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Applied Catalysis A: General 349 (2008) 148–155

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Applied Catalysis A: General


journal homepage: www.elsevier.com/locate/apcata

Activity of Gallium and Aluminum SBA-15 materials in the Friedel–Crafts


alkylation of toluene with benzyl chloride and benzyl alcohol
Maria J. Gracia a, Elia Losada a, Rafael Luque b, Juan M. Campelo a, Diego Luna a,
Jose M. Marinas a, Antonio A. Romero a,*
a
Departamento de Quimica Organica, Facultad de Ciencias, Universidad de Cordoba, Campus Universitario de Rabanales, Edificio Marie Curie (C3), E-14014 Cordoba, Spain
b
Green Chemistry Centre of Excellence, The University of York, Heslington, YO10 5DD York, United Kingdom

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

Article history: Ga-, Al- and AlGa-SBA-15 mesoporous materials were synthesized via a direct sol–gel hydrothermal
Received 19 February 2008 protocol. The SBA-15 materials were characterized using X-ray fluorescence (XRF), X-ray diffraction
Received in revised form 16 July 2008 (XRD), N2 physisorption, transmission electron microscopy (TEM) and pyridine and 2,6-dimethylpyridine
Accepted 17 July 2008
titration. The activity of the Ga- and AlGa-SBA-15 was investigated in the Friedel–Crafts alkylation of
Available online 26 July 2008
toluene with benzyl chloride (promoted by Lewis acidity) and benzyl alcohol (promoted by Brönsted
acidity). Quantitative conversion of the starting material was found for all Ga- and AlGa-SBA-15 after a
Keywords:
few hours of reaction at 110 8C in the alkylation of toluene with benzyl chloride. The mesoporous acidic
Ga- and AlGa-SBA-15
Heterogeneous catalysis
materials provided very poor activities in the alkylation of toluene with benzyl alcohol, with the
Friedel–Crafts alkylation exception of the Al-SBA-15. The activities of the Ga- and AlGa-SBA-15 were correlated to the higher
Alkylation of toluene proportion of Lewis compared to Brönsted acid sites. The solid acids were also highly reusable preserving
almost their initial catalytic activity after five reuses.
ß 2008 Elsevier B.V. All rights reserved.

1. Introduction [1], although it has also been reported to induce the creation of
Brönsted sites upon incorporation into a mesoporous network [24].
Heterogeneous catalysis plays an important role in the Friedel–Crafts alkylations are very useful reactions in Organic
replacement of liquid acids and/or superacids [1,2] for solid acids Chemistry [25,26]. The liquid-phase benzylation of benzene and
including microporous (zeolites) [3,4] and mesoporous (M41S, various aromatic substrates including benzyl chloride and benzyl
SBA) materials [5,6]. The M41S materials, exhibiting a well- alcohol is a key process to the synthesis of diphenylmethane and
ordered array of mesopores, have a low (hydro)thermal stability substituted diphenylmethanes that are building blocks in Organic
owing to their amorphous and thin (<20 Å) walls [7]. Synthesis for the preparation of important intermediates in the
The recently discovered mesoporous SBA family, prepared using pharmaceutical [27] and fine chemical industries [28,29]. These
a triblock copolymer as template in acid media, has been widely liquid-phase reactions have been traditionally catalysed by Lewis
employed in catalysis [8–15]. Such materials featuring high surface acids including AlCl3, FeCl3, BF3 and ZnCl2 [25,26,29]. The inherent
areas (600–1000 m2 g 1), highly ordered hexagonal/cubic arrays of drawbacks of all homogeneous systems are the production of
mesopores (50–300 Å) and thicker walls (30–60 Å), have improved significant quantities of hazardous waste (e.g. salts, acids, etc.) that
(hydro)thermal stabilities with respect to the M41S materials [16]. needs thorough washing and neutralisation as well as the
The hexagonal mesoporous SBA-15 structure has attracted a great difficulties in the catalysts recovery. A combination of green
deal of attention and many reports can be found on the direct or technologies is therefore needed to improve the green credentials
post-synthetic preparation of SBA-15 incorporating transition of the reaction. The replacement of the Lewis acids for more
metals (Al, V, Ti, Fe, etc.) with various catalytic applications [17– environmentally compatible catalysts can be done through the
19]. However, only few reports dealing with acidic Ga-SBA-15 implementation of the aforementioned solid acids and hetero-
materials can be found due to their weak acidity [20–23]. Gallium geneous catalysis, overcoming problems with catalyst recycling
normally confers Lewis acidity, useful for Friedel–Crafts reactions and generation of waste [30,31].
Several alternative solid acids have been reported in alkylation
processes including modified Ga- and Fe-ZSM-5 and H-b zeolites
* Corresponding author. Tel.: +34 957218638; fax: +34 957212066. [32,33], Fe2O3 or FeCl3 supported on microporous [33], mesopor-
E-mail address: qo1rorea@uco.es (A.A. Romero). ous [33,34] and macroporous materials [33,35], molecular sieves

0926-860X/$ – see front matter ß 2008 Elsevier B.V. All rights reserved.
doi:10.1016/j.apcata.2008.07.023
M.J. Gracia et al. / Applied Catalysis A: General 349 (2008) 148–155 149

containing Fe and Sn [36,37], Lewis acids supported clays and Si- area. The pore size distribution (PSD) was calculated from the
MCM-41 [38], Ga-HMS materials [39] and NiCl2 or ZnCl2 supported desorption branch of the N2 physisorption isotherms and the
aluminas [40]. H-ZSM-5 and H-b zeolites are very active in the Barret–Joyner–Halenda (BJH) formula. The cumulative mesopore
alkylation of phenols or naphthols [41,42]. However, the results volume VBJH was obtained from the PSD curve.
obtained for the benzylation of benzene were relatively poor [43]. Transmission electron microscopy (TEM) micrographs were
Choudhary et al. [33,44] recently reported the activity of H-ZSM-5 recorded on a FEI Tecnai G2 fitted with a CCD camera for ease and
and H-b zeolites can be improved via the preparation of Ga, Al or Fe speed of use. The resolution is around 0.4 nm. Samples were
oxides or chlorides supported on the microporous materials. suspended in ethanol and deposited straight away on a copper grid
Herein, we report the direct preparation of Ga- and AlGa-SBA- prior to analysis.
15 materials via sol–gel hydrothermal synthesis. The activity of the Solid State 71Ga NMR spectra have been obtained on a Bruker
materials was then investigated in the alkylation of toluene with ACP-400 spectrometer operating at 122 MHz. Approximately
benzyl chloride and benzyl alcohol. 100,000 transients were accumulated for Ga-SBA-15 with 1 s
recycling delay. The chemical shifts were referred to Ga(NO3)3 1 M
2. Experimental solution.
The surface acidity was measured in a dynamic mode by means
The parent SBA-15 materials were prepared using tetra- of a pulse chromatographic technique of gas-phase (300 8C)
ethylorthosilicate (TEOS), gallium acetylacetonate (A), gallium adsorption of PY (sum of Brönsted and Lewis acid sites) and 2,6-
nitrate (N) and aluminum isopropoxide as silica, gallium and dimethylpyridine (DMPY, Brönsted sites) as probe molecules [46].
aluminum sources, respectively. The triblock non-ionic copolymer DRIFTs characterisation of surface acidity involved the titration
EO20PO70EO20 (Pluronic P123) was employed as template. The of the acid sites with PY and DMPY. The basic probes were intro-
synthesis procedure was similar to that reported by Bonardet et al. duced by bubbling a stream of dehydrated and deoxygenated
[45] for Al-SBA-15 with some alterations. Firstly, the solution nitrogen (20 mL min 1) through the liquid and into the sample
containing 8 g Pluronic in 300 mL HCl at pH 1.5 was stirred at room chamber containing the neat (no KBr diluted) catalyst sample at
temperature for 2 h. Secondly, TEOS was employed instead of 150 8C. Samples were equilibrated for at least 1 h at each tempera-
tetramethyl orthosilicate (TMOS) as silica source. Thirdly, the ture (150, 200 or 300 8C) and reactant condition prior to collecting
quantity of precursor employed was stirred with the TEOS for the spectra. Reactant excess was purged from the sample chamber.
10 min only. Fourthly, the final solid was calcined at 600 8C under The experimental procedures used for temperature programmed
N2 (4 h) and air (4 h). desorption of PY and DMPY (PY and DMPY-TPD) was also previously
The protocol was proved to be a swift and simple route to the reported [46]. The apparatus used for pyridine adsorption/deso-
preparation of Ga- and AlGa-SBA-15 materials. rption was basically a modified gas chromatograph. The catalyst
The mesoporous SBA-15 materials were denoted as (Ga)AlGa-X- tube was made of 100 mm  4 mm s.s. tube containing about 50 mg
Y where Ga or AlGa indicates the nature of the silicate, X is the Si/Ga of catalyst packed between quartz wool plugs. Pure N2 at a flow rate
molar ratio in the synthesis gel (X = 40 or 20) and Y is the source of of 50 mL min 1 was used as the carrier gas. Prior to the adsorption
gallium (A or N, see above) employed in the synthesis procedure. The experiments, the catalyst was pretreated in situ by passing pure N2
aluminogalosilicates were prepared with a Al/Ga = 1 and Si/ at a flow rate of 50 mL min 1 and heating from 50 to 450 8C at
Al + Ga = 20 molar ratio. A pure siliceous and aluminum SBA-15 10 8C min 1 (temperature maintained at 450 8C for 10 min). The
(Si-SBA-15 and Al-20) were also prepared for comparative purposes. temperature was then lowered to 100 8C and the adsorption
The elemental analysis of the mesoporous materials (Table 1) experiment was carried out. PY and DMPY-TPD experiments were
was performed in the Laboratorio de Mineralogia Aplicada (IRICA) performed in the 50–700 8C range after saturation of the sample
at the Universidad de Castilla La Mancha (UCLM) using the X-ray followed by purging in N2 at 100 8C for 1 h.
fluorescence (XRF). The alkylation of toluene with benzyl chloride was conducted
X-ray diffraction (XRD) patterns were recorded on a Philips on a 50 mL two-neck round-bottomed flask. 122 mmol toluene,
X’PERT MPD PW3040 using Cu Ka radiation (l = 1.5418 Å) over a 9 mmol benzyl chloride and 0.1 g catalyst were heated at 110 8C at
2u range from 0.58 to 68 (18 min 1). different times. Samples were withdrawn periodically, filtered off
The textural properties were determined from the N2 adsorp- and analysed using a HP5890 Series II Gas Chromatograph
tion–desorption isotherms using a volumetric adsorption analyzer (60 mL min 1 N2 carrier flow, 20 psi column top head pressure)
Micromeritics ASAP 2000. The samples were outgassed at 130 8C fitted with a capillary HP-101 column (25 m  0.2 mm  0.2 mm)
under vacuum (p < 10 2 Pa) for 24 h and subsequently analyzed. and a flame ionisation detector (FID). All calculations including
The linear part of the BET equation (relative pressure between 0.05 activities and selectivities have been based on the use of benzyl
and 0.22) was used for the determination of the specific surface chloride or alcohol as limiting reagents.
The reusability experiments were carried out as follows:
Table 1 122 mmol toluene, 9 mmol benzyl chloride and 0.1 g catalyst
Textural properties [surface area (SBET, m2 g 1), C constant (CBET), pore diameter
were added to a 100 mL two-neck round-bottomed flask and
(DBJH, Å) and pore volume (VBJH, mL g 1)] and elemental analysis (XRF) of the SBA-
15 materials
heated at 110 8C. After reaching a >70% conversion (2–6 h), the
reaction mixture was filtered off, washed with toluene and dried at
Materials SBET CBET DBJH (Å) VBJH XRF Si/M, 100 8C for 1 h prior its use in the alkylation reaction. After five uses,
(m2 g 1
) (mL g 1
) Al/Ga
the catalyst was also calcined at 600 8C in air for 1 h to test its
Si-SBA-15 1016 116 57 (6) a 1.15 – regeneration properties after calcinations.
Ga-40-A 962 92 48 (15) 1.08 53
Ga-20-A 902 84 49 (14) 1.14 25
Ga-40-N 1031 107 45 (18) 1.00 113 3. Results and discussion
Ga-20-N 910 96 48 (15) 1.01 61
AlGa-A 866 83 51 (17) 1.02 21, 0.7 The elemental composition of the Ga-, AlGa- and Al-SBA-15
AlGa-N 867 96 48 (13) 0.93 28, 0.8 materials have been included in Table 1.
Al-20 900 117 67 (8) 0.87 25
The Si/Ga molar ratio in the calcined solids is higher than the Si/
a
The values in brackets correspond to width at half-height (from the PSD) in Å. Ga ratio in the synthesis gel. These results can be attributed to the
150 M.J. Gracia et al. / Applied Catalysis A: General 349 (2008) 148–155

Fig. 2. N2 adsorption–desorption profiles of (a) Si-SBA-15; (b) Ga-20-A; (c) AlGa-A.


Fig. 1. XRD patterns of (a) Si-SBA-15; (b) AlGa-A; (c) Ga-40-A; (d) Ga-20-A.

solubility of the Ga in acid medium which reduces its incorporation ing to the (1 0 0), (1 1 0) and (2 0 0) characteristic of the hexa-
into framework, in good agreement with reported results for Al-SBA- gonal P6mm group. These peaks cannot be observed in the Ga-, Al- or
15 [47]. Coincidental results were also found for Al-20. Interestingly, AlGa-SBA-15 suggesting that the incorporation of the Ga and/or Al
the use of gallium acetylacetonate considerably improved the induced structural changes in the hexagonal mesoporous material,
incorporation of the Ga into the mesoporous network. reducing its structural order. A long scan analysis confirmed the
XRD patterns of various SBA-15 materials are depicted in Fig. 1. Si- absence of the characteristic diffraction lines of Ga2O3, indicating the
SBA-15 exhibited three well-resolved diffraction lines correspond- incorporation of the Ga into the SBA-15 structure.

Fig. 3. TEM micrographs (300,000, 50 nm scale bar) of various SBA-15 materials: (A) Ga-20-A; (B) Al-20; (C) AlGa-A; (D) AlGa-N.
M.J. Gracia et al. / Applied Catalysis A: General 349 (2008) 148–155 151

The N2 adsorption–desorption profiles of the SBA-15 materials


(Fig. 2) were of type IV, characteristics of mesoporous materials.
The steep increase in partial pressure 0.6–0.9 corresponds to the
capillary condensation within the mesopores. The pore sizes
pointed out a width at half-height of 6 and 8 Å for the Si-SBA-15
and Al-20 materials, respectively, compared to values in the 13–
18 Å range for the Ga- and AlGa-SBA-15. The peak broadening
suggests a decrease in the structural order of the gallium
containing mesoporous materials (Table 1), in good agreement
with the results obtained by XRD.
In general, all Ga- and AlGa-SBA-15 exhibited a pore size in the
48–50 Å and 0.9–1.1 mL g 1 mesopore volumes. The surface area in
the materials was found to decrease with an increase in the gallium
content. This decrease was particularly noticeable for the AlGa-SBA-
15. The pore diameters obtained for all samples were in good
agreement with the TEM results (Fig. 3), in which a pore diameter of
50–60 Å at the pore entrance can be clearly seen (Fig. 3A). The
hexagonal array of pores was well preserved after the incorporation
of both Ga-SBA-15 and Al-SBA-15 with a minor decrease in the
structural order for the AlGa-SBA-15 materials (Fig. 3C and D).
Solid-state 71Ga NMR was recorded to confirm the gallium
incorporation into the mesoporous framework. 71Ga is a quad-
rupolar nucleus (I = 3/2) and its NMR spectra are generally affected
by the second-order quadrupolar broadening. Fig. 4 shows the
NMR spectra of Ga-20-A materials. A characteristic 160 ppm broad
band due to the tetrahedral (Td) coordinated Ga could be seen for
Ga-SBA-15 materials, indicating the gallium incorporation
(Fig. 4a). This broad band was also observed for the recycled
Ga-SBA-15 materials under the reaction conditions (122 mmol
toluene, 9 mmol benzyl chloride), proving the stability of the
samples in the reaction (Fig. 4b).
The acid properties of the mesoporous SBA-15 materials were
investigated by using a gas chromatography approach to the
adsorption of pyridine (PY) and 2,6-dimethylpyridine (DMPY) as
probe molecules at 300 8C [46]. The results are summarised in
Fig. 4. 71Ga MAS NMR of Ga-20-A materials: (a) fresh Ga-20-A; (b) used Ga-20-A
Table 2. As expected, both the Brönsted and Lewis acidity increased
after the alkylation reaction under conventional reaction conditions (122 mmol
with an increase in the gallium content in the materials. The Ga- toluene, 9 mmol benzyl chloride, 0.1 g catalyst, 110 8C); (c) used Ga-20-A after the
SBA-15 prepared using acetylacetonate as gallium source (Ga-40-A alkylation reaction under equimolar toluene/benzyl chloride ratios (46 mmol
and Ga-20-A) exhibited higher acidities compared to Ga-40-N and toluene, 46 mmol benzyl chloride, 0.1 g catalyst, 110 8C).
Ga-20-N (gallium nitrate as Ga source) due to a better Ga
incorporation as shown in Table 1. The AlGa-SBA-15 (Si/ the reaction (Table 3). This reaction has been reported to be
Al + Ga = 20) exhibited a surprising less total acidity (PY values) catalysed by Lewis acid sites [26,49]. The alkylation was then
with respect to the Ga-20 solid acids. Despite their lower total carried out at 110 8C to obtain the maximum conversion in the
acidity, the incorporation of Al generated materials with improved process (Tables 4 and 5).
Bronsted acidities (DMPY data, Table 2). The initial screening of the acidic SBA-15 (50 8C) pointed out the
PY and DMPY DRIFT experiments (Fig. 5) showed DMPY solid acids had different activities depending on the Lewis acidity
adsorption was very selective to Brönsted acid sites with clearly of the materials that decreases in the order: Ga-20-A > Ga-20-
assigned bands at 1635 cm 1 due to Brönsted bonded DMPY N > Ga-40-A > Ga-40-N. A complete selectivity to mono-alkylated
compared to Lewis bonded PY bands that appear at 1620 and products (ortho- and para-) was found for all materials, with an
1458 cm 1 [48]. approximate 1/1 o-/p- ratio. The Ga-20-A was the most active
PY-TPD experiments (Fig. 6) demonstrated the acidic materials material in the reaction. Of note was also the activity of the Al- and
exhibited a similar desorption profile regardless of the element AlGa catalysts. Such materials exhibited very poor activities after
(Ga, Al or AlGa) and the Ga or Al content. The acid strength 24 h. The activity of the AlGa-A was significantly higher compared
distribution of the Ga-SBA-15 and AlGa-SBA-15 materials was
almost identical. Four different peaks were found at in the Table 2
experiment. Ga-SBA-15 materials showed a higher contribution of Surface acidity, measured as PY and DMPY titration (mmol probe molecule per g of
the lower temperature peak compared to Al-SBA-15, implying the catalyst at 300 8C) and Lewis acidity (PY-DMPY) of the mesoporous SBA-15
incorporation of Ga led to a higher concentration of weak acid sites. Materials PY (mmol g 1
) DMPY (mmol g 1
) Lewis acidity (mmol g 1
)

Ga-40-A 86 23 63
3.1. Catalytic activity
Ga-20-A 127 28 99
Ga-40-N 72 17 55
3.1.1. Alkylation of toluene with benzyl chloride Ga-20-N 102 31 71
The liquid-phase alkylation of toluene with benzyl chloride AlGa-A 116 41 75
AlGa-N 96 56 40
(Scheme 1) was initially conducted at 50 8C in order to optimise
Al-20 171 98 73
the reaction conditions and to select the most active catalyst in
152 M.J. Gracia et al. / Applied Catalysis A: General 349 (2008) 148–155

Fig. 5. DRIFTS of adsorbed DMPY (A and C) and PY (B and D) for various SBA-15 materials. The different spectra correspond to (a) base desorbed for 1 h at 150 8C, spectra
recorded at 150 8C; (b) base desorbed for 1 h at 200 8C, spectra recorded at 200 8C; (c) base desorbed 1 h 300 8C, spectra recorded at 300 8C; (d) base desorbed for 1 h at 300 8C,
spectra recorded at 150 8C.

to that of the AlGa-N, that can be correlated to its higher acidity The activities of the AlGa-A (Si/Al = 50 and Si/Ga = 37) and AlGa-
(higher Al and Ga content, Table 2). However, long times of N (Si/Al = 61 and Si/Ga = 50) were also inferior to the expected
reaction (typically 24+ h) were needed to achieve reasonable activities in view of the acid properties of the materials (Tables 3–
conversion values. Therefore, the alkylation of toluene with benzyl 5). The unusual activity of the AlGa-SBA-15 materials in both
chloride was performed at a higher temperature (110 8C). The reactions may be due to the partial extraction of Td Ga from the
results have been included in Table 4. framework after the Al incorporation. Solid-state 27Al and 71Ga
The activities of the mesoporous solid acids were remarkably NMR of the AlGa-SBA-15 materials (not shown) showed a higher
improved in the alkylation of toluene with benzyl chloride at proportion of extra framework octahedral Al and Ga in the samples
110 8C. Quantitative conversions were found in the systems after compared to Al- and Ga-SBA-15 materials, that is correlated with a
15 min of reaction except for the Al- and AlGa-SBA-15 materials. decrease in activity.
The solid acids afforded complete selectivities to the monoalky-
lated products (2- and 4-methyl diphenylmethane) with a 1/1 o-/p- 3.1.2. Alkylation of toluene with benzyl alcohol
ratio. Interestingly, the activity of the Al-20 material was very poor The alkylation of toluene was then carried out with the less
despite its higher total and Brönsted acidity. Quantitative activated benzyl alcohol (Scheme 1) under the optimised condi-
conversion was achieved only after 24 h of reaction. These results tions (110 8C). This reaction has been reported to be catalysed by
were in good agreement with the work of Yiu and Brown [50] who Brönsted acid sites in comparison to that using benzyl chloride
demonstrated the superior activity of Fe-MCM-41 and Fe-K10 (Lewis acid catalysed) [26,49]. Data is summarised in Table 5. In
materials compared to Al-MCM-41 and Al-K10. general, all materials exhibited a poor activity in the reaction after
M.J. Gracia et al. / Applied Catalysis A: General 349 (2008) 148–155 153

Table 3
Activities [total conversion (XT, mol%)] and selectivities to 2-methyl diphenyl-
methane (S2, %) and 4-methyl diphenylmethane (S4, %) of the mesoporous SBA-15
materials in the liquid-phase alkylation of toluene with benzyl chloridea

Catalyst Time (h) XT (mol%) S2 (%) S4 (%)

Ga-40-A 3 <5 50 50
24 45 49 51

Ga-20-A 3 <10 48 52
24 94 48 52

Ga-40-N 3 <5 47 53
24 <10 48 52

Ga-20-N 3 <5 48 52
24 67 48 52

AlGa-A 24 28 48 52

AlGa-N 24 <10 52 48

Al-20 24 <5 41 59
a
Reaction conditions: 122 mmol toluene, 9 mmol benzyl chloride, 0.1 g catalyst,
50 8C.

Table 4
Activities [total conversion (XT, mol%)] and selectivities to 2-methyl diphenyl-
methane (S2, %) and 4-methyl diphenylmethane (S4, %) of the mesoporous SBA-15
materials in the liquid-phase alkylation of toluene with benzyl chloridea

Fig. 6. PY-DTP profiles of the mesoporous SBA-15 materials: (a) Ga-20-A; (b) AlGa-A Catalyst Time (min) XT (mol%) S2 (%) S4 (%)
and (c) Al-20.
Ga-40-A 15 >99 52 48

Ga-20-A 15 >99 51 49
24 h with the exception of the Al-20. Quantitative conversion was
found for Al-20 with a 1/1 o-/p- selectivity after 24 h, in good Ga-40-N 15 >99 52 48

agreement with reported results for Al-MCM-41 and Al-K10 Ga-20-N 15 >99 51 49
materials [50]. Dibenzylether was observed as by-product in the AlGa-A 15 77 52 48
reaction. However, this compound is also a good alkylating agent 60 >99 52 48
and its concentration is variable as it is consumed together with
AlGa-N 15 41 51 49
the benzyl alcohol in the alkylation reaction. A maximum of 180 >99 52 48
30 mol% of dibenzylether was obtained. For this reason, it has been
Al-20 30 10 49 51
included to the benzyl alcohol in order to work out the activity of
1440 98 49 51
the acidic SBA-15 materials.
a
The different activities of the Ga- and Al-SBA-15 materials in the Reaction conditions: 122 mmol toluene, 9 mmol benzyl chloride, 0.1 g catalyst,
110 8C.
alkylation of toluene with benzyl chloride and alcohol, respec-
tively, can be correlated to their predominant Lewis and Brönsted
acidity that is critical for the activity in each alkylation reaction. conversion after 5 min in a similar way to that of the fresh
material. El Berrichi et al. [20] reported that Ga2O3 was turned into
3.1.3. Catalyst reusability studies GaCl3 that was solubilised in the reaction mixture under similar
The reusability of the mesoporous materials was investigated. reaction conditions. The Ga leaching will obviously decrease the
Results for Ga-20-A have been included in Table 6. The catalyst activity in the materials after successive reuses. A hot filtration
was highly reusable preserving most of its initial catalytic activity test was then carried out in order to ascertain the truly
(>70%) after five cycles. DRIFTs of the deactivated catalysts (Fig. 7) heterogeneous nature of the catalysts with regards of Ga leaching.
showed the presence of organic compounds strongly adsorbed on The catalyst, employed in the alkylation of toluene with benzyl
the catalyst surface (bands at wavelengths higher and lower than chloride at 110 8C, was filtered off after reaction completion (Ga-
3000 cm 1) that could only be removed at 550 8C (they are present 40-A and AlGa-N) and the reaction mixture without the catalyst
after heating at 300 8C for 1 h), suggesting that some active sites was diluted after mixing with fresh reagents (in a proportion
were partially deactivated after the reaction. However, the 122 mmol toluene and 9 mmol benzyl chloride) to a set
reactivation of Ga-20-A (600 8C, air, 1 h) afforded quantitative conversion value (typically 35–60 mol%). The determined con-

Scheme 1. Acid catalysed alkylation of toluene using benzyl chloride or benzyl alcohol.
154 M.J. Gracia et al. / Applied Catalysis A: General 349 (2008) 148–155

Table 5 Table 7
Activities [total conversion (XT, mol%)] and selectivities to 2-methyl diphenyl- Hot filtration testa
methane (S2, %) and 4-methyl diphenylmethane (S4, %) of the mesoporous SBA-15
materials in the liquid-phase alkylation of toluene with benzyl alcohola Entry Time (h) XT (mol%) S2 (%) S4 (%)
b
Catalyst Time (h) S2 (%) S4 (%) XT (mol%) Filtrate Initial time 38 48 52
1 37 48 52
Ga-40-A 3 50 50 <5 24 39 48 52
24 55 45 <10
Filtratec Initial time 56 52 48
Ga-20-A 3 54 46 <5 1 56 52 48
24 49 51 13 24 57 52 48

Ga-40-N 3 51 49 <5 Activities [total conversion (XT, mol%)] and selectivities to 2-methyl diphenyl-
24 52 48 <5 methane (S2, %) and 4-methyl diphenylmethane (S4, %) of the diluted reaction
filtrate from the alkylation of toluene with benzyl chloride using Ga-40-A and AlGa-
Ga-20-N 3 50 50 <5
N as catalysts.
24 49 51 10 a
Alkylation reaction conditions: 122 mmol toluene, 9 mmol benzyl chloride,
AlGa-A 3 49 51 5 0.1 g catalyst, 110 8C. Then, the catalyst was filtered off, the reaction mixture was
24 56 45 55 diluted to a set conversion after adding the fresh reagents (initial time conversion
value) and subsequently reacted at 110 8C for 24 h.
AlGa-N 3 50 50 <5 b
Filtrate from the reaction mixture after the alkylation reaction (0.25 h) with Ga-
24 54 46 28 40-A mixed with fresh reagents (122 mmol toluene, 9 mmol benzyl chloride).
c
Filtrate from the reaction mixture after the alkylation reaction (3 h) with AlGa-
Al-20 3 50 50 <10
N mixed with fresh reagents (122 mmol toluene, 9 mmol benzyl chloride).
24 52 48 >95
a
Reaction conditions: 94 mmol toluene, 10 mmol benzyl alcohol, 0.1 g catalyst,
110 8C. Table 8
Hot filtration test (II)a
Table 6 Time of reaction (h) XT (mol %) S2 (%) S4 (%)
Reusability experiments of Ga-20-A in the alkylation of toluene with benzyl
chloridea Initial time 47 49 51
3 88 49 51
Number of uses Time (min) XT (mol%) S2 (%) S4 (%) 24 >99 49 51
1 5 89 51 49 Activities [total conversion (XT, mol%)] and selectivities to 2-methyl diphenyl-
2 60 86 51 49 methane (S2, %) and 4-methyl diphenylmethane (S4, %) of the diluted reaction
3 60 80 52 48 filtrate from the alkylation of toluene with benzyl chloride using Ga-40-A as
4 120 75 52 48 catalyst.
5 300 87 51 49 a
Reaction conditions: 46 mmol toluene, 46 mmol benzyl chloride, 110 8C. Then,
Regenerated Ga-20-A (600 8C, 1 h in air) the catalyst was filtered off, the reaction mixture was diluted to a set conversion
1 5 >99 51 49 (initial time 47% conversion) after adding fresh reagents (46 mmol toluene,
2 60 >95 52 48 46 mmol benzyl chloride) and further reacted at 110 8C for 24 h.
3 60 91 52 48
a
Reaction conditions: 122 mmol toluene, 9 mmol benzyl chloride, 0.1 g catalyst,
No changes in conversion were observed, excluding the
110 8C.
presence of any Ga leached species in solution. These results were
version of the reaction mixture was defined as initial time corroborated by solid-state 71Ga NMR of the recycled catalysts and
conversion (initial time – 0 h – data, Table 7) and then the final ICP and AAS analysis of the reaction mixture after the reaction.
71
diluted mixture was further reacted for a period of 24 h. Results Ga NMR results proved that under the reaction conditions
are summarised in Table 7. employed (122:9 reagent ratio, 110 8C, 24 h reaction), the
characteristic peak at 160 ppm due to tetrahedral Ga was present
in the recycled catalysts. ICP of the reaction mixture showed less
than 10 ppm Ga in solution, in good agreement with the Ga NMR
data. Interestingly, the HCl generated with a 1:1 toluene:benzyl
chloride ratio (46:46 mmol) causes the extraction of the frame-
work Td Ga (Fig. 4c, disappearance of the 160 ppm signal) giving
rise to a 1 ppm signal due to hexacoordinated extra framework Ga
[51]. These data are in good agreement with the high activities of
the filtrate after the reaction and ICP results that show the presence
of high quantities of Ga in solution (Table 8).
All these facts suggest the catalytic activity of the reusable
materials under the selected reaction conditions can be ascribed to
the incorporation of the Ga into the mesoporous network and not
to the presence of leached Ga species (Ga2O3, GaCl3) in solution.

4. Conclusions

The preparation of Ga- and AlGa-SBA-15 materials was


successfully accomplished. The incorporation of Ga and/or Al
rendered mesoporous materials that retained the hexagonal array
Fig. 7. DRIFT spectra of Ga-20-A materials: (a) fresh Ga-20-A; (b–e) reused Ga-20-A
after the alkylation reaction; (b) reused material treated at 100 8C for 1 h; (c) reused
of pores with a slightly inferior structural order. In general, the
catalyst treated at 200 8C for 1 h; (d) reused material treated at 300 8C for 1 h; (e) SBA-15 solid acids exhibited both Brönsted and Lewis acid sites,
reused material treated at 550 8C for 1 h. increasing the total and Lewis acidity with an increase in the
M.J. Gracia et al. / Applied Catalysis A: General 349 (2008) 148–155 155

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