Applied Catalysis A: General 321 (2007) 109–116

www.elsevier.com/locate/apcata

Synthesis of nano-sized porous g-alumina powder

via a precipitation/digestion route
H.S. Potdar, Ki-Won Jun *, Jong Wook Bae, Seung-Moon Kim, Yun-Jo Lee
Micro-Chemical Technology Research Team, Korea Research Institute of Chemical Technology, P.O. Box 107,
Yu-seong, Daejeon 305-600, Republic of Korea
Received 28 September 2006; received in revised form 21 December 2006; accepted 9 January 2007
Available online 9 February 2007

Abstract
As a part of a study for the preparation of nano-sized g-Al2O3 powder with controlled porosity and pore size distribution, a precipitation/
digestion route was exploited to generate a boehmite precursor having a narrow size distribution of spherical nano-sized particles: size 3.5 nm with
surface area 261 m2/g, average pore diameter of 4.86 nm, and pore volume 0.377 cm3/g. In this route, aqueous solution of aluminum nitrate and
sodium carbonate were added simultaneously drop by drop to a well-stirred 200 ml volume of deionized water (taken in a round-bottom flask) at
70 8C to precipitate boehmite precursor in the pH range of 7.5–8.5 after digestion at the same temperature for 3 h. The boehmite precursor thus
obtained is further washed with deionized water first to avoid ‘Na’ contamination and then by ethanol/acetone. The digested precipitate was finally
air dried at room temperature. The calcinations of as-dried boehmite precursor at 550 8C/5 h in air produced porous nano-sized g-Al2O3 powder
particles having spherical shape with size of 4.5 nm. These powder particles showed BET surface surface area 220 m2/g with average pore
diameter of 7.0 nm and pore volume 0.487 cm3/g. However, room temperature precipitation/digestion produces non-crystalline boehmite that
gave poorly crystallized g-Al2O3 powder particles with lower surface area 133.90 m2/g; these had higher average pore diameter of 26.67 nm with
pore volume of 1.02 cm3/g. In methanol conversion to DME reaction, g-Al2O3 catalyst made from precipitation/digestion at 70 8C gave a similar
yield of DME when compared with the yield for g-Al2O3 prepared from commercial Catapal-B boehmite sample.
# 2007 Elsevier B.V. All rights reserved.

Keywords: Precipitation; Digestion; Boehmite; Nanocrystals; g-Al2O3

1. Introduction hydrolysis of aluminum alkoxides and (b) precipitation from

Boehmite (aluminum oxyhydroxide, AlOOH) is the main
precursor exploited to produce porous g-Al2O3 powder with
controlled and reproducible properties i.e. controlled particle
size, morphology, pore size and pore distribution [1,2]. There-
fore, controlling particle size, morphology and porosity is of
prime importance to improve the potentialities of g-Al2O3
powder in catalysis, composite reinforcement applications,
coatings and alumina derived ceramics [3,4]. Many wet chemical
protocols/procedures based on liquid phase reaction [5,6], gas
phase synthesis [7] or hydrothermal reaction at high pressures
[3,8] have been tried to control the particle size and the
morphology of boehmite precursors as well as that of resulting g-
Al2O3 powders. Several liquid phase reactions namely (a)
* Corresponding author. Tel.: +82 42 860 7671; fax: +82 42 860 7388.
E-mail address: kwjun@krict.re.kr (K.-W. Jun).
0926-860X/$ – see front matter # 2007 Elsevier B.V. All rights reserved.
doi:10.1016/j.apcata.2007.01.055
aqueous/semi-aqueous inorganic salt solutions have been
utilized to synthesize boehmite precursor with controlled
chemistry, morphology and textural properties, as reported in
the literature [8]. Yoldas investigated hydrolysis of aluminum
secondary butoxide or aluminum isopropoxide [9] and found that
the boehmite precursor (AlOOH) is produced by hydrolysis with
hot water, whereas bayerite Al(OH)3 is precipitated at room
temperature through conversion of the initially formed
amorphous phase. However, sol–gel methods face problems
especially during drying i.e. cracking of gels. Moreover, it is
tedious and expensive because of the high cost of the starting
chemicals and the moisture sensitive-nature of alkoxides [8].
Therefore, simple liquid phase reaction routes for synthesis of
boehmite precursor using inorganic salts are still pursued,
seeking for g-Al2O3 powders with controlled chemistry and
textural characteristics [10,11]. In the case of precipitation route
[12], precipitation of boehmite is performed either with
aluminates or by the more usual ways of direct addition of a
110 H.S. Potdar et al. / Applied Catalysis A: General 321 (2007) 109–116
base like NaOH or NH4OH or thermal decomposition of urea in
aqueous medium. Many preparation parameters, like pH, nature
of salts and bases and their addition sequence, have to be
judiciously controlled to obtain boehmite/g-Al2O3 powders with
enhanced and reproducible properties, such case explains the
persistence of intense research in the area of chemical processing
of inorganic materials in general and of boehmite/g-Al2O3 in
particular [10,12,13]. It is reported [14] that, at pH  8,
gelatinous alumina monohydrate AlO(OH) or boehmite is
formed, which decomposes to g-Al2O3 after calcinations at 400–
500 8C in air whereas pH above 9.0 favors formation of beta
alumina trihydrate {Al(OH)3} or bayerite. Chuah et al. [14]
studied the effects of digestion on textural properties of the
boehmite precursor and g-Al2O3 powders obtained by its
calcination in air at various temperatures. They conducted
precipitation reactions at room temperature using 0.75 M
solution of ammonia as precipitant and 0.5 M solution of
aluminum nitrate; fractions of these precipitates were digested
further at 100 8C for different time durations. During precipita-
tion, it is necessary to keep pH  6.0 by controlled addition of
ammonium hydroxide and or nitric acid solution. To solve such
problems, sodium carbonate was used as precipitant and co-
precipitation/digestion simultaneously was carried out at 70 8C
for 3 h. The in situ generated OH ions produced by hydrolysis of
sodium carbonate in aqueous medium were used for the
precipitation process. A temperature of 70 8C and a pH of 7.5–8.5
was maintained to enhance kinetics of precipitation/digestion
reaction. Therefore, the main objective of the present work is to
use a simple precipitation/digestion method to produce boehmite
precursor with controlled chemistry and geometry using cheaper
starting chemicals like aluminum nitrate and sodium carbonate at
pH  7.5–8.5 and to generate g-Al2O3 powders possessing high
surface area with controlled porosity, pore size distribution and
crystallinity by its calcinations in air. Another aspect of present
work is to characterize both boehmite precursor and g-Al2O3
powders employing various physico-chemical characterization
techniques. Thus we can further test the performance of g-Al2O3
in dehydration reactions of methanol to DME and compare the
results with those for a standard g-Al2O3 catalyst derived from
commercial Catapal-B boehmite sample. All these results related
to synthesis, characterization and methanol to DME conversion
reaction are presented in this paper.
2. Experimental
2.1. Syntheses
Aluminum nitrate {Al(NO3)39H2O, 99.5%} (Aldrich),
sodium carbonate {Na2CO3, 98%} (Junsei) and deionized water
were used as starting chemicals. Initially, aluminum nitrate
(0.041 M) solution is made by dissolving 15.614 g in 400 ml of
deionized water. Similarly (0.075 M) solution of sodium
carbonate is prepared by dissolving 7.95 g in 400 ml of
deionized water. Two hundred milliliters of deionized water is
taken in a 2 l capacity round-bottom flask and stirred well using
magnetic stirrer. Then sodium carbonate and aluminum nitrate
solutions are added to 200 ml of deionized water (from separate
burettes) drop by drop to precipitate Al cations in the form of
hydroxides. The temperature was maintained 70 8C during
precipitation/digestion experiment. The pH after precipitation
was found to be in the range of 7.5–8.5. The precipitates were
further digested at 70 8C for 3 h. The digested precipitates were
filtered and re-dispersed again in hot 2 l of deionized water,
filtered and finally washed with ethanol first followed by acetone
to avoid contamination of ‘Na’ ions; and air dried at room
temperature. The as-dried precipitates were calcined in a
programmable furnace at 550 8C/5 h in air with heating rate
of 2 8C/min to produce nano-sized g-Al2O3 powders. To
compare the effect of temperature on physical/chemical
characteristics of as-prepared boehmite/g-Al2O3 powders and
their effect in methanol to DME conversion, we carried out
precipitation/digestion experiments at RT keeping similar
precipitation/digestion conditions.
2.2. Characterization
Thermo-gravimetric analysis of the samples was conducted
in TGA/DTA (TA Instrument: DMA, SDT 2960) in flowing
nitrogen atmosphere at a heating rate of 10 8C/min up to
1200 8C using an alumina as the reference material. This
showed the various decomposition reactions occurring in as-
dried precursor as a function of temperature and we could
decide the calcination temperature of the as-dried precursor.
To identify phases and their crystallinity in as-dried and
calcined materials, we carried out powder X-ray diffraction
(XRD) studies was carried out with a Rigaku diffractometer
using Cu Ka radiation. The BET surface areas and pore volumes
were estimated from nitrogen adsorption and desorption
isotherm data obtained at 196 8C on a constant-volume
adsorption apparatus (Micromeritics, ASAP-2400). The pore
volumes were determined at a relative pressure (P/Po) of 0.99.
The as-prepared samples were degassed at 150 8C for 3 h before
measurements. The pore size distributions in as-prepared
samples were verified by a BJH (Barett–Joyner–Halenda) model
from the adsorption branch of the nitrogen isotherms [15]. The
microstructures of both as-prepared and calcined samples were
studied by transmission electron mocroscope (TEM) images
obtained on a JEOL JEM 2100F (Field Emission Electron
Microscope) instrument operated at 200 kV. The PL spectra were
recorded on a Perkin-Elmer LS50B spectrometer using 325 nm
excitation wavelength from a pulsed Xenon lamp. The
temperature desorption of ammonia (NH3-TPD) experiment
was performed to determine the surface acidity of various
samples. A 0.1 g sample was initially flushed with He at 500 8C
for 5 h and then cooled down to 100 8C and further saturated with
NH3. After NH3 exposure, the sample was purged with He until
equilibrium, and then heated from 100 to 700 8C at a heating rate
of 10 8C/min. A BEL-CAT instrument was employed to monitor
the amount of ammonia in the effluent.
2.3. Catalyst testing in methanol to DME conversion
The g-Al2O3 catalysts made by the precipitation/digestion
method were tested for their activity in methanol dehydration
 H.S. Potdar et al. / Applied Catalysis A: General 321 (2007) 109–116
reactions to dimethyl ether (DME). Their performance was
compared with that of a standard g-Al2O3 catalyst prepared
from Catapal-B (SASOL) boehmite under similar operating
reaction conditions. All catalysts were pretreated separately,
keeping a He flow of 50 ml/min at 500 8C for 1 h, and then the
activity was measured with 0.5 g catalyst in a fixed bed reactor
at the reaction conditions given below: T = 250 and 270 8C,
P = 101.30 kPa, WHSV = 1.0 h1. The reaction products were
analyzed using a FID detector equipped with 30 m GS-Q
capillary column.
3. Results and discussion
A transparent gel like precursor containing Al cations is
precipitated at pH  7.5–8.5 when sodium carbonate and Al
nitrate salt solutions are added drop by drop to 200 ml
deionized water. The mixture was stirred and maintained at a
temperature of 70 8C. The following chemical reaction
occurred:
Na2 CO3 þ 2HOH ! 2NaOH þ H2 O þ CO2
AlðNO3 Þ3 þ 3NaOH ! AlðOHÞ3 # þ 3NaNO3
AlðOHÞ3 ! AlOOH # þ H2 O
The hydrolysis of sodium carbonate in aqueous medium gen-
erates OH1 ions by reaction (1). The precipitate obtained by
reaction (2) is digested at a temperature 70 8C, which helped
to homogenize it due to the slow ripening process. The pre-
cipitate is further processed by washing with deionized water
first, followed by washing with alcohol and acetone to avoid the
contamination of sodium ions. The digestion step is found to be
essential to convert it to crystalline boehmite precursor by
reaction (3). EDAX analysis of as-dried precursor showed
the presence of Al and oxygen elements, no signal correspond-
ing to sodium element was detected, indicating its absence in
the material. To confirm further the formation of boehmite by
reaction (3), we performed a systematic characterization of the
as-dried precursor. The thermal behavior of as-dried precursor
was studied by DTA/TGA and experimental curves for the same
are depicted in Fig. 1. Two major endothermic weight losses
Fig. 1. DTA/TGA curves of as-dried boehmite.
111
were observed in TGA curve, at 90 and 300 8C respectively, and
a very small weight loss above 500 8C is also shown. The first
endothermic weight loss at 90 8C is related to removal of
physically adsorbed water/ethanol/acetone, while the second
weight loss at above 300 8C is ascribed to dehydroxylation
process and nitrate decomposition. The broad exothermic peak
at 500 8C with a very minor loss in weight in TGA curve may be
attributed to crystallization of transition alumina and or decom-
position of residual organics and further continuation of dehy-
droxylation process. A total weight loss of 28.63% is seen
during the three-step decomposition process. If bayerite phase
only would have formed by reaction (2), then in that case a total
theoretical weight loss of 34.62% would have been expected
due to following decomposition reaction (4):
2AlðOHÞ3 ! Al2 O3 þ 3H2 O (4)
However, the total weight loss of 28.63% is shown in the
experimentally observed TGA curve. If we presume that the
single phase boehmite is precipitated by reaction (3), then the
total weight loss of 15% would have been expected by follow-
(1)
ing reaction (5) leading to the formation of g-Al2O3 powder:
(2) AlOOH ! Al2 O3 þ H2 O (5)
(3) The results in our thermal analysis study indicate that the as-
dried precursor may have composition AlOOH corresponding
to the boehmite precursor as the total loss of 28.63% shown in
TGA is higher than theoretically calculated for reaction (5) i.e.
15%. This additional loss of 13.63% in TGA curve may be
related to adsorption of water and or alcohol/acetone/nitrate
species in boehmite precursor. As we do not know the exact
ratio of adsorbed water/acetone + ethanol and the concentration
of our associated nitrate species, it is not possible for us to
calculate the corrected molecular weight of boehmite precursor
with adsorbed species and to match experimentally observed
weight loss of 28.63% with that theoretically calculated from
the corrected molecular weight of precursor [16]. To support
our argument, that the as-dried precursor that is formed by
reaction (3) is boehmite and crystallization of g-Al2O3 take
place above 500 8C, as is seen by DTA/TGA studies, XRD and
IR studies were under taken on as-dried precursor and powder
obtained by its calcination at 550 8C. Fig. 2A(a–c) depicts XRD
patterns of as-dried precursor formed by precipitation/digestion
at RT and 70 8C and of commercial Catapal-B boehmite
sample. Fig. 2A(a) shows the as-dried precursor to be non-
crystalline in nature, as a broad hump is seen in XRD pattern,
whereas Fig. 2A(b, c) showed all reflections matching with
boehmite [JCPDS 21-1307] phase. The boehmite prepared at
70 8C appears to be more crystalline than that prepared at RT. It
seems that precipitation/digestion at 70 8C for 3 h helps to
generate crystalline boehmite due to a fast ripening process. It
is very clear from Fig. 2A(b, c) that the boemite precursor
particles show nano-size nature as is seen from line broadening
due to the presence of small crystallite sizes. The crystallite
sizes were calculated the using Scherrer equation:
kl
D¼ ;
b cos u
112 H.S. Potdar et al. / Applied Catalysis A: General 321 (2007) 109–116
Fig. 2. XRD patterns of (A) as-dried boehmite and (B) g-Al2O3 powder. (a)
Precipitated precursor at RT, (b) precipitated precursor at 70 8C, and (c)
Captapal-B.
where k is a constant 0.9, l is the wavelength of the X-rays, b
is the full width of diffraction peak at half maximum intensity
and u is the Bragg angle. The calculated crystallite sizes were
found to be in the range of 3.5–4.5 nm. Since it is established
[10–14] that conversion of aluminum hydroxide to single phase
boehmite precursor is dependent on many parameters like
temperature, nature of base and type of Al salt, the present
result proves that precipitation/digestion at 70 8C was able to
produce boehmite as a single phase precursor with crystallinity
comparable to that of the commercial Catapal-B sample.
Fig. 2B(a–c) shows the XRD patterns of powder obtained by
calcination of as-dried boehmite precursor precipitated at RTand
70 8C of Catapal-B boehmite at 500 8C/5 h in air. Fig. 2B(a)
indicates the formation of poorly crystallized alumina, as broad
peaks indexed for g-Al2O3 are seen in the XRD patterns.
However, all reflections shown in Fig. 2B(b, c) are indexed for the
reported g-Al2O3 phase having spinel lattice [ICPDS File no. 29-
63]. The crystallite sizes calculated by using Scherrer equation
were found to be in the range of 4.5–5.5 nm for 70 8C digested
and commercial Catapal-B derived samples. The broadening of
the XRD peaks revealed the nano-size nature of g-Al2O3
particles in these samples. The calcination temperature 550 8C/
5 h was selected based on DTA/TGA data of as-dried boehmite
precursor as discussed earlier. To support our conclusion drawn
from XRD results that the as-dried precursor precipitated at
70 8C is boehmite and that calcination produces well crystallized
Fig. 3. IR spectra of (a) as-dried boehmite and (b) g-Al2O3 powder.
g-Al2O3 powders, we carried out systematic IR studies on as-
dried precursor (Fig. 3a) and calcined powders (Fig. 3b). Fig. 3a
shows an intense band centered around 3447 cm1 and a broad
band at 1640 cm1, these are assigned to stretching and bending
modes of adsorbed water [17]. The Al–O–Al bending stretching
vibrations observed at 1073 cm1 and a shoulder at 1163 cm1
are due to symmetric and asymmetric bending modes,
respectively [18]. The OH torsional mode observed at
750 cm1 overlaps with Al–O stretching vibrations [18]. The
weak band at 2091 cm1 is assigned to a combination band [18].
The bands observed at 617 and 481 cm1 are attributable to
stretching and bending modes of AlO6 [18]. The peak at
1380 cm1 seen in Fig. 3a corresponds to NO31 ion [19] or OH
stretching due to presence of adsorbed alcohol [16,19]. The
absence of peaks in the region 1490–1410 and 880–860 cm1
implies that the boehmite precursor is free from CO32 species
[17]. Thus, the IR analysis of as-dried precursor confirmed that
the boehmite is formed by reaction (3). In the spectrum of
calcined powder shown in Fig. 3b, the peaks in the region of 500–
750 cm1 are assigned to n-AlO6, whereas the shoulder at 890
and the line at 800 cm1 are assigned to n-AlO4. Thus, g-Al2O3
phase contains both tetrahedral and octahedral coordination [19].
The broad band at 3447 cm1 and the weak band at 1640 cm1
are due to adsorbed water [19].
The surface area, pore size distribution and pore volume data
obtained for as-dried boehmite precursor and the g-Al2O3
powder obtained by its calcination at 550 8C/5 h in air are
tabulated in Table 1 for the shake of comparison. It is clear from
Table 1 that comparable or better properties were obtained in
the present investigation when compared with those for a
commercial sample if precipitation/digestion is carried out at
70 8C. The digestion temperature/time of 100 8C/48 h is needed
to get the properties mentioned in Table 1 by Chuah et al. [14].
However, the digestion temperature/time of 70 8C/3 h is just
sufficient to get comparable or better properties in the present
investigation. Higher values of pore volumes are obtained for
boehmite precursor as well as for resulting g-Al2O3 powders
when compared to those reported by Chuah et al. [14]. This may
be attributable to direct precipitation/digestion reaction at
 H.S. Potdar et al. / Applied Catalysis A: General 321 (2007) 109–116 113

Table 1
Surface area, average pore diameter, and pore volume of boehmite and g-Al2O3 powder
Item Surface area Average pore Pore volume
(m2 g1) diameter (nm) (cm3 g1)
Boehmite (70 8C precipitated precursor) 261 4.86 0.377
g-Alumina (made from 70 8C precipitated precursor) 220 7.02 0.485
Boehmite (RT precipitated precursor) 178 20.39 1.021
g-Alumina (made from RT precipitated precursor) 134 26.67 1.026
Boehmite (Ref. [14]) 294 3.90 0.200
g-Alumina (Ref. [14]) 258 5.14 0.270
Boehmite:Catapal-B 274 4.78 0.396
g-Alumina from Catapal-B 198 6.94 0.435

70 8C and the in situ generation of OH ions shown by reaction
(1). Thus, the condition required for fast nucleation of Al(OH)3
and controlled growth is achieved by maintaining a slight
alkaline pH of 7.5–8.5 and in situ generation of OH ions is
achieved by using Na2CO3 as precipitant. Chuah et al. [14]
maintained a slightly acidic pH  6.0 during precipitation at
room temperature and used 0.75 M solution of ammonia as
precipitant; digestion was subsequently carried out at 100 8C/
48 h. Thus, a better control of pH and in situ generation
of OH ions help to obtain nano-sized boehmite precursor with
comparable textural properties when compared to with those
reported by Chuah et al. [14]. The pH of 7.5–8.5 in the present
investigation helps the boehmite particles to acquire a positive
charge and may help to maintain them in an un-agglomerated
state, because the reported isoelectric point of boehmite
particles is 9.7 [20]. As the particles of boehmite carry positive
charge, there is some possibility that NO31 species may get
adsorbed on the surface of it, which is reflected in the IR

Fig. 4. N2 adsorption and desorption isotherms of (A) as-dried boehmite and Fig. 5. BJH pore size distribution of (A) as-dried boehmite and (B) g-Al2O3
(B) g-Al2O3 powder. (a) Precipitated precursor at RT, (b) precipitated precursor powder. (a) Precipitated precursor at RT, (b) precipitated precursor at 70 8C, and
at 70 8C, and (c) Captapal-B. (c) Captapal-B.
114 H.S. Potdar et al. / Applied Catalysis A: General 321 (2007) 109–116
spectrum of as-dried precipitate where the presence of nitrate
species is confirmed. The nature of N2 adsorption and
desorption isotherm remains type IV, as is seen from
Fig. 4A(a–c) and Fig. 4B(a–c) for as-dried boehmite precursor
and calcined g-Al2O3 powders with changes in hysteresis,
indicating thereby changes in pore structure in these materials
[21]. The BJH pore size distribution curves are reproduced in
Fig. 5A(a–c) and Fig. 5B(a–c), respectively. The pore size
distribution is wide and pore size lies between 2 and 100 nm for
as-dried boehmite precursor if precipitation/digestion is carried
out at RT. Most of the pores lie in the macro porous range. On
the other hand, a broad pore size distribution in the range of 2–
100 nm is maintained in the sample that is made by
precipitation/digestion at 70 8C for 3 h. The Catapal-B
boehmite sample shows a narrow pore size distribution in
the 2–100 nm range. The RT precipitated/digested sample after
calcinations in air gave a pore size distribution in the range of
10–100 nm {Fig. 5B(a)}. However, the pore size becomes
narrower, as is seen in Fig. 5B(b), and the pore size lies in the
range of 2–50 nm, i.e. in mesoporous range, in the case of
samples precipitated/digested at 70 8C after calcinations in air.
The commercial sample, however, gave a narrow pore size
distribution in the range of 2–20 nm. The important finding is
Fig. 6. SEM photographs of (a) as-dried boehmite and (b) g-Al2O3 powder.
that a total pore volume of, 0.487 cm3/g, which is much
higher than that reported by Chuah et al. [14], is obtained for
samples digested at 70 8C for only 3 h in the present study. They
could obtain similar values of pore volume but longer durations
of digestion time of 96 h or more are required. The lower pore
volume 0.435 cm3/g is maintained in commercial g-Al2O3.
Fig. 6(a, b) shows the SEM micrographs for as-dried boehmite
and g-Al2O3 powders. The boehmite and g-Al2O3 indicated
strong agglomeration of particles with varied sizes. The
boehmite and g-Al2O3 powder, showed similar morphological
features. Therefore, to get more information of morphological
features of as-dried boehmite and calcined g-Al2O3 powders,
we undertook TEM studies. Fig. 7(a, b) represents typical TEM
images of as-dried boehmite precursor and calcined g-Al2O3
Fig. 7. TEM images of (a) as-dried boehmite and (b) g-Al2O3 powder.
 H.S. Potdar et al. / Applied Catalysis A: General 321 (2007) 109–116
Fig. 8. PL spectrum of g-Al2O3 powder.
powders. Fig. 7a reveals that the boehmite particles are
spherical in nature, having a narrow size distribution with size
of 3.0–3.5 nm. These particles are aggregated to form pores of
varying sizes. This observation is consistent with BJH pore size
distribution curve {Fig. 5A(b)} where wide pore size
distribution is evident. Fig. 7b shows the TEM of g-Al2O3
powders obtained by calcinations of as-dried boehmite
precursor. The results indicate the presence of spherical
particles of 4–4.5 nm size. Some particles aligned to form
rods whereas most of them remain with spherical shape,
thereby producing pores of narrow size distribution which is
consistent with a BJH pore size distribution curve {Fig. 5B(b)}.
Further characterization of g-Al2O3 powders was carried out by
measuring the PL spectrum that is shown in Fig. 8. The
spectrum indicated two peaks: a strong one centered at 415–
420 nm and a weak one centered at 650 nm. The emission at
415–420 nm is ascribed to singly ionized oxygen vacancies
[22]. The origin of the peak at 650 nm is not clear at present. It
may be associated with defects other than oxygen vacancies
generated during decomposition of the boehmite precursor.
3.1. NH3-TPD
Fig. 9 shows the NH3-TPD spectra of the g-alumina powder
and the data obtained for the same are summarized in the
Table 2. It is evident from the Table 2 that the amount of
ammonia desorbed from the sample precipitated/digested at
70 8C is more (1.6701 mmol/g) than that of the sample
Table 2
NH3-TPD data on g-alumina obtained from precipitated precursor at RT, 70 8C
and Catapal-B
Region I Region II Total amount of
(mmol/g) (mmol/g) acid sites (mmol/g)
RT 0.4112 0.4586 0.8698
70 8C 0.9814 0.6887 1.6701
Catapal-B 0.6527 0.4918 1.1445
115
Fig. 9. NH3-TPD profiles of g-alumina obtained from (a) Catapal-B, (b) RT,
and (c) 70 8C.
precipitated/digested at RT (0.8698 mmol/g). The g-alumina
powder derived from the commercial boehmite (Catapal-B)
sample also gave the lower value of the desorbed ammonia
(1.14 mmol/g).
The TPD spectra (Fig. 9) of the g-alumina powder contain
two main intense peaks in the temperature range of 300–
600 8C. These peaks can be assigned to the NH3 desorbed from
the acidic sites with medium to high strengths [23]. The
intensity of these two peaks is found to be higher in the sample
precipitated/digested at 70 8C than that of the samples
precipitated/digested at RT and commercial Catapal-B,
respectively. From these results, it can be concluded that the
g-alumina powder possesses strong surface acidic sites as
compared to the g-alumina powder obtained from the RT
precipitated/digested and the commercial Catapal-B boehmite
sample. The precipitation/digestion at 70 8C not only helped to
improve surface area of the boehmite/g-Al2O3 powder
(Table 1) but also helped to enhance the surface acidity of
the resulting g-Al2O3 powders (Table 2). This is an interesting
finding or important result of the present investigation. Thus,
the g-Al2O3 obtained through precipitation/digestion route
gave more Lewis acidity and acid density resulting in a higher
performance as a catalyst.
3.2. Catalyst performance
The catalyst activity tests was conducted at two different
temperatures of 250 and 270 8C under similar reaction
conditions for three g-Al2O3 catalysts, two prepared from
precipitation/digestion experiments at RT and 70 8C, and one
commercially available Catapal-B sample; results are depicted
in Fig. 10. The catalyst made from 70 8C precipitation/
digestion boehmite precursor shows much higher conversion of
methanol to DME compared to the conversion for the one made
from room temperature precipitation/digestion material. The
performance of g-Al2O3 catalyst (70 8C precipitation/diges-
tion) is comparable with that of commercially Catapal-B
(SASOL Company) calcined sample. However, it is found that
116 H.S. Potdar et al. / Applied Catalysis A: General 321 (2007) 109–116
Fig. 10. Catalytic activity test of g-aluminas at reaction temperatures of 250
and 270 8C obtained from precipitated precursor at RT and 70 8C and from
Catapal-B in the methanol dehydration to DME synthesis.
the rate of light hydrocarbon formation such as CH4 at a
temperature of 270 8C is higher, as is seen from Fig. 10. The
yield of DME is found to be slightly decreased at 270 8C in
precipitated/digested catalyst due to the formation methane of
as compared to the yield for commercial catalyst. The higher
activity in the catalyst made from 70 8C precipitation/digestion
material is correlated to high surface area, better crystallinity
better pore size, better pore distribution and higher surface
acidity.
4. Conclusion
A simple precipitation/digestion method is successfully
utilized to produce boehmite precursor having narrow size
distribution of spherical nano-sized particles of size 3.5 nm
with surface area 261 m2/g, average pore diameter of
48.64 nm, and pore volume 0.3773 cm3/g. The calcinations
of the same at 550 8C for 5 h in air produced porous nano-sized
g-Al2O3 powder particles with the presence of oxygen
vacancies; the particles have a spherical shape with 4.5 nm
size. These powders showed BET surface surface area
220 m2/g with average pore diameter of 7.0 nm and pore
volume 0.4878 cm3/g. It is found that the performance of g-
Al2O3 catalyst (70 8C precipitation/digestion) is comparable
with that of commercially Catapal-B calcined sample. The
higher catalytic activity in catalyst made from 70 8C
precipitation/digestion material is due to high surface area,
surface acidity and better crystallinity, and pore size, and
distribution.
Acknowledgements
This research was supported as Eco-technopia 21 Program
funded by the Ministry of Environment, Republic of Korea. Dr.
H.S. Potdar is thankful to KOSEF for giving Brain-Pool
fellowship and to the Director, National Chemical Laboratory,
Pune 411008, for granting EOL. We are thankful to Dr. K.N.
Kim for doing PL measurements of our samples.
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