5522 Langmuir 2003, 19, 5522-5525

Synthesis of Ordered Hexagonal Mesostructured Nickel

Oxide
Sumit Banerjee,† Ashwin Santhanam,† Aruna Dhathathreyan,*,‡ and
P. Madhusudhan Rao*,†
Department of Chemical Engineering, Sathyabama Institute of Science and Technology,
Chennai 600 119, India, and Chemical Laboratory, Central Leather Research Institute,
Chennai 600 020, India

Received March 12, 2003. In Final Form: April 16, 2003

An ordered hexagonal mesoporous nickel oxide was prepared for the first time using sodium dodecyl
sulfate as the surfactant and urea as the hydrolyzing agent. The resulting oxide showed mesoporous
structure with pore size ranging from 4 to 7 nm. Calcination at different temperatures was carried out,
and the mesoporosity did not collapse even after calcination at 773 K although the surface area decreased
drastically (from 279 to 72 m2/g) and a broader pore size distribution was observed.

Introduction tion,9 and functionalization of the walls with sulfate or

The discovery of M41S materials by the supramolecular
templating mechanism ushered in a new era in synthesis
chemistry.1 These mesoporous materials exhibit high
surface area, narrow pore size distribution, large pore
volume, and high thermal and hydrothermal stability.
The semicrystalline nature of the walls owing to long-
range ordering, unlike the rigid crystalline walls of zeolites,
allows the tuning of the pore sizes. Several mechanisms
such as liquid crystal templating,2-4 cooperative tem-
plating,2,4 neutral templating,2,3 and recently a ligand-
assisted templating5 have been proposed to account for
the occurrence of mesophasic structures. The extension
of this synthesis protocol led to the preparation of non-
siliceous mesoporous oxides with high surface areas.4 The
early synthesis procedures predominantly yielded meso-
phases with lamellar structures attributed to a high
packing factor.2 However, innovative synthesis conditions
coupled with appropriate choice of precursors and surf-
actants resulted in the preparation of hexagonally ordered
mesoporous oxides such as zirconia, alumina, tantala,
niobia, hafnia, and tin oxide.
Two common features associated with the mesophasic
structures of non-siliceous materials are their low thermal
stability and difficulty in removing the surfactant without
destroying the structural integrity.6-8 Unlike silica, the
inorganic precursors of other oxides do not network
extensively. Methods to increase the thermal stability of
non-siliceous materials include the use of silica as a
cosupport,9 hydrothermal treatment,9 partial crystalliza-
* Corresponding authors. E-mail: adhatha@md5.vsnl.net.in
(Aruna Dhathathreyan); madhusr@yahoo.com (Madhusudhan Rao).
† Sathyabama Institute of Science and Technology.
‡ Central Leather Research Institute.
(1) Beck, J. S.; Vartuli, J. C.; Roth, W. J.; Leonowicz, M. E.; Kresge,
C. T.; Schmitt, K.D.; Chu, C. T. W.; Olson, D. H.; Shepard, E. W.;
McCullen, S. B.; Higgins, J. B.; Schlenker, J. L. J. Am. Chem. Soc. 1992,
114, 10834.
(2) Sayari, A.; Liu, P. Microporous Mater. 1997, 12, 149.
(3) Tanev, P. T.; Pinnavaia, T. J. Science 1995, 267, 865.
(4) Huo, Q.; Margolese, D. I.; Stucky, G. D. Chem. Mater. 1997, 8,
1147.
(5) Antonelli, D. M.; Ying, J. Y. Angew. Chem., Intl. Ed. Engl. 1995,
34, 2014.
(6) Reddy, J. S.; Sayari, A. Catal. Lett. 1996, 38, 219.
(7) Ayyappan, S.; Rao, C. N. R. Chem. Commun. 1997, 575.
(8) Ulagappan, N.; Rao, C. N. R. Chem. Commun. 1996, 1685.
phosphate groups.10,11
Recently, Wong et al.9 prepared mesoporous tungstated
zirconia, stable up to ca. 973 K, by nanoparticle/surfactant
templating using colloidal zirconia and a triblock copoly-
mer as the surfactant.
Additionally, it is important to control the hydrolysis
rate of the inorganic precursor to achieve high-quality
materials. Antonelli and Ying12 have demonstrated the
importance of controlling the hydrolysis rate of the
inorganic precursor to achieve a uniform hexagonal phase.
They prepared mesoporous titania in the presence of
acetylacetone which inhibited the hydrolysis rate. Simi-
larly Sachtler et al.11 used acetylacetone as a hydrolysis
inhibitor in the preparation of mesoporous zirconia.
Cationic and anionic templates failed to give SnO2 and
TiO2 mesophases.8 The mesoporic structure formed with
dioctyl sulfo succinate collapsed on calcining at 700 K for
12 h. Moreover, the surfactant could not be removed by
solvent extraction. Unlike mesoporous silica, the small-
angle X-ray scattering (SAXS) investigations on meso-
porous non-siliceous materials did not yield X-ray de-
tectable ordering although the mesoporous nature of the
materials was confirmed by Brunauer-Emmett-Teller
(BET) measurements.13-16
It has been reported that functionalization of the oxide
surface by sulfate preserves the textural properties of
oxides.11,13 Hexagonal mesoporous zirconia was prepared
using sodium lauryl sulfate and ammonia as the tem-
plating and hydrolyzing agents, respectively. Ayyappan
and Rao7 reported the synthesis of mesoporous aluminum
borates using sodium dodecyl sulfate while the use of
(9) Wong, M. S.; Jeng, E. S.; King, J. Y. Nano Lett. 2001, 1, 637.
(10) Ciesla, U.; Schacht, S.; Stucky, G. D.; Unger, K. K.; Schüth, F.
Angew. Chem., Int. Ed. Engl. 1996, 35, 541.
(11) Huang, Y. Y.; McCarthy, T. J.; Sachtler, W. M. H. Appl. Catal.
1996, 148, 135.
(12) Antonelli, D. M.; Ying, J. Y. Chem. Mater. 1996, 8, 874.
(13) Larsen, G.; Lotero, E.; Nabity, M.; Petkovic, L. M.; Shobe, D. S.
J. Catal. 1996, 164, 246.
(14) Parvulescu, V. I.; Bonnemann, H.; Enduschat, U.; Rufinska, A.;
Lehmann, Ch. W.; Tesche, B.; Poncelet, G. Appl. Catal., A 2001, 214,
273.
(15) Pacheo, G.; Zhao, E.; Garcia, A.; Sklyaruv, A.; Fripiat, J. J. Chem.
Commun. 1997, 497.
(16) Kundo, J. N.; Takahara, Y.; Domen, K. Chem. Mater. 2001, 13,
1200.

10.1021/la034420o CCC: $25.00 © 2003 American Chemical Society

Published on Web 05/14/2003
Ordered Hexagonal Mesostructured Nickel Oxide Langmuir, Vol. 19, No. 13, 2003 5523

cationic surfactants or long-chain amines did not result

in the mesophase.
Nickel oxide is a material extensively used in catalysis,
battery cathodes, gas sensors, electrochromic films, and
magnetic materials. In this paper, we have synthesized
mesostructured nickel oxide, which has been shown to be
an excellent electrode material for energy storage ap-
plications.
In the present study, we have attempted to apply the
current understanding on non-siliceous materials to
synthesize mesostructured nickel oxide. We have used an
anionic sulfate based surfactant to understand its role in
improving thermal stability and employed urea hydrolysis Figure 1. Adsorption isotherms of the as-synthesized (leached),
to control the hydrolysis rate. calcined, and unleached samples of mesoporous nickel oxide.

Experimental Section
Synthesis. The synthesis protocol adopted in the present study
is as follows: Nickel chloride, (Indian Scientific, AR Grade),
sodium dodecyl sulfate (SDS) (Sigma Chemicals USA, >99%
pure), urea (Indian Scientific, AR Grade), and double-distilled
water were taken in the mole ratios of 1:2:30:60. These were
stirred at 313 K for 1 h to yield a transparent solution. The
contents were then heated to 353 K and maintained at that
temperature for 1 h. The resulting mixture was cooled to room
temperature to prevent further hydrolysis of urea. After cen-
trifugation, the solid was washed with water a few times and
then dried in air. To remove the excess surfactant, the solid was
mixed with a 0.05 M ethanolic solution of sodium acetate and
stirred at 313 K for an hour. The resulting solid was washed with
ethanol extensively and then dried in air. The samples were
then calcined at 673 K for 4 h and at 773 K for 2 h.
Characterization. Nitrogen adsorption and desorption ex-
periments were carried out at 77 K on a Quantachrome
instrument, Nova1000 series analyzer. Surface area was cal- Figure 2. Pore size distribution plots of the as-synthesized
(leached), calcined, and unleached samples of mesoporous nickel
culated using the BET equation. Pore size distributions were
oxide.
calculated by the BJH (Barrett, Joyner, and Halender) method
using the desorption branch of the isotherm. Transmission
electron micrographs were taken at a operating voltage of 200 hexagonal pore system with a narrow pore size distribu-
kV using a Philips STEM instrument, and the sample was tion. The BJH pore size distribution is narrow, and the
prepared by dipping a copper grid, coated with a holey carbon pore diameter is centered at 4.0 nm. Such well-defined
film, into a colloidal suspension of particles dispersed in methanol pore filling steps have been observed previously in other
which was then air-dried and stored in a vacuum chamber. oxides.7,14,15 Calcination at 673 K resulted in an expected
Infrared spectra were recorded on a Perkin-Elmer spectrum RXI decrease in volume absorbed and the pore-filling step
series Fourier transform infrared (FTIR) spectrophotometer using
KBr pellets containing 1% weight sample in KBr. Thermogravi-
shifted to higher pressure revealing the presence of pores
metric analysis (TGA) was performed on a DuPont 951 ther- of wide-ranging sizes. The mean BJH pore diameter was
mogravimetric analyzer. The samples were heated at a rate of found to be 7.0 nm. However, the mesoporous nature of
10 K/min. the oxide was preserved. Increasing the calcination
In this study, we decided on a sulfate-based surfactant because temperature to 773 K did not significantly alter the shape
the presence of sulfate or phosphate groups preserves the porous of the isotherm nor did the pore size distribution vary
structure upon calcination.11,15 Another factor was the facile markedly. The failure to observe an expected collapse of
removal of SDS. Larsen et al.13 reported that SDS could be the mesoporous structure is a significant feature in this
removed by repeated washing with ethanol and water. Earlier study. Parvulescu et al.14 reported a similar resistance to
reports had mentioned the difficulty in removing the surfactant.7
collapse in mesoporous zirconia after calcination at 773
A high surfactant/Ni ratio was employed since it is reported
that sodium dodecyl sulfate undergoes a spherical to rod
K.
transition at high concentrations leading to high-quality materi- The transmission electron micrograph of the oven-dried
als.13 sample displayed in Figure 3a shows a hexagonal mor-
Precipitation of the inorganic precursor had been widely phology that is ordered and periodic with the pores in the
performed with liquid ammonia. Yada et al.17 employed urea as nanometer scale. The 110-lattice fringe characteristic of
the hydrolyzing agent in the preparation of mesoporous alumina. the hexagonal phase is clearly seen. The corresponding
In the present study, the hydrolysis rate of the nickel oxide selective area diffraction is shown in Figure 3b. Since the
precursor was controlled differently by adopting the urea sample is oven-dried after repeated washing with ethanol
hydrolysis method. At ca. 353 K, ammonia is generated in situ (drying at T ) 200 °C), any packing order seen could be
due to urea decomposition.
only due to the hexagonal channels of the nickel oxide
Results and Discussion formed and such structures should be fairly stable even
on heating. To our knowledge, this is the first instance of
The adsorption isotherms and BJH pore size distribu- ordered hexagonal mesoporous nickel oxide by this
tions of mesoporous nickel oxide are shown in Figures 1 synthetic route. Earlier investigations on the preparation
and 2, respectively. A well-defined pore filling step at 0.4P/ of mesoporous nickel oxide resulted in lamellar phases.18,19
P0 in the oven-dried sample is indicative of a well-ordered
(18) Nelson, P. A.; Elliot, J. M.; Attard, G. S.; Owen, J. R. Chem.
(17) Yada, M.; Machinda, M.; Kijma, T. Chem. Commun. 1996, 769. Mater. 2002, 14, 524.
5524 Langmuir, Vol. 19, No. 13, 2003 Banerjee et al.

Figure 4. FTIR spectra of the as-synthesized sample.

Table 1. Textural Properties of Mesoporous Nickel

Oxide
pore
BET pore diameter (nm)
area volume mean avg
samples (m2 g-1) (mL g-1) (BJH) (4PV/SA)
air-dried (110 °C) 278.41 0.457 3.68 6.58
400 °C calcined (4 h) 161.99 0.454 7.14 10.84
500 °C calcined (2 h) 72.61 0.156 6.84 8.6
air-dried unleached 213.53 0.28 3.72 5.26
(110 °C)

where S is the surface area (cm2/g) and F and D are the

Figure 3. Transmission electron micrograph of the as-
synthesized sample.
Liu et al.19 prepared nickel oxide using nickel sulfate in
the presence of a cationic surfactant with ammonia as the
precipitating agent. The contents were autoclaved for 20
h at 398 K. The lamellar phase obtained showed no X-ray
detectable ordering after calcination, and the surface area
was 31 m2/g after calcination at 773 K. However, direct
synthesis using sodium silicate resulted in an ordered
hexagonal mesophase. Nelson et al.18 synthesized meso-
porous nickel/nickel oxide using the liquid crystal tem-
plating approach involving high concentrations of nonionic
surfactants (>30 wt %) and nickel acetate as the precursor.
The transmission electron micrographs showed lamellar
structure. Sayari and Liu have postulated that assembled
precursors of type S-I+ would yield lamellar phase nickel
oxide.2
The textural properties of mesoporous nickel oxide are
tabulated in Table 1. An expected decrease in surface area
with increasing calcination temperature is seen, but the
pore sizes are typical of mesoporous materials. The surface
area of the samples is close to the maximum theoretical
surface area calculated from the expression S ) 6000/FD
(19) Liu, X.; Chu, C. M.; Aksay, I. A.; Shih, W. H. Ind. Eng. Chem.
Res. 2000, 39, 684.
density (g/cm3) and pore diameter (nm) of a spherical
particle, respectively. The study shows that the pore
volume of the as-synthesized sample is larger than that
of any other forms. This is possibly due to the presence
of nanoporous channels of the mesoporous nickel oxide
formed, and these do not collapse even after calcinations
at higher temperature.
Previous studies involving different precursors of nickel,
surfactants, and synthesis conditions have reported only
the existence of the lamellar phase.18,19 Interestingly,
Wirnsberger et al.20 prepared mesostructured iron oxy-
hydroxides using FeCl3 in the presence of sodium dodecyl
sulfate and other long-chain sulfate-containing surfactants
with ammonia as the precipitating agent. Initially am-
monia was added to the precursor solution followed by
the surfactant after 2 h of stirring. On aging, a lamellar
phase was obtained, and prolonged aging times increased
only the layer thickness.
The FTIR spectrum of the oven-dried sample is shown
in Figure 4. The prominent bands at 2850-3000 and
1370-1380 cm-1 are typical C-H symmetric stretching
and bending vibrations, respectively, confirming the
incomplete removal of surfactant even after extensive
leaching with ethanol. However, Larsen et al.,13 employing
a similar washing procedure in preparing mesoporous
zirconia, could completely remove the dodecyl sulfate
surfactant.13 However, in the calcined samples no peaks
typical of C-H stretch vibrations corresponding to the
alkyl tails of the surfactants were observed.
The TGA profiles of the leached and unleached samples
are shown in Figure 5. In the leached sample (Figure 5a),
ca. 6 wt % of the surfactant is chemically bound to the
walls since it is not removed even after extensive leaching
with ethanol. The complete removal of the surfactant, a
vexing problem in other studies,8 is observed at ca. 673
(20) Wirnsberger, G.; Gatterer, K.; Fritzer, H. P.; Grogger, W.; Pillep,
B.; Behrens, P.; Hansen, M. F.; Bender Koch, C. Chem. Mater. 2001,
13, 1453.
Ordered Hexagonal Mesostructured Nickel Oxide
Figure 5. TGA-differential thermogravimetry (DTG) plots of
(a) the as-synthesized sample and (b) the unleached sample.
K. The TGA results confirm that strongly bound surfactant
is needed for the retention of mesoporosity after treatment
at high temperatures.14,21 A high percentage of weight
loss (ca. 55 wt %) observed in the unleached sample (Figure
(21) Knowles, J. A.; Hudson, M. J. J. Mater. Chem. 1996, 6, 89.
Langmuir, Vol. 19, No. 13, 2003 5525
5b) is due to the high surfactant/Ni ratio used and skipping
of the ethanol washing step. It can be seen that the bulk
of the surfactant is loosely held and can be easily removed
by ethanol washing. From the TGA studies, it can be
inferred that the low pore volume observed in the
unleached sample (Table 1) is due to pore blockage by the
surfactant.
The results are in agreement with studies on meso-
porous zirconia that the presence of surfactant during
calcination is essential to achieve improved textural
properties.14,21
Crucial to the formation of the ordered mesoporous
phase in non-siliceous materials is the controlled hy-
drolysis of the inorganic precursor, which allows a stronger
interaction between the inorganic precursor and the
organic template. A hydrolysis inhibitor such as acetyl-
acetone has been employed widely.12,13,14,22 In the present
study, the inorganic precursor was hydrolyzed by ammonia
generated in situ by urea decomposition at 353 K. A similar
control over hydrolysis rate achieved with in situ generated
ammonia may be responsible for the highly ordered
hexagonal phase achieved in our study.
An increase in the aging period from 1 h, maintained
in this study, should definitely improve the textural
properties since non-siliceous materials do not form
network structures easily. Aging periods of g6 h are
routinely employed in the synthesis of non-siliceous
materials.8,12,13 Efforts are presently on to improve the
textural properties by increasing the aging period. More-
over, the effects of varying the surfactant/Ni ratio, the
nature of the nickel precursor, and the surfactant on the
morphology of the mesophase are under investigation.
This study indicates clearly that it is possible to design
ordered mesoporous structures of transition metal oxides
using anionic surfactants and the use of urea for hydro-
lyzing the inorganic precursor seems to be an added
advantage in stabilizing the template structure. Further
calcinations even at high temperatures did not destroy
the mesoporosity.
Acknowledgment. The authors thank the Director,
Central Leather Research Institute, Chennai, for extend-
ing the facilities of the institute for the experimental work.
LA034420O
(22) Kaneko, E. Y.; Pulcinelli, S. H.; Vteixeira da Silva; Santilli, C.
V. Appl. Catal., A 2002, 235, 71.