Solegel synthesis of mesoporous assembly of Nd

2
O
3
nanocrystals
with the aid of structure-directing surfactant
Thammanoon Sreethawong
a,
*
, Sumaeth Chavadej
a
,
Supachai Ngamsinlapasathian
b
, Susumu Yoshikawa
b
a
The Petroleum and Petrochemical College, Chulalongkorn University, Soi Chula 12, Phyathai Road, Pathumwan, Bangkok 10330, Thailand
b
Institute of Advanced Energy, Kyoto University, Uji, Kyoto 611-0011, Japan
Received 14 May 2007; received in revised form 3 August 2007; accepted 23 August 2007
Available online 2 September 2007
Abstract
The aim of this work was to demonstrate a simple route to synthesize mesoporous assembly of nanocrystalline neodymium oxide (Nd
2
O
3
)
with predominant pore size distribution in the mesopore region, which was successfully done for the rst time under mild conditions by a modi-
ed solegel process with the aid of structure-directing surfactant. Properly manipulated hydrolysis and condensation steps of neodymium
n-butoxide modied with acetylacetone in the presence of laurylamine hydrochloride surfactant aqueous solution were performed to obtain the
assembled Nd
2
O
3
nanocrystal. Various techniques, including thermogravimetric and differential thermal analyses (TGeDTA), X-ray diffraction
(XRD), N
2
adsorptionedesorption, BrunauereEmmetteTeller (BET) surface area analysis, BarretteJoynereHalenda (BJH) pore size distribu-
tion analysis, scanning electron microscopy (SEM), transmission electron microscopy (TEM), and selected-area electron diffraction (SAED),
were used to characterize the synthesized Nd
2
O
3
nanocrystal. The N
2
adsorptionedesorption isotherm of the synthesized Nd
2
O
3
nanocrystal
calcined at 500

C exhibited single hysteresis loop with IUPAC type IV-like pattern, indicating the existence of foremost mesopore. BJH
pore size distribution result revealed that the synthesized Nd
2
O
3
nanocrystals possessed mostly mesopore due to their assembly with a small
extent of macropore, resulting in very small mean pore diameter in the mesopore region. The particle size determined from both SEM and
TEM micrographs was also extremely small of approximately 10 nm.
2007 Elsevier Masson SAS. All rights reserved.
Keywords: Neodymium oxide; Nanocrystal; Solegel process; Structure-directing surfactant; Mesoporous assembly; Porosity
1. Introduction
Spurred by much development in nanotechnology in the re-
cent years, powders with particles of uniform shape and nar-
row size distribution lying in the nanometer range have been
shown to possess interesting properties. Nanosized oxide par-
ticles are gaining increasing technical importance for classic
areas of applications, such as catalysts, passive electronic
components, and ceramic materials [1e5]. In particular, rare
earth oxides have been used in many elds, such as ceramic
industry and catalysis, due to their special properties. For
example, they can be used as catalysts for dehydrogenation,
hydrogenation, and esterication reactions. What is most im-
portant is that they can be reclaimed and do not corrode the
equipment [6]. With the development of nanotechnology, ul-
trane rare earth oxides are needed in many elds. As widely
known, the smaller the particle size, the larger the specic sur-
face area and consequently the higher the chemical activity.
Hence, it is of great interest to obtain nanosized rare earth
oxides.
Among several rare earth oxides, neodymium oxide
(Nd
2
O
3
) is widely used in photonic applications, e.g. as phos-
phors providing yellow-to-violet upconversion emission [7], as
components for advanced materials (e.g. high-temperature ce-
ramics and superconductors) [8,9], as components of catalytic
systems (oxidative coupling of methane, N
2
decomposition,
* Corresponding author. Tel.: 66 2 218 4144; fax: 66 2 215 4459.
E-mail address: thammanoon.s@chula.ac.th (T. Sreethawong).
1293-2558/$ - see front matter 2007 Elsevier Masson SAS. All rights reserved.
doi:10.1016/j.solidstatesciences.2007.08.010
Available online at www.sciencedirect.com
Solid State Sciences 10 (2008) 20e25
www.elsevier.com/locate/ssscie
dehydrogenation of alcohols, high-temperature processes)
[10e12], and in many special applications (among others, to
simulate the actinide oxides during testing the new materials
as a host matrix for long life nuclear wastes) [13]. Moreover,
thin lms of Nd
2
O
3
are of interest for many other purposes,
such as optical antireection coatings, gate insulators, and
protective coatings [14,15]. For most of these applications,
the ultrane (in nanosized scale) neodymium oxide with well-
dened particle morphology is the most interesting and highly
functionalized material.
From literature, nanosized Nd
2
O
3
has been synthesized di-
rectly in one process or by thermal treatment of a suitable
precursor. The rst group of methods includes inverse micro-
emulsion [16], precipitation in high boiling polyalcohol solu-
tions [17], solegel auto-combustion [18], and hydrothermal/
solvothermal synthesis [19,20], while the precursors used are
in the forms of hydroxide, carbonate, acetate, or nitrate. How-
ever, these direct routes could produce Nd
2
O
3
nanopowders
with high degree of agglomeration and irregular large particle
morphology.
To our knowledge, the utilization of structure-directing sur-
factant for the solegel synthesis of mesoporous assembly of
nanosized Nd
2
O
3
has not yet been reported. Recently, nanocrys-
talline mesoporous oxide materials were successfully synthe-
sized by this combined solegel process [21e24]. Therefore,
it is interesting to apply this technique to prepare nanosized
Nd
2
O
3
with specic pore size characteristic. In this contribu-
tion, it is the rst attempt to synthesize Nd
2
O
3
nanocrystal
with mainly mesoporous assembly feature by utilizing this pro-
posed facile technique under mild conditions. Several tech-
niques, including TGeDTA, XRD, N
2
sorption, BET and BJH
analyses, SEM, TEM, and SAED, were systematically used to
characterize and identify the products physical properties.
2. Experimental
2.1. Materials
Neodymium n-butoxide (NB, Hokko Chemical Industry
Co., Ltd.), laurylamine hydrochloride (LAHC, Tokyo Chemi-
cal Industry Co., Ltd), and acetylacetone (ACA, Nacalai Tes-
que, Inc.) were used for this study. The molecular structures of
these chemicals are illustrated in Fig. 1. All chemicals were of
analytical grade and used without further purication. LAHC
was used as a surfactant behaving as a structure-directing
agent. ACA serving as a modifying agent was applied to
moderate the hydrolysis and condensation steps of the neo-
dymium precursor.
2.2. Synthesis procedure
Firstly, a specied amount of analytical grade ACA was
rst introduced into NB with a molar ratio of unity. The solu-
tion was then gently shaken until homogeneous mixing. After-
wards, 0.1 M LAHC aqueous solution of pH 4.2 was added
into the ACA-modied NB solution, in which the molar ratio
of NB to LAHC was adjusted to 4:1. The mixed solution was
continuously stirred at room temperature for an hour and fur-
ther aged at 40

C for a day to attain sol-containing solution as
a result of complete hydrolysis of the NB precursor. Then, the
condensation reaction-induced gelation was allowed to pro-
ceed by placing the sol-containing solution into an oven at
80

C for several days to ensure complete gelation. Subse-
quently, the gel was dried overnight at 80

C to eliminate
the solvents. The dried sample was calcined at 300e500

C
for 4 h to remove the LAHC surfactant and to consequently
produce the desired Nd
2
O
3
nanocrystal.
2.3. Characterization techniques
Simultaneous thermogravimetric and differential thermal
analyses (TGeDTA, Shimadzu DTG-50) with a heating rate
of 10

C/min in a static air atmosphere were used to study
the thermal decomposition behavior of the as-prepared (dried)
sample with a-Al
2
O
3
as the reference. Crystalline phase pres-
ent in the samples was identied by X-ray diffraction (XRD)
analysis. A Rigaku RINT-2200 rotating anode XRD system
generating monochromated Cu Ka radiation with continuous
scanning mode at a rate of 2

/min and operating conditions

of 40 kV and 30 mA was used to obtain XRD patterns. A
nitrogen adsorption apparatus (Quantachrome, Autosorb 1)
was employed to measure adsorptionedesorption isotherms
at a liquid nitrogen temperature of 196

C. Brunauere
EmmetteTeller (BET) approach using adsorption data over the
relative pressure ranging from0.05 to 0.35 was utilized to deter-
mine the surface area of the samples. BarretteJoynereHalenda
(BJH) approach was used to calculate pore size distribution of
the samples using the desorption data. The samples were de-
gassed at 200

C for 2 h to remove physisorbed gases prior to
the measurement. The sample morphology was examined by
a scanning electron microscope (SEM, JEOL JSM-6500FE)
and a transmission electron microscope (TEM, JEOL JEM-
200CX) with selected-area electron diffraction (SAED) mode
operated at 15 and 200 kV, respectively.
3. Results and discussion
The thermal decomposition behavior of the as-synthesized
(dried) sample was studied using TGeDTA analysis. In addi-
tion, the TGeDTA results were also used to select appropriate
condition for calcining the dried sample. Fig. 2 shows typical
TG and DTA curves of the dried gel sample. The weight loss
up to the temperature of 250

C is basically attributable to the
LAHC: CH
3
-CH
2
-CH
2
-CH
2
-CH
2
-CH
2
-CH
2
-CH
2
-CH
2
-CH
2
-CH
2
-CH
2
-NH
2
HCl
ACA: CH
3
-C-CH
2
-C-CH
3
O O
NB: CH
3
-CH
2
-CH
2
-CH
2
-O-Nd-O-CH
2
-CH
2
-CH
2
-CH
3
O-CH
2
-CH
2
-CH
2
-CH
3
LAHC: CH
3
-CH
2
-CH
2
-CH
2
-CH
2
-CH
2
-CH
2
-CH
2
-CH
2
-CH
2
-CH
2
-CH
2
-NH
2
HCl
ACA: CH
3
-C-CH
2
-C-CH
3
O O
CH
3
-C-CH
2
-C-CH
3
OO OO
NB: CH
3
-CH
2
-CH
2
-CH
2
-O-Nd-O-CH
2
-CH
2
-CH
2
-CH
3
O-CH
2
-CH
2
-CH
2
-CH
3
CH
3
-CH
2
-CH
2
-CH
2
-O-Nd-O-CH
2
-CH
2
-CH
2
-CH
3
O-CH
2
-CH
2
-CH
2
-CH
3
Fig. 1. Molecular structures of neodymium n-butoxide (NB), laurylamine
hydrochloride (LAHC), and acetylacetone (ACA).
21 T. Sreethawong et al. / Solid State Sciences 10 (2008) 20e25
removal of water physisorbed at the surface of the sample and
residual solvents, which is evidenced by the existence of endo-
thermic peak centered at 221.7

C in the DTA curve. The
weight loss in the temperature range of 250e400

C is due
to the burnout of the organic LAHC surfactant species situated
inside the porous structure of the sample. Between this tem-
perature range, DTA curve exhibits a dominant exothermic
peak centered at 362.9

C plausibly due to the removal of
the surfactant species bound among very tiny neodymium
moieties, which eventually resulted in Nd
2
O
3
nanocrystal
with small particle size as described later. It is evident that
the exothermic reaction of the surfactant molecules through
oxidation is responsible for the heat release. Thus, this peak
can be assigned to the oxidative decomposition of the organic
surfactant. In the temperature range of 400e500

C, the exo-
thermic peak centered at 432.5

C mainly results from not
only the crystallization process [25] but also involves with
the burnout of a small portion of organic residues, as well as
the dehydration and evaporation of water released from con-
densation reactions [26,27]. Interestingly, there was no signif-
icant weight loss observed beyond 500

C. The total weight
loss estimated from the TG result was 38.2%. Therefore, the
results from TGeDTA analysis suggest that the calcination
temperature of 500

C is adequate for both complete surfactant
removal and crystallization processes of the dried sample to
obtain the desired neodymium oxide with porous assembly
structure.
XRD analysis, which is the most powerful technique for
identication of crystalline structure, was employed to inves-
tigate the crystallinity and purity of the prepared samples.
As shown in Fig. 3, the XRD pattern of the Nd
2
O
3
sample cal-
cined at 500

C for 4 h reveals that the diffractogram can be
assigned as hexagonal phase Nd
2
O
3
(space group of P3m1)
with lattice constant a of 0.38 nm and c of 0.60 nm (JCPDS
Card No. 6-408) [28]. No peaks of impurity were found in
the XRD pattern, indicating that the nanocrystalline Nd
2
O
3
obtained via this synthesis method consists of ultrapure phase.
However, the amorphous hump can still be observed from the
XRD pattern, implying that the sample is not well crystallized
at the calcination temperature of 500

C. In order to achieve
the Nd
2
O
3
sample with more crystalline structure, the increase
in calcination temperature can be easily applied, despite un-
avoidably obtaining lower specic surface area. Additionally,
the XRD patterns of the Nd
2
O
3
samples calcined at 300 and
400

C are also included in Fig. 3. The diffractograms show
only amorphous phase, without any crystalline phase at all.
This is because there was no crystallization process occurring
at calcination temperatures below 400

C, as stated above in
the TGeDTA analysis. Hence, these XRD results can help
to verify the evolution of crystallization process as well.
The N
2
adsorptionedesorption measurement at a liquid N
2
temperature of 196

C was used to study the porosity and
textural properties of the synthesized Nd
2
O
3
nanocrystal.
Fig. 4 depicts the N
2
adsorptionedesorption isotherms and
pore size distributions of the samples. For the sample calcined
at the temperature of 300

C, at which the surfactant removal
process had not yet taken place, the isotherm exhibits a type II
sorption behavior without the existence of hysteresis loop, as
shown in Fig. 4(a), indicating the presence of macroporous
structural characteristic according to the classication of IU-
PAC [29]. This can be obviously seen from the pore size dis-
tribution obtained from the BJH method by calculating from
the desorption branch of the isotherm, as illustrated in
Fig. 4(b), that large extent of pore size is in the macropore re-
gion (pore size larger than 50 nm). When increasing the calci-
nation temperature to 400

C, at which the surfactant was
-50
-40
-30
-20
-10
0
100 200 300 400 500 600
Temperature / C
W
e
i
g
h
t

l
o
s
s

/

0
1
2
3
4
5
6
D
T
A

/

V
m
g
-
1
TG
DTA
Fig. 2. TG and DTA curves of the as-synthesized (dried) sample.
10 30 50 70 90
2theta / degree
I
n
t
e
n
s
i
t
y

/

a
.
u
.
N
d
2
O
3
N
d
2
O
3
N
d
2
O
3
N
d
2
O
3
N
d
2
O
3
N
d
2
O
3
N
d
2
O
3
N
d
2
O
3
N
d
2
O
3
500C
400C
300C
Fig. 3. XRD patterns of the nanocrystalline Nd
2
O
3
calcined at 300, 400, and
500

C.
22 T. Sreethawong et al. / Solid State Sciences 10 (2008) 20e25
(a) (b)
(c) (d)
(e) (f)
(g) (h)
0
3
6
9
12
15
60 90 0 30 120 150
Pore diameter / nm
60 90 0 30 120 150
Pore diameter / nm
60 90 0 30 120 150
Pore diameter / nm
Mean pore diameter = 4.8 nm
0
20
40
60
80
100
120
0 0.2 0.4 0.6 0.8 1
Relative Pressure, P/P
0
A
d
s
o
r
b
e
d

a
m
o
u
n
t

/

c
m
3
(
S
T
P
)
g
-
1
0
3
6
9
12
15
0 30 60 90 120 150
Pore diameter / nm
d
v
/
d
R

/

m
m
3
n
m
-
1
g
-
1
d
v
/
d
R

/

m
m
3
n
m
-
1
g
-
1
0
3
6
9
12
15
d
v
/
d
R

/

m
m
3
n
m
-
1
g
-
1
0
3
6
9
12
15
d
v
/
d
R

/

m
m
3
n
m
-
1
g
-
1
0
20
40
60
80
100
120
0 0.2 0.4 0.6 0.8 1
Relative Pressure, P/P
0
0 0.2 0.4 0.6 0.8 1
Relative Pressure, P/P
0
0 0.2 0.4 0.6 0.8 1
Relative Pressure, P/P
0
A
d
s
o
r
b
e
d

a
m
o
u
n
t

/

c
m
3
(
S
T
P
)
g
-
1
0
20
40
60
80
100
120
A
d
s
o
r
b
e
d

a
m
o
u
n
t

/

c
m
3
(
S
T
P
)
g
-
1
0
20
40
60
80
100
120
A
d
s
o
r
b
e
d

a
m
o
u
n
t

/

c
m
3
(
S
T
P
)
g
-
1
Adsorption
Desorption
Adsorption
Desorption
Adsorption
Desorption
Adsorption
Desorption
Mean pore diameter = 9.1 nm
Fig. 4. N
2
adsorptionedesorption isotherms and pore size distributions of the nanocrystalline Nd
2
O
3
synthesized with LAHC surfactant and calcined at 300

C ((a)
and (b)), 400

C ((c) and (d)), and 500

C ((e) and (f)), and N
2
adsorptionedesorption isotherm and pore size distribution of Nd
2
O
3
precipitates synthesized without
LAHC surfactant and calcined at 500

C ((g) and (h)).
23 T. Sreethawong et al. / Solid State Sciences 10 (2008) 20e25
completely removed from the structure, the isotherm differ-
ently shows a type IV-like sorption behavior with apparent
hysteresis loop, as shown in Fig. 4(c), representing the pre-
dominant mesoporous structural characteristic [29]. The ap-
parent step in the adsorption branch combined with the
sharp decline in the desorption branch is an obvious verica-
tion of the presence of mesoporosity. An abrupt increase in ad-
sorption volume of adsorbed N
2
was observed and located in
the P/P
0
value greater than 0.5. This sharp increase is typically
ascribed to the result of capillary condensation, indicating the
good homogeneity of the sample and fairly small pore size
since the P/P
0
position of the inection point is related to
the pore size. From Fig. 4(d), the pore size distribution shows
that the distribution of pore size is mostly in the mesopore re-
gion (pore size between 2 and 50 nm) due to the single hyster-
esis loop, in spite of the presence of very small extent of pore
size in the macropore region (pore size larger than 50 nm).
The textural properties of the Nd
2
O
3
nanocrystal calcined at
400

C are given as follows: a BET specic surface area of
31 m
2
g
1
with a BJH mean pore diameter and total pore vol-
ume of 4.8 nm (within mesopore region) and 113 mm
3
g
1
, re-
spectively. With further increase in the calcination temperature
to 500

C, at which the partially crystalline phase was ob-
served, the isotherm and pore size distribution are in similar
pattern to those of the sample calcined at 400

C, as presented
in Fig. 4(e) and (f), respectively. However, the textural proper-
ties markedly changed to be as follows: a BET specic surface
area of 25 m
2
g
1
with a BJH mean pore diameter and total
pore volume of 9.1 nm (within mesopore region) and
94 mm
3
g
1
, respectively. These changes can be attributed to
the pore collapse and metal oxide moiety coalescence upon
the more severe thermal treatment for the crystallization pro-
cess, leading to decrease in the specic surface area and total
pore volume, but increase in the mean pore diameter. From the
XRD and N
2
adsorptionedesorption analyses, the synthesized
Nd
2
O
3
calcined at sufciently high temperature of 500

C pos-
sesses prevalent nanocrystalline mesoporous structure. For the
sake of comparison, the similar synthesis of Nd
2
O
3
in the ab-
sence of LAHC was also performed. It was apparently seen
that the dissolution of the precipitates to obtain sol could not
be acquired, resulting in the impossibility of the solegel pro-
cess. These precipitates were then dried and calcined at the
thermal treatment condition of 500

C. From the N
2
adsorp-
tionedesorption isotherm and pore size distribution analyses
shown in Fig. 4(g) and (h), it was found that the resulting prod-
uct exhibited no hysteresis loop and consequently no longer
contained predominant mesoporous structure, but large macro-
porous structure was mostly obtained. These experimental re-
sults completely clarify the great inuence of the LAHC
surfactant in mesopore formation in the obtained Nd
2
O
3
nano-
crystal prepared from the proposed technique.
In order to obtain the insight information about the surface
morphology and particle size of the sample, SEM and
TEM analyses were performed. Figs. 5 and 6(a) show the
SEM and TEM micrographs of the synthesized Nd
2
O
3
. The
formation of Nd
2
O
3
aggregates comprising very tiny three-
dimensional disordered monodispersed nanoparticles was visibly
observed. The particle size of the sample is quite uniform of
approximately 10 nm. From the selected-area electron diffrac-
tion (SAED) pattern presented in Fig. 6(b), all of the electron
diffraction rings can be indexed to the hexagonal phase
Nd
2
O
3
, which also agree very well with the XRD analysis.
In consequence of N
2
adsorptionedesorption, SEM, and
TEM results, the porous structure of the synthesized Nd
2
O
3
nanocrystal can be plausibly attributed to the pores formed
among the nanocrystalline Nd
2
O
3
particles due to their assem-
bly as a consequence of the surfactant removal, which is
equivalently in the same track as other nanocrystals with mes-
oporous assembly formerly reported in the literature [30e33].
Additionally, it is denitely worth being deduced that the
Nd
2
O
3
nanocrystal with highly mesoporous assembly texture
and nanosized particle could be achieved by this proposed
synthetic technique.
4. Conclusions
The porous Nd
2
O
3
nanocrystal was successfully prepared
by a combined solegel route with structure-directing surfac-
tant of laurylamine hydrochloride/neodymium n-butoxide
modied with acetylacetone system. The N
2
adsorptione
desorption isotherm and BJH pore size distribution of the
synthesized Nd
2
O
3
nanoparticles indicate the existence of pre-
dominant mesoporous structural characteristic owing to their
assembly with very small mean pore diameter located in the
mesopore region. The XRD and SAED results conrm that
the synthesized Nd
2
O
3
possessed hexagonal phase crystallin-
ity. The SEM and TEM images showed that the porosity of
the synthesized Nd
2
O
3
was reliably formed among their
assembled nanoparticles. This is the rst successful attempt
Fig. 5. SEM image of the nanocrystalline Nd
2
O
3
calcined at 500

C.
24 T. Sreethawong et al. / Solid State Sciences 10 (2008) 20e25
reported on the synthesis of mesoporous assembly of nano-
crystalline Nd
2
O
3
particle, which is a capable candidate for
being applied for various mentioned purposes.
Acknowledgments
This work was nancially supported by the National Excel-
lence Center for Petroleum, Petrochemicals, and Advanced
Materials under the Ministry of Education, Thailand and the
Grant-in-aid for Scientic Research under the 21COE Pro-
gram and the Nanotechnology Support Project, Japan. The
Research Unit of Applied Surfactants for Separation and
Pollution Control under Ratchadapisek Somphot Fund, Chula-
longkorn University, Thailand is also acknowledged for
providing a partial support.
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Fig. 6. (a) TEM image and (b) selected-area electron diffraction (SAED)
pattern of the nanocrystalline Nd
2
O
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calcined at 500

C.
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