J Sol-Gel Sci Technol (2007) 44:177–186

DOI 10.1007/s10971-007-1631-x

ORIGINAL PAPER

Synthesis and characterization of sol–gel alumina nanofibers

Geik Ling Teoh Æ Kong Yong Liew Æ
Wan A. K. Mahmood

Received: 5 December 2006 / Accepted: 11 September 2007 / Published online: 3 October 2007
Ó Springer Science+Business Media, LLC 2007

Abstract Alumina nanofibers of high aspect ratio with 1 Introduction

surface area of [300 m2 g–1 has been prepared success-
fully in bulk quantities by the sol–gel method. The Nanostructured materials have attracted increasing interest
synthesis parameters including the binary water–alcohol because of their novel characteristic properties and
solvent system to aluminium isopropoxide ratio, pH, type potential technological applications [1]. Among such
of solvent and aging temperature affect the uniformity and materials, nanomaterials of high aspect ratio have
formation of nanofibers. It is proposed that alumina emerged as promising candidates for applications in nano-
nanofibers were formed by the curling of the nanosheets devices, in embedding semiconducting materials, as well
upon condensation after the hydrolysis. The phase evolu- as in advanced nano-composite fabrication [2]. Several
tion of alumina nanofibers from pseudoboehmite to a phase techniques have been successfully used for fabricating
has been shown by XRD and FTIR. 27Al NMR investiga- some inorganic nano-tubular materials, such as chemical
tions show that the Al atoms are six and four coordinated. vapour deposition, laser ablation, templating, hydrother-
The morphology of the alumina nanofibers does not change mal, sono-chemical methods and so on [3]. Of particular
much as the calcination temperature was increased. In interest in this respect is the ability to obtain tubular
addition, the average pore size increases and the BET materials by simple routes without involving sophisticated
surface area decreases as a function of calcination tem- equipment and complex procedures. Advanced synthesis
perature. The thermal behavior of alumina nanofibers was of tubular and fibrous morphology of mesoporous
investigated by TGA. molecular sieves has been demonstrated [4]. Yada et al.
[5] has reported the morphologically controlled synthesis
Keywords Alumina
Nanofibers
Synthesis
Sol–gel of aluminium-based surfactant mesophases by the homo-
geneous precipitation method using urea. The
mesostructured materials initially appear in a layer
structure and grow into a hexagonal phase with various
G. L. Teoh
W. A. K. Mahmood (&) morphologies such as curved wormlike, funneled, and
School of Chemical Sciences, University Science Malaysia,
tubular particles. In another approach, large-scale syn-
Minden 11800, Penang, Malaysia
e-mail: [email protected] thesis of one dimensional a-Al2O3 nanostructures was
demonstrated by Proost and Boxel [6] via simple electron-
Present Address: beam evaporation of the commercial high-purity oxide
G. L. Teoh
powders, followed by vapour condensation onto a sap-
Polymer Research Centre, Texchem Polymers Sdn. Bhd, Prai
13600, Penang, Malaysia phire substrate under controlled conditions of
supersaturation without the presence of catalyst.
K. Y. Liew (&) Alumina, one of the most versatile ceramic oxides, has
Hubei Key Laboratory for Catalysis and Materials Science,
exhibited application as active catalysts, catalyst supports,
College of Chemistry and Materials Science, Wuhan
430074, China and as adsorbents [7]. The metastable aluminas, including
e-mail: [email protected] the c, d, g, h, j, b and v polymorphs, have also gained

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178 J Sol-Gel Sci Technol (2007) 44:177–186

growing importance [8]. In particular, c-Al2O3 has been 2.2 Synthesis

well established as a catalyst and catalyst support, in wear
abrasives, in structural composites, and as part of burner The procedure adopted for the synthesis of the alumina
systems in miniature power supplies. The fabrication of nanofibers was as follows: A known quantity (0.25–
nanoscale alumina particles with narrow size distribution 11.0 mmol) of aluminium isopropoxide was hydrolyzed in
and high aspect ratio is of special interest in terms of their known amount (0.55–167.0 mmol) of water and (0.13–
potential in strengthening composites over conventional 0.93 mol) alcohol (methanol, ethanol, propan-1-ol, propan-
alumina fibers [9] and microtubes [10]. Significant efforts 2-ol or 2-buthanol) under vigorous stirring. The stirring
have, therefore, been directed towards the large-scale was continued for a further 24 h. Besides, samples were
synthesis of alumina nanostructures by a variety of meth- collected at different time intervals (20 min, 1, 3, 4, 5 and
ods, resulting in nanowires [11], nanotubes [12] and 24 h) in order to determine the influence of hydrolysis
nanobelts [13]. For instance, Ren et al. [14] have synthe- period on the formation of nanofibers by using TEM. The
sized the mesoporous–macroporous aluminium oxides with product was allowed to age at different temperatures, viz.
crystalline boehmite AlOOH phase by either hydrothermal at room temperature (30 °C) and in oven at 50, 100 and
treatment or microwave heating. The well-defined macro- 150 °C for 72 h. The solid was filtered by suction filtration,
porous frameworks of these materials were found to be thoroughly rinsed with ethanol, and subsequently dried at
composed of fibrous nanoparticles. ambient temperature. Finally, the solid was calcined at
The sol–gel method is valuable for producing alu- 540 °C in air for 5 h.
mina and other nanoparticles and much work has been To investigate the effect of calcination temperatures
done on the preparation and characterization of alumina on the morphology changes of the product, the solid was
nanoparticles comprised mainly of grain nanostructures. calcined at 300, 400, 540, 800, 1,000 and 1,050 °C in air
The sol–gel spinning process has been applied to pre- for 5 h. In another series of experiments, hydrochloric
pare alumina microfibers for various applications [15]. acid of concentration 1 mol dm–3 was slowly added to
However, there is no documentation to-date in the lit- the mixture of 11 mmol of aluminium isopropoxide in
erature on the synthesis of alumina nanofibers via sol– water and propan-1-ol (9:1 ratio) under vigorous stirring
gel process, except for reports on the use only of until a pH of 0.95 was obtained. Likewise, in another
commercial sol–gel alumina nanofibres for applications comparison experiment, ammonia solution of concen-
to enhance osteoblast adhesion and fabrication of tur- tration 1 mol dm–3 was added to the mixture until a pH
bidity filter [16]. No details of the preparation and their of 12. The subsequent treatments were same as described
characterization were reported. Varying the preparation above.
parameters in the sol–gel process markedly leads to final
products with different characteristics [17]. It was thus
of interest to explore the effects of change in the 2.3 Characterization
parameters on the sol–gel preparation of alumina
nanofibers. This article reports a practical and simple The nanostructured morphologies of the samples were
approach for the sol–gel preparation of alumina nano- determined by transmission electron microscope (TEM) on
fibers without peptization in acidic condition, templates a Philips TEM CM12 equipped with analysis Docu Version
or chelating agents, and on the characterization of the 3.2 image analysis system, using an accelerating voltage of
material thus obtained. 80 keV. Powder X-ray diffraction patterns were collected
to estimate crystallinities and the structural changes of the
synthesized materials on a Siemens Model D500 diffrac-
tometer using Cu Ka radiation (k = 0.154 nm), employing
2 Experimental procedure a scanning rate of 0.02° s–1 in the 2h range from 1° to 80°.
The peak positions and relative intensities were charac-
2.1 Materials terized by comparison with standard ICDD files. Fourier
transform infrared (FTIR) spectrometer was used to iden-
Materials used for the synthesis included aluminium iso- tify the species present in the synthesized samples. The
propoxide (Sigma, 98%), methanol (Merck, 99.8%), powdered samples were mixed with potassium bromide
ethanol (Systerm, 99.5%), propan-1-ol (Fisher, 99.90%), (KBr) powder and pressed to disks, and then measured.
propan-2-ol (Merck, 99.7%) and 2-buthanol (Fluka, 99%). FTIR spectrum was recorded on a Perkin-Elmer spec-
Distilled water was used throughout the synthesis. All trometer (model 2000) with a resolution of 4 cm–1
glasswares were scrupulously cleaned with chromic acid scanning from 4,000 to 400 cm–1 at room temperature.
27
solution and rinsed with distilled water. Al MAS NMR experiments were carried out at room

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J Sol-Gel Sci Technol (2007) 44:177–186 179

temperature on a Bruker AVANCE-400 spectrometer temperature (30 °C) and near neutral pH, the propan-1-ol
operating at 104.3 MHz. A 7 mm doubly bearing MAS to water ratio 9:1 and the water to aluminium isopropoxide
probe was used with a spinning speed of 12 kHz. The ratio of 60:1 provides the optimal conditions for the
thermogravimetric analysis (TGA) was carried out on a preparation of alumina nanofibers. EDX of the calcined
Perkin-Elmer Thermogravimetric Analyzer Model TGA7. sample confirms that the material consists of aluminium
The sample was heated under nitrogen atmosphere between and oxygen without the presence of residual carbon.
the ambient temperature and 900 °C at the rate of 20 °C To investigate the formation of the alumina nanofibers,
min–1. The specific surface area of the sample was deter- samples after various hydrolysis periods were taken and
mined from the nitrogen adsorption data at liquid nitrogen characterized using TEM. Figure 1a, b depicts the TEM
temperature using the Brunauer–Emmet–Teller (BET) micrographs and size distribution histograms counting 200
technique by means of a Micromeritics ASAP 2000 particles of each alumina nanostructures after hydrolysis
apparatus. The sample was outgassed for 24 h at 100 °C times of 20 min and 1 h, respectively. It is observed that
prior to the adsorption measurements. The pore size dis- the nanoparticles are spherical. The average size of the
tribution were calculated using the Barret–Joyner– materials hydrolyzed for 20 min and 1 h are 50.3 ± 11.4
Hallender (BJH) method on the desorption branch. and 55.1 ± 10.6 nm, respectively. These spherical nano-
particles are the sol particles. The aluminium isopropoxide
is hydrolyzed by mixing with water in which initiation
3 Results and discussion occurs via hydrolysis of alkoxy ligands to yield an alcohol
(ROH) and hydroxylated aluminium centers (Al–OH). In
3.1 Formation of alumina nanofibers this initial stage of the sol–gel reactions, small three-
dimensional oligomeric species are formed, with –Al–OH
Preliminary works showed that amorphous alumina groups on their outer surface as expressed in Eqs. 1 and 2
nanofibers of high aspect ratio with diameter of around [18]. Linkage of –Al–OH groups occurs via polyconden-
2 nm and length of about 70 nm have been prepared via sation and eventually results in oxypolymers with Al–O–Al
sol–gel process with aluminium isopropoxide under suit- network (Eq. 3). When sufficient interconnected Al–O–Al
able conditions. Typically, it has been found that at room bonds are formed in a region, they respond cooperatively as

Fig. 1 TEM micrographs and (a)

size distribution histograms of
nanoscale alumina particles
120
hydrolyzed for 20 min (a) and
1 h (b) 100

80
Count

60

40

20

0
35 45 55 65 75 85
Diameter of particle (nm)

(b)

90

80

70

60
Count

50
40

30

20

10

0
35 45 55 65 75 85
Diameter of particle

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180 J Sol-Gel Sci Technol (2007) 44:177–186

colloidal particles or a sol [19]. The larger particle size of synthesis duration for all the samples was allowed to pro-
the sample hydrolyzed for 1 h suggests that the numbers of ceed for 24 h in order to ensure the complete hydrolysis of
Al–O–Al bonds increases with time, the individual mole- the precursors (Fig. 2c). TEM micrographs of the as-
cules are further bridged and aggregated to form larger prepared and the calcined sample indicate that the samples
sols. Al2O3 forms upon dehydration from of the Al–O–Al posses fibril structure. Moreover, the fibrillar morphology
or pseudoboehmite as in Eq. 4. of the calcined sample identified by TEM is the same as
that of the as-prepared one. Besides, the TEM micrographs
of the sample taken at random locations and at several
AlðORÞ3 þ H2 O ! AlðORÞ2 ðOHÞ þ ROH ð1Þ
magnifications, show that alumina nanofibers in bulk
quantities is formed. In particular, close inspection at high
AlðORÞ2 ðOHÞ þ H2 O ! AlOðOHÞ þ 2ROH ð2Þ magnification of such nanofibers suggests that they exhibit
hollow internal cavity (Fig. 2d). The relatively lighter grey
center suggests that the nanofiber is hollow, indicating that
AlOHþAlOX!AlOAlþXOH ðX¼HorRÞ ð3Þ the nanofibers may have resulted from the curling of the
nanosheets. The driving force for the curling behavior can
be attributed to the minimizing of the surface free energy.
2AlOðOHÞ ! Al2 O3 þ H2 O ð4Þ Similar findings and explanation have been forwarded by
Chen et al. [20] in the synthesis of monolayer-dispersed
Interestingly, when the hydrolysis was extended up to two-dimensional nickel sulfide nanosheets and similarly
3 h, nanosheets surrounding the outer sol particles Yuan et al. [21] in the preparation of titanium oxide
aggregate and condense, as can be observed in Fig. 2a. nanofibers.
Polycondensation continues within the gel network as XRD analysis of the as-prepared sample showed broad
long as neighboring –Al–OH groups are close enough. and low-intensity peaks assignable to pseudoboehmite
This increases the connectivity of the three dimensional (Fig. 3). The XRD patterns of pseudoboehmite and
network forming AlOOH nanoclusters with pseudoboeh- boehmite exhibit almost the same peak positions but
mite phase. broader peaks with lower intensity are observed in the
Upon further hydrolysis for 4 h, an abundance of ran- former [22]. The peaks however disappeared after calci-
domly distributed nanofibers is observed (Fig. 2b). The nation and exhibited amorphous phase.

Fig. 2 TEM micrographs of

nanoscale alumina particles
hydrolyzed for 3 h (a); 4 h (b);
24 h (c); and TEM micrograph
at high magnification of the
sample calcined at 540 °C after
hydrolysis for 24 h (d)

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J Sol-Gel Sci Technol (2007) 44:177–186 181

Fig. 3 XRD patterns of * Pseudoboehmite

uncalcined sample and samples
calcined at various calcination θ
temperatures θ θ
θ δ θ θδ δ α
θ θ 1050 °C

400

θ θθ θδ θ θ δ α
1000 °C

θγ δγ δγ
800 °C

Intensity
540 °C
200

400 °C

*
* * * * * 300 °C
* *

* *
* * *
* Uncalcined
0
0 10 20 30 40 50 60 70 80
2-Theta

3.2 Effects of various synthetic parameters value of Rw is expected to promote and accelerate the
hydrolysis reaction. Additionally, higher values of Rw
As has already been noted, the sol–gel reactions are known caused more complete hydrolysis of monomers before
to be affected by many synthetic parameters such as water significant condensation occurs. Therefore, increasing the
to precursor ratio, pH, type and amount of solvent as well water content (Rw) generally favors the formation of small
as aging temperature. By controlling these factors, it is three-dimensional oligomeric species with –Al–OH groups
possible to vary the structure and properties of the sol–gel over Al–O–Al groups and limits the polycondensation
derived inorganic network over wide range. reaction which then inhibits the folding of nanosheets into
nanofibers. However, a decrease in Rw would lead to a
reaction system of high viscosity and incomplete hydro-
3.2.1 Effect of water to aluminium isopropoxide ratio (Rw) lysis of the precursors.

The water to aluminium isopropoxide ratios (Rw) has an

apparent influence in the preparation of alumina nanofibers. 3.2.2 Effect of pH
The alumina nanofibers can only be fabricated in a narrow
range of water content (Rw about 60–65). Beyond this Sol–gel reactions of metal alkoxides are typically acid–
range, the formation of the fibril structure is inhibited, and base catalyzed. The reaction mechanisms for acid and base
the morphology of the products consist of microparticles catalysis are very different [24]. Additionally, the reaction
and no nanofibers are formed. Under most conditions, rates for hydrolysis and condensation have a different
condensation commences before hydrolysis is completed dependence on the pH. Yoldas et al. [25] based on study on
[23]. However, conditions such as pH and H2O/Al molar silica concluded that the hydrolysis reaction and the con-
ratio (Rw) can force completion of hydrolysis before con- densation reaction take place simultaneously. It has been
densation begins as in fibrous silica synthesis. An increased well established that the presence of H3O+ in the solution

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182 J Sol-Gel Sci Technol (2007) 44:177–186

increases the rate of the hydrolysis reaction, whereas OH– Table 1 BET surface area and average pore size of the samples aged
ions increase the condensation reaction. In the present at various temperatures
approach, synthesis in pH 0.95 and 12 do not lead to the Aging BET surface Average pore
formation of nanofibers. This implies that under acidic temperature area (m2 g–1) size (nm)
conditions, hydrolysis is favored and condensation is the
Room temperature 340 12.0
rate-determining step. A great number of small-hydroxyl-
50 °C 317 13.1
ated oligomers with reactive –Al–OH groups are
100 °C 296 17.1
simultaneously formed and thus fewer sites are available
150 °C 248 18.4
for condensation. In contrast, hydrolysis is the rate-
determining step at pH 12 and hydrolyzed species are Synthesis parameters: aluminium isopropoxide, 11 mmol; water and
immediately condensed because of the faster rate. The propan-1-ol, 9:1 ratio; time, 24 h; reaction, 30 °C
hydrolysis could be incomplete and polycondensation
reaction continues immediately to form interconnected 3.2.4 Effect of aging temperature
three-dimensional networking of AlOOH resulting in larger
particles. Thus, from these results, it is likely that the Aging at room temperature and in an oven at 50, 100 and
dominant factor governing the formation of nanofibers is 150 °C for 72 h were found to have no significant effect on
the degree of hydrolysis and condensation. Thus, moderate the morphology of nanofibers. The nanofibers are generally
hydrolysis and condensation conditions, without acid or formed at room temperature (30 °C). However, there are
base, is essential for the formation of well-defined changes in physical properties of the gel as shown in
nanofibers. Table 1. Upon higher aging temperature, the surface area
begins to decrease while the pore size increases. This is
similar with the earlier reports on silica by Iller [28] that
3.2.3 Effect of the type of solvent once the gel structures has been formed it can be further
modified in the wet state by thermal treatment to enlarge
The type of alcohol used has a significant effect on the the pore size and reduce the surface area, thereby coars-
formation of alumina nanofibers. When the solvent is ening the gel structure. During aging, polycondensation
changed to methanol, ethanol, propan-2-ol or butanol, continues with localized solution and reprecipitation of the
instead of propan-1-ol, with the same mol ratio to water gel network, the strength of the gel thus increases with
ranging from 0.13 to 0.93 mol, aggregated nanoparticles aging. Therefore, heating the gel at 50–150 °C generally
are observed. The solvent is important to homogenize the brings about reinforcement but does not modify the pore
reaction mixture, especially at the beginning of the reaction structure.
[26]. With the presence of this homogenizing agent,
hydrolysis is facilitated. One has to keep in mind that all
mechanisms discussed are, in principle, reversible. This 3.3 Sintering and phase evolution
means that Al–O–Al bonds can be cleaved by alcohols and
OH–, and –Al–OH groups can react with alcohol to form The XRD patterns of the samples calcined at various
alkoxy groups. The degree to which the back reactions may temperatures are shown in Fig. 3. The as-prepared sample
occur depends mainly on the pH and the amount of water. shows broad peaks assigned to pseudoboehmite and the
Consequently, the alcohol not only serves as solvent but solid retains the XRD line with lower intensity even after
also as a reactant for the reverse reaction. As discussed by calcination at 300 °C for 5 h. After calcination at 400 °C,
Orcel [27] the nature of the solvent could influence the the pseudoboehmite phase transforms into Al2O3, in
reaction rate and thus the structure of the final sol–gel agreement with a previous report [29]. It is observed that
material. In the present work, propan-1-ol is proven to be the sample remains amorphous up to 540 °C. However,
the most suitable solvent to fabricate the nanofibers. It further heating to 800 °C gives rise to peaks attributed to c
might be due to that propan-1-ol has a greater affinity for phase (ICDD card no. 10–425), but there are small amounts
stabilizing the precursor to promote the hydrolysis than the of h-Al2O3 (ICDD card no. 11–517) and d-Al2O3 (ICDD
other solvents. Furthermore, the synthesis appears to be card no. 16–394) present in the sample, as shown in the
facilitated by the high affinity of propan-1-ol to stabilize corresponding XRD spectra. In samples calcined at 1,000
very small clusters of aluminium oxohydroxides (AlOOH) and 1,050 °C, a mixture of d and h alumina phases was
and to organize them into a three-dimensional network. identified with traces of a-Al2O3 observed on the pattern.
Nevertheless, it must be noted that the amount of the The h phase is the major component.
propan-1-ol added should be in a suitable range (0.85– The changes in shape and size of the nanofibers are
0.93 mol) in order to obtain the fibril morphology. studied as a function of the thermal treatment by TEM

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J Sol-Gel Sci Technol (2007) 44:177–186 183

Fig. 4 TEM micrographs of the

samples calcined at 300 °C (a);
400 °C (b); 540 °C (c); 800 °C
(d); 1,000 °C (e); and 1,050 °C
(f)

(Fig. 4). Figure 4a–c shows that, up to 540 °C, the fiber phase in agreement with the XRD pattern. The peaks at
sizes do not change significantly and the morphology of the around 1,633 cm–1 for both the as-prepared and the cal-
products are retained, indicating that the transformation of cined samples was due to the bending vibration of weakly
pseudoboehmite to Al2O3 did not result in nanostructural bound molecular water. The peaks observed between
change. This result is similar to the result obtained by 1,516 and 1,385 cm–1 in the samples could be due to the
Nortier et al. [30] in which during dehydration of boehmite presence of carbon–oxygen (C=O), carbon-carbon (C–C)
crystals to conventional Al2O3, the particles retained their and carbon–hydrogen (CH3) deformation. For the as-pre-
morphology. In addition, the particles might experience a pared sample, the sharp absorption bands at 1,100 cm–1
relatively low sintering rate in comparison with the sin- could be attributed to the bending modes of hydroxyl
tering rate at 800 °C. Upon subsequent calcination at groups in alcohol, water and Al–OH–Al groups and dis-
800 °C for 5 h, the particle sizes have grown, indicating appears after calcination. The disappearance of this band
that the sintering process have already started at this tem- could be due to the evaporation of the alcohol and water
perature Further calcination up to 1,050 °C leads to the after calcination. The shoulder at 1,145 cm–1 corresponds
coarsening of the nanofibers which are somewhat elon- to the stretching modes of Al–OH–Al groups [31].
gated, with a lower aspect ratio and the structures showed Absorption bands in the region 600–800 cm–1 arise from
slight disorderness. stretching modes of AlO4 and AlO6 as well as the libra-
FTIR characterization of the alumina nanofibers is tional mode of OH groups. Absorption bands below
presented in Fig. 5. The absorption bands around 600 cm–1 are attributed to the bending modes of vibra-
3,400 cm–1 arise from stretching modes of hydroxyl tions of AlO6 groups. The out-of-plane, m(OH), bending
groups that are involved in hydrogen bonding, as well as vibration of AlO4 are observed at 734 cm–1, whereas the
bridged hydroxyl groups [31]. The appearance of a vibrations due to the bending modes of AlO6 units occur
shoulder at 3,091 cm–1 ascertains the pesudoboehmite at 608, 502 and 474 cm–1.

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184 J Sol-Gel Sci Technol (2007) 44:177–186

Fig. 5 FTIR spectra of as-

prepared sample (a) and the
sample calcined at 540 °C (b);
(a)
1515
1385
800°C (c); and 1,050°C (d)

(b)
1635

1514 1397
1160
1633

(c)
879
%T
3103
(d) 1637 1071

3413 734
3460 1633
502
607
474
3420
3446 874
569

833 560

4000.0 3600 3200 2800 2400 2000 1800 1600 1400 1200 1000 800 600 400.0
cm-1

With increasing calcination temperature, the definition physically adsorbed water and organic molecules such as
in the Al-O stretching and bending vibrations (608, 502 and residual alcohol. Desorption of chemisorbed water mol-
474 cm–1) are gradually lost and replaced by two broad ecules and residual organic groups occur between 150
bands centered at 568 and 830 cm–1. The broadening of the and 250 °C and produce a weight loss of 2.0 wt.%. The
modes is probably ascribed to the transformation of the pronounced weight loss of 15.1 wt.%, observed between
hydrate into an oxide and affirmed the conversion from 250 and 510 °C, is probably produced by dehydroxyla-
Al(OOH) to Al2O3. This finding corresponds with the tion of the sample during transformation of
results of XRD analysis. pseudoboehmite into c-Al2O3. The weight loss in this
The dehydration behavior is also illustrated by TGA region can be related primarily to the AlOOH to Al2O3
results. The TGA weight loss and derivative curve of the dehydration, since the determined values agree well with
as-prepared sample reveals three weight loss regions as the theoretical value of 15.0% for this reaction. This
shown in Fig. 6. The weight loss of 4.1 wt.% between result shows that boehmite decomposition was almost
30 and 150 °C is attributed to the desorption of complete in this temperature range. Above 510 °C, the
sample did not show any weight loss. This is caused by
the gradual loss of the hydroxyl groups in the amorphous
structure, or possibly loss of water within the cores of
the nanofibres.
7
Al MAS NMR Spectroscopy was used to study the
local environment of the aluminium atoms in the samples.
For the samples calcined below 540 °C, a chemical shift at
around 5 ppm can be attributed to the six-coordinated
aluminium, i.e. octahedral, AlO6. This represents the main
component in the NMR spectra of all of the solids inves-
tigated. No 5-coordinated aluminium with resonance at
around 35 ppm and 4-coordinated aluminium at around
60 ppm are discernible by NMR for these solid. However,
calcination at higher temperature creates a new environ-
Fig. 6 Thermogravimetric curve and corresponding derivative curve ment at around 60 ppm, which is due to tetrahedral
of the as-prepared sample framework aluminium AlO4.

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J Sol-Gel Sci Technol (2007) 44:177–186 185

Table 2 Powder properties of the as-prepared sample and the sam- pressure point (P/Po), where the adsorption and desorption
ples calcined at various temperatures branches coincide is affected by the calcination tempera-
Sample BET surface Average pore Micropore ture of the samples, appearing at higher relative pressure
area (m2 g–1) size (nm) volume (cm3 g–1) (P/Po) as the severity of treatment increases. The sample
calcined at 540 °C shows the maximum adsorption. Since
As-prepared 340 12.0 0.000816
the changes in the adsorption isotherms in the high P/Po
300 °C 311 14.9 0.003351
range correspond to the capillary condensation, the slope
400 °C 333 16.0 0.006614
ratio is related to the pore size distribution. Therefore, it
540 °C 335 23.3 0.005988
can be concluded that the steep change in the isotherms of
800 °C 168 23.8 0.005030
this sample is due to its narrow pore size distribution.
1,000 °C 117 27.6 0.002921
1,050 °C 98 23.8 0.002096
Synthesis parameters: aluminium isopropoxide, 11 mmol; water and
propan-1-ol, 9:1 ratio; time, 24 h; reaction, 30 °C 4 Conclusion

Alumina nanofibers with diameter of around 2 nm and

The surface area, micropore volume and average pore
length of about 70 nm have been successfully fabricated in
size data for the samples calcined at various temperatures
bulk quantities by sol–gel process with controlled amounts
are compiled in Table 2. The surface area is seen initially
of water and alcoholic solvent. The reaction conditions
to decrease and is expected to be due to the contribution of
have significant effects on the formation of nanofibers. The
the removal of physically absorbed water and the residual
simple one-pot synthesis described herein, coupled with the
alcohol from the interconnected pore network as confirmed
mild temperature conditions, has the potential for ready
by FTIR and TGA results. The subsequent heating of the
applications in the catalysis and composite fields, both in
sample results in a rapid increase in surface area, which
the laboratory and industry.
achieves a maximum of over 335 m2 g–1 when the
pseudoboehmite is transformed at around 400 °C into Acknowledgements We are grateful to Mr. R. Patchamuthu for
Al2O3. The retention of high surface areas and large pore assistance with TEM characterization. Financial support from USM
volumes is seen during the conversion of pseudoboehmites short term IRPA grant is also greatly appreciated. One of the authors
(GLT) is thankful to Prof. V. G. Kumar Das and Prof. Helen Nair for
to Al2O3 by calcinations at 540 °C. It is particularly
their valuable suggestions and help during various phases of this
noteworthy that the Al2O3 reported in Table 2 has BET work.
surface areas substantially larger than those of conven-
tional Al2O3 of \250 m2 g–1.
On further heating the surface area decreases and at References
1,050 °C the surface area reduces to 98 m2 g–1 due to
sintering on heating past its maximum surface area. It is 1. Uvarov NF, Boldyrev VV (2001) Russ Chem Rev 70:265
2. Huang Y, Lieber CM (2004) Pure Appl Chem 76:2051
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