Journal of Alloys and Compounds 389 (2005) 165–168

Preparation of Y2 O3-doped CeO2 nanopowders by

microwave-induced combustion process
Yen-Pei Fu∗ , Cheng-Hsiung Lin
Department of Chemical Engineering, Wu-Feng Institute of Technology, Ming-Hsiung, Chiayi 621, Taiwan, ROC

Received 19 March 2003; accepted 20 May 2004

Abstract

Y2 O3 -doped CeO2 nanopowders were successfully synthesized by microwave-induced combustion process using cerium nitrate hexahydrate,
yttrium nitrate hexahydrate, and urea. The process took only a few minutes to obtain Y2 O3 -doped CeO2 powders. The nanopowders were
investigated by differential thermal analyzer/thermogravimeter (TG/DTA), X-ray diffractometer (XRD), transmission electron microscopy
(TEM), and specific surface area measurements (BET). The as-received Y2 O3 -doped CeO2 powders revealed that the average particle size
ranged from 19 to 25 nm, crystallite dimension varied from 14 to 16 nm, and the distribution of specific surface range from 33 to 43 m2 /g.
© 2004 Elsevier B.V. All rights reserved.

Keywords: Microwave-induced combustion; Yttrium-doped ceria; Nanopowders

1. Introduction microwave oven, heat is generated within the sample itself

Nanopowders have many excellent properties, which are
suitable for various applications such as ceramics, gas sen-
sor, rechargeable ceramic batteries, and ceramic fuel cells. In
addition, they can significantly enhance sintering rates, de-
crease sintering temperature, and improve optical, electrical,
and magnetic properties compared to the micrometer-sized
powders [1,2]. Solid oxide fuel cells attract widespread at-
tention due to their high-energy conversion efficiency and
low pollution. Y2 O3 -doped CeO2 has been considered as the
solid electrolyte for moderate temperature solid oxide fuel
cells [3]. Several methods such as hydrothermal synthesis
[4], thermophoresis-assisted vapor phase synthesis [5], and
sol–gel techniques [6] have been reported for the preparation
of Y2 O3 -doped CeO2 nanopowders.
In the present work, we have attempted a new method,
the microwave-induced combustion synthesis process, to
produce Y2 O3 -doped CeO2 nanopowders. Microwave-
processing of materials is fundamentally different from the
conventional processing due to its heating mechanism. In a
∗ (2) simple equipment units: complicated equipment units are
Corresponding author. Tel.: +886 5 206 3264; fax: +886 5 206 3264.
E-mail address: ypfu@wfc.edu.tw (Y.-P. Fu).
by the interaction of microwaves with the material. Whereas,
in conventional heating, the heat is generated by heating el-
ements and then it is transferred to the sample surfaces [7].
The microwave-induced combustion synthesis pro-
cess involves the dissolution of cerium nitrate hex-
ahydrate (Ce(NO3 )3 ·6H2 O), yttrium nitrate hexahydrate
(Y(NO3 )3 ·6H2 O), and urea (CO(NH2 )2 ) in water followed
by heating the solution in a microwave oven. The urea and
metal nitrate decompose and generate flammable gases such
as NH3 , HNCO, O2 , and NO. After the solution reaches the
point of spontaneous combustion, it burns and becomes a
solid which burns at the temperature over 1000 ◦ C. Com-
bustion is not complete until all the flammable substances
are consumed, and the resulting material is a loose, highly
friable substance exhibiting voids and pores formed by the
escaping gases during the combustion reaction [8]. The whole
process takes only a few minutes to yield Y2 O3 -doped CeO2
nanopowders.
The advantages of microwave-induced combustion pro-
cess are (1) simplicity: the reactions take only a few minutes,
not like the other methods that require tedious processes;
not needed in this method; (3) cheap source: all the materi-

0925-8388/$ – see front matter © 2004 Elsevier B.V. All rights reserved.
doi:10.1016/j.jallcom.2004.05.088
166 Y.-P. Fu, C.-H. Lin / Journal of Alloys and Compounds 389 (2005) 165–168

als used in this method are cheap, unlike special materials

needed in sol–gel process. In this study, nano-scale pow-
ders of Y2 O3 -doped CeO2 of the size range 19–25 nm are
prepared by microwave-induced combustion synthesis pro-
cess. The CeO2 powders doped with various amount of Y2 O3
amount are further characterized by TG/DTA, XRD, TEM,
and BET measurements.

2. Experimental procedures

2.1. Sample synthesis

The synthetic process involved the combustion of redox

mixtures, in which the metal nitrate acted as an oxidizing
reactant and urea as a reducing agent. The initial composi-
tion of the solution containing cerium nitrate, yttrium nitrate
hexahydrate, and urea was based on the total oxidizing and
reducing valences of the oxidizer and the fuel using the con-
cepts of propellant chemistry [9].
Stoichiometric amounts of cerium nitrate
hexahydrate(Ce(NO3 )3 ·6H2 O), yttrium nitrate hexahy-
drate (Y(NO3 )3 ·6H2 O), and urea (CO(NH2 )2 ) dissolved in
a minimum quantity of water, were placed in a crucible.
The crucible containing the solution was introduced into
a microwave oven (CEM, MDS 81D, 650W). Initially, the
solution boiled and underwent dehydration followed by
the decomposition with the evolution of large amounts of
gases (N2 , NH3 , and HNCO). The solution, upon reaching
the spontaneous combustion point, it vaporized yielding a
solid which burned at the temperature over 1000 ◦ C. The
entire combustion process of Y2 O3 -doped CeO2 powders in
a microwave oven took only 15 min.
Fig. 1. DTA/TG curves for CeO2 powders doping with 1 mol% Y2 O3 pre-
pared by microwave-induced combustion process.
3. Results and discussion
Phase transformation of as-received CeO2 powders doped
with 1 mol% Y2 O3 was studied by using DTA/TG mea-
surements. Fig. 1 shows the DTA/TG curves for as-received
CeO2 powders doped with 1 mol% Y2 O3 . Similar DTA/TG
curves were also observed in CeO2 powders that are doped
with various amounts of Y2 O3 . The TG/DTA data of CeO2
doped with 1 mol% Y2 O3 shows one exothermic peak be-
tween 250–300 ◦ C and 2–3 wt.% loss in the TG curve, which
is associated with the redox reactions of the organic matter
involved urea. The sharp weight loss before 100 ◦ C are due to
water loss. From 100 to 500 ◦ C, it shows about 3–4 wt.% loss
in TG curve may be attributed to the combustion of organic
matter. This is agreement with DTA curve, which shows one
exothermic peak at 270 ◦ C. Finally, the weight of as-prepared

2.2. Characterization measurements

A computer-interfaced X-ray powder diffractometer

(XRD) with Cu K␣ radiation (Rigaku D/Max-II) was used
to identify the crystalline phase. Differential thermal anal-
ysis and thermogravimetry (TG/DTA, Rigaku Thermalplus
TG 8120) were used to study the exo–endo temperature of
as-received CeO2 powders doped with 1 mol% Y2 O3 . A heat-
ing rate of 10 ◦ C/min was used in both the DTA and TG
measurements up to 1000 ◦ C in air. BET surface area mea-
surements were made by nitrogen adsorption employing a
Micromeritics ASAP 2000 instrument and calculated using
the five points Brunauer–Emmit–Teller (BET) theory. Mean
particle size (DBET ) was calculated from the BET data ac-
cording to DBET = 6/[ρth SBET ], where SBET is the measured
surface area and ρth is the theoretical density of the com- Fig. 2. XRD patterns of ultrafine CeO2 prepared by microwave-induced
pound [10]. The morphological features of the particle were combustion processing for (a) the undoped powder; (b) the powder doping
with 1 mol% Y2 O3 ; (c) the powder doping with 3 mol% Y2 O3 ; (d) the powder
examined by transmission electron microscope (TEM, JOEL doping with 5 mol% Y2 O3 ; (e) the powder doping with 7 mol% Y2 O3 ; (f)
JEM-200CX) with an accelerating voltage of 200 kV. the powder doping with 9 mol% Y2 O3 .
 Y.-P. Fu, C.-H. Lin / Journal of Alloys and Compounds 389 (2005) 165–168 167

Table 1 cooling rate. It can be found that the XRD peaks are quite
Properties of CeO2 and Y2 O3 -doped CeO2 sample broad and indicate the fine particle of the product. The parti-
Y2 O3 -doped Surface area Particle sizea Crystallite sizeb cle size, DXRD was calculated according to Scherer equation
amount (mol%) (m2 /g) (nm) (nm) [11]: DXRD = 0.9λ/B cos θ, where λ is the wavelength of the
0 43.47 19.14 16.18 radiation, θ is the diffraction angle, and B is the corrected
1 37.18 22.38 14.62 half-width of the diffraction peak, given by B2 = Bm 2 − B2 ,
s
3 38.55 21.57 15.57
5 35.88 23.18 15.34
here Bm is the measured half-width of the diffraction peak
7 33.26 25.01 16.36 and Bs is the half-width of a standard CeO2 with a crystal
9 33.72 24.66 14.89 size greater than 100 nm. The reflection from (1 1 1) plane,
a Particle size measured from specific surface area. occurring at 28.6◦ 2θ, was used to calculate the crystallite
b Crystallite size measured from XRD line broadening. size. The particle size determined from the broadened peak
is about 14–16 nm in CeO2 and Y2 O3 -doped CeO2 samples.
CeO2 powder doped with 1 mol% Y2 O3 appears to be con- When using the Scherer equation, we assume that the particle
stant for temperatures above 550 ◦ C. It indicates that Y2 O3 - size effects are the only source of peak broadening; however,
doped CeO2 nanopowders are formed completely without if compositional non-uniformity occurs in particles, the par-
any impurities including organic matters and un-reacted ni- ticle size will be underestimated.
trate. Fig. 3 shows the transmission electron micrographs of
The X-ray diffraction patterns of the Y2 O3 -doped CeO2 CeO2 doped with different amounts of Y2 O3 specimens,
powders prepared by microwave-induced combustion pro- which have a very broad distribution of particle size and form
cess were identical. Fig. 2 shows that the CeO2 and Y2 O3 - particle agglomerates. The van der Waals force can be re-
doped CeO2 powders contain only the cubic fluorite struc- sponsible for the formation of agglomerates of Y2 O3 -doped
ture. The formation of single phase is due to the high in CeO2 powders. The broad particle size distribution was prob-
situ temperature generated during combustion and the rapid ably due to the occurrence of local combustion, as shown

Fig. 3. Transmission electron micrograph of CeO2 powder (a) doping with 1 mol% Y2 O3 ; (b) doping with 5 mol% Y2 O3 ; (c) doping with 9 mol% Y2 O3 ; (d)
electron diffraction pattern of CeO2 powder doping with 5 mol% Y2 O3 .
168 Y.-P. Fu, C.-H. Lin / Journal of Alloys and Compounds 389 (2005) 165–168
in Fig. 3(a)–(c), the CeO2 powder doped with 1, 5, 9 mol%
Y2 O3 shows that the particle sizes are very small, and the
average particle size ranges from 20 to 30 nm. The particle
size obtained by TEM does not depend on the amount of yt-
trium dopant. As shown in Fig. 3(d), the electron diffraction
patterns of CeO2 powder doping with 5 mol% Y2 O3 shows
ring patterns, revealing poly-crystallinity of individual crys-
tallites and also confirm the formation of cubic fluorite struc-
ture. This result is in good agreement with the XRD pattern.
Table 1 summarizes the data of surface area, particle size, and
crystallite size of the Y2 O3 -doped CeO2 powder with differ-
ent yttrium contents, prepared by the microwave-induced pro-
cess. Mean particle size, DBET was calculated from the BET
data according to DBET = 6/[ρth SBET ]. In this equation, we as-
sume that all particles are spheres. The particle size calculated
from specific surface area of the powders range from 19 to
25 nm and does not depend on the amount of yttrium dopant.
4. Conclusions
Recently, Y2 O3 -doped CeO2 powders have been widely
studied due to its importance in solid oxide fuel cells. In
this study, using cerium nitrate, yttrium nitrate hexahydrate,
and urea as starting materials, nano-sized Y2 O3 -doped CeO2
powders have been synthesized successfully by microwave-
induced combustion process. The synthesized CeO2 pow-
ders with various amounts of Y2 O3 dopant reveal that the
particle size ranged from 19 to 25 nm, crystallite size var-
ied from 14 to 16 nm with the specific surface area is about
33–43 m2 /g.
References
[1] H. Hahn, J. Mater. Res. 5 (1990) 609.
[2] Y.C. Zhou, M.N. Rahaman, J. Mater. Res. 8 (1993) 1680.
[3] N.Q. Minh, J. Am. Ceram. Soc. 76 (3) (1993) 563.
[4] K. Yamashita, K.V. Ramanujachary, M. Greenblatt, Solid State Ionic
81 (1995) 53.
[5] W. Bai, K.L. Choy, N.H.J. Stelzer, J. Schoonman, Solid State Ionics
116 (1999) 225.
[6] X. Luo, B. Zhu, C. Xia, G.A. Niklasson, C.G. Granqvist, Solar
Energy Mater. Solar Cell 53 (1998) 341.
[7] D.E. Clark, W.H. Sutton, Ann. Rev. Mater. Sci. 26 (1996) 299.
[8] O.A. Lopez, J. McKittrick, L.E. Shea, J. Lumin. 71 (1997) 1.
[9] S.R. Jain, K.C. Adiga, V.R.P. Verneker, Comb. Flam. 40 (1981) 71.
[10] R. Doshi, C.B. Alock, J.J. Carberry, Catal. Lett. 18 (1993) 337.
[11] H.P. Klug, L.E. Alexander, X-Ray Diffraction Procedures, second
ed., Wiley, New York, 1974.