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C. The
products obtained were O-tert-butyl phenol (OTBP), 2-tert-butyl phenol (2TBP) and 4-tert butyl phenol (4TBP). O-Butenyl phenol (OBP) and
2-butenyl phenol (2BP) were also observed along with normal alkylated products. The phenol conversion drastically increased with temperature
over all the catalysts. The activity of the catalysts followed the order of Co,Al-MCM-41 (20) > Co,Al-MCM-41 (50) > Co,Al-MCM-41
(80) > Al-MCM-41 (23). The inuences of various parameters such as temperature, reactant feed ratio and feed rate, time on stream on
conversion and products selectivity were studied and the salient results are discussed.
2004 Elsevier B.V. All rights reserved.
Keywords: Mesoporous materials; Co,Al-MCM-41; t-Butylation; Phenol; Isobutanol
1. Introduction
The M41S family of mesoporous materials has attracted
substantial research attention since its report by Mobil Cor-
poration in 1991 [1,2]. The past decade has witnessed a
dramatic increase in the design, synthesis, characterization
and property evaluation of mesoporous molecular sieves for
catalysis, adsorption and separation of bulky molecules and
environmental pollution control. MCM-41, the most impor-
tant member of the M41S family, possesses a regular hexag-
onal array of uniform pores with diameters in the range
210 nm. These hexagonal MCM-41 molecular sieves have
attracted much research attention owing to their high surface
area, thermal and hydrothermal stability and ordered meso-
C for
24 h. After cooling to room temperature, the resultant solid
was recovered by ltration, washed with distilled water and
dried in an oven at 100
C for 10 h.
2.2. Characterization
The powder X-ray diffraction patterns of the Co,Al-
MCM-41 materials were collected on a Siemens D5005
diffractometer using Cu K ( = 0.154 nm) radiation. The
diffractograms were recorded in the 2 range from 0.8 to
10
C on a Quantachrome Autosorb 1
sorption analyzer. All the samples were outgassed for 3 h at
250
C for 6 h
under vacuum (10
5
mbar). The sample was then cooled
to room temperature and the spectra were recorded. Then
pyridine was adsorbed at room temperature. The physically
adsorbed pyridine was removed by heating the sample at
150
C, respectively, are
attributed to the decomposition of loosely bound organic
template within the framework. The fourth weight loss is
centered around 390
C, it increases as the n
Si
/(n
Co
+ n
Al
)
ratio decreases and develops at the expense of the second
and third weight loss centered at 210 and 265
C, respec-
tively. This could be attributed to the strongly bonded tem-
plate cation with the metallosilicate framework. As more
aluminum and cobalt atoms are incorporated into the frame-
work, more of occluded template molecule is protonated so
as to balance the resulting negative charge. This indicates
that most of the aluminum and cobalt atoms are incorporated
inside the framework of the materials.
The n
Si
/n
Al
and n
Si
/n
Co
molar ratios of all the samples
under investigation are summarized in Table 1. It can be seen
from the table that incorporation of Si, Co and Al into the
solid is in close agreement with the input gel composition.
In the case of Co,Al-MCM-41 (80), the Co and Al content in
the solid phase is higher than that of the input gel, suggesting
preferential incorporation of both metal atoms compared to
silicon. Similar observations were previously reported in the
case of zeolites [21].
The nitrogen adsorption isotherms of purely siliceous
MCM-41 and Co,Al-MCM-41 samples are shown in Fig. 3.
All the samples exhibit isotherms of type 1V of IUPAC
classication, featuring a narrow step due to the capil-
lary condensation of N
2
in the primary mesopores. The
samples containing Co and Al possess an often observed
type-H4 hysteresis loop at p/p
o
between 0.5 and 1. The
assignment of hysteresis is made according to de Boers
classication. Such a hysteresis loop has already been ob-
served in aluminum containing MCM-41 materials and is
attributed to the capillary condensation of nitrogen within
interparticles and/or some impurity phases generated dur-
ing synthesis [22]. The incorporation of Co and Al into
the walls of MCM-41 has a signicant effect on the spe-
cic surface area and specic pore volume of the materials
Fig. 3. Nitrogen adsorption isotherm (adsorption: closed symbols; des-
orption: open symbols) of Co,Al-MCM-41 with different n
Si
/(n
Co
+n
Al
)
ratios: () Co,Al-MCM-41 (80); () Co,Al-MCM-41 (50); ()
Co,Al-MCM-41 (20).
(Table 1). With increasing metal content, the pore volume
is reduced from 0.85 to 0.66 cm
3
/g and the specic surface
area declines from 1270 to 1015 m
2
/g. This is attributed to
a slight reduction in the structural integrity of the samples
with increasing metal content. A similar behavior has also
been observed in monometal-substituted MCM-41 materi-
als [23,24]. Moreover, it is interesting to note that the pore
diameter of Co,Al-MCM-41 samples is larger than the pure
silica MCM-41. As the unit cell parameter is almost identi-
cal for both Si-MCM-41 and Co,Al-MCM-41 samples, the
increase in the pore diameter of Co,Al-MCM-41 samples
indicates the reduction in wall thickness. However, the pore
diameter of Co,Al-MCM-41 (20) is smaller than those of
Co,Al-MCM-41 (50) and (80). This could be due to the
formation of more metal oxide clusters in the mesopores of
Co,Al-MCM-41 (20) than in (50) and (80).
The coordination geometry of cobalt incorporated in
Al-MCM-41 is indicated by the UV-Vis absorption spec-
tra. Fig. 4 shows the absorption spectra of calcined
Co,Al-MCM-41 samples. It exhibits a strong absorption
around the 15 50020 000 cm
1
region. This absorption
consists of three components, with maxima at 19 685,
17 241 and 15 384 cm
1
. These bands can be assigned to
4
A
2
(F)
4
T
1
(P) transition of the tetrahedrally coordi-
nated divalent cobalt species [25]. A broad band between
20 800 and 22 000 cm
1
centered at 21 505 cm
1
is also
observed for all the samples. The intensity of this band
increases monotonically with increasing Co content. This
band could be assigned to the strong bonding of oxygen
ligands to Co
2+
ions. A similar band has also been reported
in the zeolites with low Si/Al ratio [26]. However, the de-
tailed geometry of the Co
2+
ion is not clearly known [27].
Moreover, a broad band in the UV region between 34 400
and 45 500 cm
1
centered at 40 816 cm
1
is also observed
for all samples. This has been assigned to a low-energy
charge transfer between the oxygen ligands and central
Co
2+
ion in tetrahedral symmetry [28] or to self-absorption
of the molecular sieves [26,27]. All these results reveal that
Fig. 4. UV-Vis spectra of calcined Co,Al-MCM-41 with various
n
Si
/(n
Co
+n
Al
) ratios: (a) Co,Al-MCM-41 (20); (b) Co,Al-MCM-41 (50);
(c) Co,Al-MCM-41 (80).
M. Karthik et al. / Applied Catalysis A: General 268 (2004) 139149 143
Fig. 5. ESR spectra of calcined Co,Al-MCM-41 with various
n
Si
/(n
Co
+n
Al
) ratios: (a) Co,Al-MCM-41 (20); (b) Co,Al-MCM-41 (50);
(c) Co,Al-MCM-41 (80).
the majority of the cobalt ions in the Co,Al-MCM-41 sam-
ples occupy framework positions in the surface layer of the
Co,Al-MCM-41 channel walls.
ESR spectroscopy is a sensitive technique to study
the coordination of high spin Co
2+
ions in molecular
sieves. The X-band ESR spectrum at 267
C of calcined
Co,Al-MCM-41samples synthesized with different n
Si
/n
Co
ratios in the synthesis gel is shown in Fig. 5. The spectrum
shows two major components, at g = 5.4 and 2.05. With
increasing n
Si
/n
Co
ratio from 160 to 40, the correspond-
ing spectra show ESR signal increases in intensity. The
ESR signal at g = 5.4 and 2.05 are attributed to Co
2+
in
an elongated tetrahedral environment [29]. Similar spectra
were also reported in cobalt-substituted aluminophosphate
molecular sieves [30,31]. It is important to note that the in-
tensity of ESR signal in the calcined material is higher than
in the as-synthesized material. The increase in the intensity
of ESR signal in the calcined materials indicates that there
is no oxidation of Co
2+
to Co
3+
during calcination [31].
Fig. 6. DRIFT spectra of pyridine adsorption region of mesoporous materials: (a) Co,Al-MCM-41 (20); (b) Al-MCM-41 (23); (c) Co,Al-MCM-41 (50);
(d) Co,Al-MCM-41 (80); (L: Lewis acid; B: Bronsted acid; L +B: Lewis and Bronsted acid sites).
Table 2
Bronsted and Lewis acidity values for Al-MCM-41 and Co,Al-MCM-41
Catalyst Bronsted (B) acid
site (mmol/g)
Lewis (L) acid
site (mmol/g)
B/L acid
site ratio
Al-MCM-41 (23) 0.114 0.121 0.942
Co,Al-MCM-41 (20) 0.190 0.284 0.669
Co,Al-MCM-41 (50) 0.117 0.107 1.093
Co,Al-MCM-41 (80) 0.057 0.026 2.192
The in situ DRIFT spectra of pyridine adsorbed on meso-
porous Al-MCM-41 and Co,Al-MCM-41 molecular sieves
are shown in Fig. 6. The acidity of the catalysts was cal-
culated using extinction coefcients of the bands of Bron-
sted and Lewis acid sites adsorbed pyridine [18] and the
acidity values are given in Table 2. The DRIFT spectra of
chemisorbed pyridine have shown that Co,Al-MCM-41 and
Al-MCM-41 contain both Bronsted and Lewis acid sites.
The existence of Bronsted acid sites in the samples is clearly
shown by the bands at 1545 and 1636 cm
1
due to ring vibra-
tions of pyridine bound to Bronsted acid sites [32,33]. The
bands at 1451, 1493 and 1617 cm
1
are assigned to pyridine
associated with Lewis acid sites [34]. The band at 1493 cm
1
is attributed to pyridine chemisorbed on both Bronsted and
Lewis acid sites [32,35]. The band at 1400 cm
1
is attributed
to pyridine hydrogen bonded to defective SiOH groups
[17,36]. The peak at 1230 cm
1
is assigned to the asymmet-
ric TOT vibration of the framework [37,38]. Comparison
of spectra reveals that Co,Al-MCM-41 (20) has a greater
amount of acid sites (Bronsted and Lewis) than Al-MCM-41
(23) as the corresponding bands in the former are more in-
tense than those in the latter. The acid sites are found to be
same in both Co,Al-MCM-41 (50) and Al-MCM-41 (23),
whereas Co,Al-MCM-41 (80) has a smaller amount of acid
sites than either Co,Al-MCM-41 (50) or Co,Al-MCM-41
(20). The intensity of the bands due to Lewis acid sites in
Co,Al-MCM-41 (20) is more than in either Co,Al-MCM-41
144 M. Karthik et al. / Applied Catalysis A: General 268 (2004) 139149
(50) or Co,Al-MCM-41 (80). This is ascribed to the forma-
tion of more cobalt oxide in Co,Al-MCM-41 (20) upon cal-
cination. It is obvious that, with increasing cobalt content
in Al-MCM-41, the number of surface acid sites increases.
This study reveals that the acidity of the catalysts decreases
in the order Co,Al-MCM-41 (20) > Al-MCM-41 (23)
Co,Al-MCM-41 (50) > Co,Al-MCM-41 (80). Hence, it is
concluded that the isomorphic substitution of Co
2+
into the
framework of mesoporous Al-MCM-41 creates more acid
sites (Bronsted and Lewis) and enhances the catalytic activ-
ity of Co,Al-MCM-41.
3.2. Catalytic activity
Alkylation of phenol with isobutanol was studied over
Co,Al-MCM-41 (20, 50 and 80) and Al-MCM-41 (23) at
200, 250, 300, 350, 400, 450 and 500
C by co-feeding
phenol and isobutanol in the feed ratio of 1:3 and feed
rate of 3 ml/h. The plot of conversion versus temperature
is shown in Fig. 7. There is a nearly linear increase of
phenol conversion with temperature over all the catalysts.
It can be seen from the gure that the butylation activity
in Co,Al-MCM-41 (20) is more than in other catalysts.
Al-MCM-41 (23) possesses less density of acid sites than
Co,Al-MCM-41 (20), as isomorphic substitution of Al
3+
by Co
2+
would provide two Bronsted acid sites, and hence
the former shows less activity than the latter. As the reac-
tion requires formation of isobutyl cation in order to have
electrophilic attack on either the chemisorbed phenol or the
free phenol, the density of Bronsted acid sites, which are
the active sites in this reaction, is important. As the density
of acid sites in Co,Al-MCM-41 decreases in the following
order: Co,Al-MCM-41 (20) > Co,Al-MCM-41 (50) >
Co,Al-MCM-41 (80), the conversion also follows the same
trend as that shown in Fig. 7. The density of acid sites are
Fig. 7. Effect of temperature on conversion of phenol. Phenol:
isobutanol1:3; feed rate3 ml/h; catalyst weight0.5 g. Conversion
of phenol() Co,Al-MCM-41 (20); () Co,Al-MCM-41 (50); ()
Co,Al-MCM-41 (80); () Al-MCM-41 (23).
in good agreement with DRIFT (pyridine adsorption) mea-
surements. The activity of Co,Al-MCM-41 (80) is expected
to be less than Al-MCM-41 (23), but the results indicate the
reverse trend. Hence, in addition to acidity, the associated
hydrophilic and hydrophobic properties of the catalysts are
also important factors to account for the difference in the
activity of the catalysts. Though Al-MCM-41 (23) pos-
sesses more density of acid sites, it is less hydrophobic than
Co,Al-MCM-41 (80). Hence, the adsorption of hydropho-
bic isobutanol on the active sites is to be less and for this
reason the former gives less conversion than the latter. This
trend is similar to the previously reported hydrophilic and
hydrophobic properties of molecular sieves in acetalyzation
[35] and isopropylation of m-cresol [37]. In a similar way,
Co,Al-MCM-41 (20) can be expected to give less conversion
than even Al-MCM-41 (23), but it gives more conversion.
There might be yet another route to yield isobutyl carbo-
nium ion in addition to the above Bronsted acid-assisted
route. The formation of non-framework cobalt oxide in the
channels of MCM-41 may provide an alternate route to yield
tert-butyl cations as shown in reaction (Scheme 1). Such
dissociative adsorption of phenol on the Lewis acid sites,
so that the released proton can rest on the adjacent basic
site, has already been proposed by many workers [39,40].
Isobutyl alcohol should be chemisorbed on the Bronsted
site in order to yield isobutyl cation. This cation without or
with rearrangement is to react with the adjacent phenoxide
to yield O-or C-alkylated product, as shown in the reac-
tion (Scheme 1(a)(c)). Based on the conversion, the order
of activity of Co,Al-MCM-41 catalysts is Co,Al-MCM-41
(20) > Co,Al-MCM-41 (50) > Co,Al-MCM-41 (80),
which is also the order of the amount of non-framework
cobalt oxide in the pores of MCM-41. These particles are
also expected to be of nanodimensions close to 1 nm, so that
the reactants and products can very well diffuse in and out of
the pores of the catalysts without any diffusional constraints.
In general, alkylation of phenol is a reaction sensitive to
the acidbase properties of the catalysts employed. It has
been observed that O-alkylation of phenol is favored by
strong acid sites [41], while C-alkylation is favored by weak
acidic (or) strong basic sites [42]. Tleimaat-Manzaliji et al.
[43] and Marczewski et al. [44] have claimed that weak
acids sites favor C-alkylation, while Velu and Swamy [45]
reported that C-alkylation occurred due to the presence of
higher acidity. The formation of O-alkylated products de-
pends on the intrinsic properties of the alcohol and acidbase
properties of the catalysts [46]. Based on the above obser-
vations, we have also tried to explain the formation of prod-
ucts as a function of acidity and activity of the catalysts for
the t-butylation of phenol.
Table 3 shows the selectivity of the products obtained over
the catalysts in the temperature range 350500
C. The prod-
ucts were identied by GC and GC-MS. The main products
of the catalytic butylation of phenol were O-tert butyl phe-
nol (OTBP), 2-tert-butyl phenol (2TBP), 4-tert-butyl phe-
nol (4TBP), O-butenyl phenol (OBP) and 2-butenyl phenol
M. Karthik et al. / Applied Catalysis A: General 268 (2004) 139149 145
Scheme 1.
Table 3
Effect of temperature on t-butylation of phenol over Al-MCM-41 and Co,Al-MCM-41
Catalyst
a
Temperature (
C.
a
Catalyst weight: 0.5 g.
Fig. 8. Effect of feed ratio and feed rate on conversion of phenol over
Co,Al-MCM-41 (20). Catalyst weight0.5 g; temperature400
C. Con-
version of phenol in the feed ratio (phenol:isobutanol)() 1:2; ()
1:3; () 1:4.
The effects of feed ratio and feed rate on conversion were
studied at 400
C.
a
Catalyst weight: 0.5 g.
Co,Al-MCM-41. The reaction was carried out at different
feed rates at 400