998) 265–275.
[44] Z. Liu, G.M. Crumbaugh, R.J. Davis, J. Catal. 159 (1996) 83.
[45] S.M. Jung, P. Grange, Appl. Catal. A: Gen. 228 (2002) 65.
[46] J.M. Miller, L.J. Lakshmi, J. Phys. Chem. B 102 (1998) 6465.
[47] C. Contescu, V.T. Popa, J.B. Miller, E.I. Ko, J.A. Schwarz, J. Catal. 157 (1995) 244.
[48] R. Andrianainarivelo, D. Leclercq, P.H. Mutin, A. Vioux, J. Mater. Chem. 6 (1996)
1665.
[49] J.E. Swain, M.V. Juskelis, J.P. Slanga, J.G. Miller, M. Uberoi, N.D. Spencer, Appl.
Catal. A 139 (1996) 175–187.
[50] C. Beck, T. Mallat, T. Bürgi, A. Baiker, J. Catal. 204 (2001) 428.
[51] M.A. Aramendía, V. Borau, C. Jiménez, J.M. Marinas, A. Porras, F.J. Urbano, J.
Catal. 161 (1996) 829.
[52] Y. Shinohara, T. Nakajima, S. Suzuki, J. Mol. Struct. (Theochem.) 460 (1999)
231–244.
[53] J.E. Rekoske, M.A. Barteau, J. Catal. 165 (1997) 57.
[54] D. Haffad, A. Chambellan, J.C. Lavalley, J. Mol. Catal. 168 (2001) 153–164.
[55] K.- Yu Kim, B.D. Kay, J.M. White, Z. Dohnalek, Surf. Sci. 602 (2008) 511–516.
[56] H. Bahrujia, M. Bowkera, C. Brookesa, P.R. Daviesa, I. Wawataa, Appl. Catal. 454
(2013) 66–73.
[57] J. Bedia, R. Ruiz-Rosas, J. Rodríguez-Mirasol, T. Cordero, J. Catal. 271 (2010)
33–42.
[58] J. Bedia, J.M. Rosas, J. Marquez, J. Rodríguez-Mirasol, T. Cordero, Carbon 47
(2009) 286–294.
[59] V.S. Lusvardi, M.A. Barteau, W.E. Farneth, J. Catal. 153 (1995) 41.
[60] V.S. Lusvardi, M.A. Barteau, W.R. Dolinger, W.E. Farneth, J. Phys. Chem. 100
(1996) 18183–18191.