PRODUCT ENGINEERING AND CHEMICAL TECHNOLOGY

Chinese Journal of Chemical Engineering, 19(6) 1047ü1051 (2011)

Preparation of Nano-MnFe2O4 and Its Catalytic Performance of

Thermal Decomposition of Ammonium Perchlorate*

HAN Aijun (‫**)ࢋ̙ۂ‬, LIAO Juanjuan (ॷࡹࡹ), YE Mingquan (ྜྷੜ௥), LI Yan (हཀྵ) and
PENG Xinhua (଎໭‫)ܟ‬
School of Chemical Engineering, Nanjing University of Science and Technology, Nanjing 210094, China

Abstract Nano-MnFe2O4 particles were synthesized by co-precipitation phase inversion method and low-temperature
combustion method respectively, using MnCl2, FeCl3, Mn(NO3)2, Fe(NO3)3, NaOH and C6H8O7. X-ray diffraction
(XRD), transmission electron microscope (TEM), Fourier transform infrared spectroscopy (FT-IR), thermogravim-
etry-differential thermal analysis (TG-DTA) and differential scanning calorimetry (DSC) were used to characterize
the structure, morphology, thermal stability of MnFe2O4 and its catalytic performance to ammonium perchlorate.
Results showed that single-phased and uniform spinel MnFe2O4 was obtained. The average particle size was about
30 and 20 nm. The infrared absorption peaks appeared at about 420 and 574 cm1, and the particles were stable be-
low 524 °C. Using the two prepared catalysts, the higher thermal decomposition temperature of ammonium per-
chlorate was decreased by 77.3 and 84.9 °C respectively, while the apparent decomposition heat was increased by
482.5 and 574.3 J·g1. The catalytic mechanism could be explained by the favorable electron transfer space pro-
vided by outer d orbit of transition metal ions and the high specific surface absorption effect of MnFe2O4 particles.
Keywords MnFe2O4, co-precipitation phase inversion method, low-temperature combustion method, ammonium
perchlorate, catalysis

1 INTRODUCTION chemical methods, such as microemulsion method,

Ammonium perchlorate (AP), as the important
high energy ingredient of solid propellants in the na-
tional defense field, occupies a large proportion in the
formula. The thermal decomposition of AP can di-
rectly affect the burning velocity and energy features
of propellants. Therefore, an extensive study on the
thermal decomposition of AP was carried out by re-
searchers [1]. Result shows that a small amount of
catalyst can reduce the thermal decomposition tem-
perature of AP, especially the higher pyrolytic tem-
perature, increase apparent decomposition heat of AP,
so as to improve the burning velocity and efficiency of
propellant. Up till now, many scholars have achieved
certain results on the catalytic performance of Co3O4,
Fe2O3, NiO, PbO, CuO and other metal oxide powders
[16]. MnFe2O4 is a composite metal oxide with two
transition metal elements in its formula and it is com-
patible with other components in propellant. However,
the catalytic performance of MnFe2O4 to thermal de-
composition of AP has not been reported yet.
MnFe2O4 is a composite spinel material with cu-
bic and face-centered lattice structure. Transition
metal elements Mn and Fe lie in the tetrahedral and
octahedral gap, and there are strong ionic bonds with
the same intensity, force, thermal conductivity and
thermal expansion between the metal ion and oxygen
ion. Owing to the particularity of the element nature
and the crystal structure, MnFe2O4 has been widely
used in coating, magnetic recording media, catalysis
and many other fields [7, 8].
Now MnFe2O4 is commonly prepared by soft
hydrothermal method, sol-gel method and co-precipitation
method [914]. Due to the low cost, convenient opera-
tion, small particle size and potential of industrializa-
tion, the co-precipitation phase inversion method and
low-temperature combustion method are known to
have a good application prospect. Moreover, the reports
on MnFe2O4 prepared by these two methods have not
been seen as yet. In this paper, co-precipitation phase
inversion method and low-temperature combustion
method will be adopted to prepare MnFe2O4 samples.
The structure and composition, particle size, morphol-
ogy, infrared characteristics, thermal stability of sam-
ples and their catalytic performance to thermal decom-
position of AP are studied, and a preliminary analysis
of catalytic mechanism is conducted, in order to ex-
plore a new catalyst to thermal decomposition of AP.
2 EXPERIMENTAL
2.1 Preparation
2.1.1 Sample prepared by co-precipitation phase
inversion method
MnCl2·4H2O and FeCl3·6H2O were taken in mo-
lar ratio of Mn2+ΉFe3+ 1Ή2 to prepare 0.3 mol·L1
metal ion solution of 100 ml containing 0.1 mol·L1
Mn2+ and 0.2 mol·L1 Fe3+, which was then dropped
slowly into 100 ml NaOH solution of 3 mol·L1 at the
preheated temperature of 95 °C. After aging for 2 h
with continuous stirring. the solution was filtered,
washed and dried at 60 °C for 12 h to get sample A.
All reagents used in this study are of analytical grade.

Received 2011-05-12, accepted 2011-11-03.

* Supported by the National Natural Science Foundation of China (90305008, 51077072).
** To whom correspondence should be addressed. E-mail: gjchaoxi@yahoo.com.cn
1048 Chin. J. Chem. Eng., Vol. 19, No. 6, December 2011
2.1.2 Sample prepared by low-temperature combus-
tion method
Mn(NO3)2 and Fe(NO3)3ǜ9H2O were taken in
molar ratio of Mn2+ΉFe3+ 1 : 2 to form 50 ml nitrate
solution (0.3 mol·L1), which was then dropped slowly
into the prepared citric acid (0.3 mol·L1) of pH 5
with continuous stirring. Molar ratio of total metal
ions and citric acid was kept 1Ή1, chelating for 2 h at
60 °C. Next, water was evaporated to form a dry gel,
then it was treated in a muffle furnace at 450 °C for
1 h to get sample B. All reagents used in this study are
of analytical grade.
2.2 Characterization
The crystal structure and composition of the
samples were characterized by Bruker’s D8 Advance
X-ray diffraction (using Cu-target, KĮ, 1.5406×1010 m,
2ș, 15°70°). The morphological analysis was per-
formed with Tecnai-12 transmission electron micro-
scope (Philips). The thermal stability was tested by
TG-DTA-50 thermo gravimetric differential thermal
analysis (Shimadzu, Japan, heating rate 20 °C·min1
and temperature from 50 °C to 1000 °C) and the FT-IR
features was characterized by FTIR-8400S Fourier
transform infrared spectrometer (Shimadzu, Japan).
2.3 Catalytic performance to thermal decomposi-
tion of AP
AP and the prepared samples were taken in mass
ratio of 97Ή3, and then blended and grinded in a cer-
tain amount of ethanol. After the volatilization of
ethanol, the thermal decomposition analysis was car-
ried out by DSC-823e (Mettler Toledo, Swiss). The
temperature ranges from 50 to 500 °C with the heating
rate 20 °C·min1 and the flow rate of N2 20 ml·min1,
the catalytic activity of samples was measured by the
changes of decomposition temperature and the appar-
ent decomposition heat of AP.
3 RESULTS AND DISCUSSION
3.1 Phase analysis
XRD patterns of samples A and B are presented
as curves 1 and 2 in Fig. 1. It can be found that dif-
fraction peaks appear at (111), (220), (311), (400),
(511) and (440) planes in both curves 1 and 2. Com-
pared with the standard PDF (Portable Document
Format) card, they are recognized as the diffraction
peaks of spinel MnFe2O4 (Joint Committee on Powder
Diffraction Standards No. 10-0319), indicating that
single phase spinel MnFe2O4 can be prepared by the
above two methods.
Using the co-precipitation phase inversion
method, Fe(OH)3 was first formed, then į-FeOOH
was generated [15], and part of Fe3+ in į-FeOOH
was easy to be replaced by Mn2+ to get [(Mn2+)
Figure 1 XRD patterns of nano-MnFe2O4
1üsample A ; 2üsample B
(Fe3+)2(OH)4(O2)2], Finally MnFe2O4 was generated
by aging [16, 17] in aqueous solution. The crystal nu-
cleus grew and the lattice improved gradually under
certain conditions, which results a high crystallinity
and regular arrangement of the internal particles. So
the intensity of crystal diffraction peak in curve 1 is
higher and the peak shape is sharp and symmetrical.
Homogeneous dry gel was first formed using cit-
ric acid and metal nitrate by the low temperature
combustion method, then the dry gel was ignited and
combusted quickly to get MnFe2O4. The particle size
of the synthesized sample is small and in narrow dis-
tribution because of the good homogeneity of mixture
of raw materials. However, the sample prepared by
low temperature combustion method has a low crys-
tallinity, and crystal dislocations and defects exist in
the crystal of the sample, because of the relatively
short reaction time. Therefore, the intensity of crystal
diffraction peak in curve 2 is weaker and the peak
shape is relatively broad.
3.2 Morphology analysis
The TEM images of sample A and B are pre-
sented in Fig. 2. The particles are cube-shaped corre-
sponding to the cubic crystal system and they have
regular morphology, uniform size and good dispersion.
The average particle size of samples A and B is about
30 and 20 nm respectively.
3.3 FT-IR analysis
The FT-IR spectra of sample A and B correspond
respectively to curves 1 and 2 as presented in Fig. 3. It
is clear that there is no large difference in the infrared
spectra between two samples. According to the struc-
ture analysis of spinel MnFe2O4, M2+ (such as Mg2+,
Mn2+, Ni2+) occupies the Td symmetrical position, Fe3+
and O2 occupy the molecular position of D3d and C3v
respectively. There are a total of 13 vibration freedom
degrees in the molecule, of which four are infrared
active and all of them are represented as F1u. More-
over, two high-frequency (ȣ1, ȣ2) IR absorption peaks
appear at 600400 cm1 [18]. Hence the absorption
peak about 420 and 574 cm1 of the two samples can
 Chin. J. Chem. Eng., Vol. 19, No. 6, December 2011 1049

(a) Sample A (b) Sample B

Figure 2 TEM images of nano-MnFe2O4

Figure 3 IR spectra of nano-MnFe2O4

1üsample A; 2üsample B
(a) Sample A

be identified as the infrared absorption peaks of

MnFe2O4. But the attribution of each characteristic
absorption peak is still controversial. As each O2 is
shared by a tetrahedral cation and three octahedral
cations, the vibration of O2 can not only belong to
tetrahedral or octahedral. Bujoreanu and Segal’s study
1
[19] shows that the absorption peak at 600400 cm
of MnFe2O4 mainly depends on the vibration of the
octahedral group. In addition, there is a wider peak at
574 cm1 of curve 2 with low absorption intensity,
which belongs to the decreased molecular vibrational
probability and vibrational dipole moment caused by
the low crystallinity, crystal dislocations and defects (b) Sample B
of MnFe2O4 prepared by low temperature combustion
method. Figure 4 TG-DTA curves of nano-MnFe2O4

3.4 TG-DTA analysis endothermic peak located at about 300 °C is caused by

The TG-DTA curves of samples A and B are pre-
sented in Fig. 4, which can be used to characterize the
thermal stability of the samples. The thermal stability
of two samples is almost the same. It can be seen from
TG that there is no mass loss below 792 °C. Small
endothermic peaks appear at 524 °C and 527 °C
corresponding to samples A and B in DTA curves
while intensive endothermic peaks appear at 792 °C
and 793 °C, respectively. Chen et al. [20] show that the
the crystal structure change of MnFe2O4, which is
driven by the distribution change of manganese cation
in tetrahedral and octahedral. However, the tempera-
ture is not high enough to generate new materials.
According to the study of Bonsdorf et al. [21], at this
point the MnFe2O4 lattice is metastable. In Ref. [22], it
can be seen from the XRD patterns of samples cal-
cined in muffle furnace at different temperatures that
the intensity of diffraction peak of MnFe2O4 becomes
weaker and the crystallinity is decreased with increasing
1050 Chin. J. Chem. Eng., Vol. 19, No. 6, December 2011
temperature. The characteristic peaks of Į-Fe2O3 and
Į-Mn2O3 appear until 800 °C, indicating that the in-
tensive endothermic peak at about 793 °C is caused by
the partial decomposition of MnFe2O4 to Į-Mn2O3 and
Į-Fe2O3. Therefore, it can be known that the prepared
MnFe2O4 shows a good thermal stability below 524 °C
and it can be used as the catalyst to thermal decompo-
sition of AP below that temperature.
3.5 Evaluation of catalytic performance
3.5.1 Characterization of the catalytic performance
of the samples to AP
The thermal decomposition of pure AP can be di-
vided into three stages [23]. The first stage corresponds
to the phase transition endothermic process of AP,
which transforms from orthorhombic to cubic crystal
with the temperature ranging from 240 to 250 °C. The
second stage corresponds to the low-temperature de-
composition exothermic process of AP with the tem-
perature ranging from 300 to 330 °C. The third stage
corresponds to the higher temperature decomposition
exothermic process of AP with the temperature rang-
ing from 420 to 480 °C.
Curves 1, 2 and 3 in Fig. 5 correspond to the dif-
ferential scanning calorimetry (DSC) curves for pure
AP, AP added sample A, and AP added sample B. It
can be seen from the graph that the higher thermal
decomposition temperature in curves 2 and 3 are
352.9 and 345.3 °C, respectively, decreased by 77.3
and 84.9 °C compared with pure AP (430.2 °C). The
low-temperature exothermic decomposition peaks
( 289.2 and 284.6 °C) overlap with the higher tem-
perature exothermic decomposition peak, and are not
obvious in Fig. 5 owing to the large decreased tem-
perature of the higher temperature decomposition peak.
Moreover, the crystal transition temperatures locate at
near 247 °C with no significant change. The DSC re-
sults also show that the apparent decomposition heat
of AP added samples A or B are 1071.9 or 1163.7 J·g1
respectively, increasing greatly by 482.5 or 574.3 J·g1
compared with pure AP (589.4 J·g1).
Figure 5 DSC curves of AP catalyzed by nano-MnFe2O4
1üAP; 2üAP + sample A; 3üAP + sample B
Therefore, both MnFe2O4 samples show good
catalytic performance to the thermal decomposition of
AP and are better than nano metal Ni [24], nano alloy
NiB [25] and nano metal oxide Fe2O3 [26]. MnFe2O4
prepared by low-temperature combustion method
shows better catalytic activity.
3.5.2 Catalytic mechanism analysis
A great deal of research on the thermal decompo-
sition mechanism of AP has been done in recent years
[2729]. The catalytic mechanism of MnFe2O4 to the
thermal decomposition of AP lies in the following two
aspects: Firstly, both transition metal ions Mn2+ and
Fe3+ in the structure of MnFe2O4 have outer d orbital
with 3d5 electronic configurations, and the d orbitals
are not filled with electrons and have hole conductiv-
ity. By accepting electrons transferred from the deg-
radation process of ClO4, their own hole annihilation
is achieved, which objectively provides a useful space
to the electron transfer in the thermal decomposition
of AP, serves a bridge role and promotes the degrada-
tion of ClO4. Secondly, owing to the high specific
surface area and large amount of surface active sites
of nano-MnFe2O4 particle, it is easy to adsorb gas
phase redox reaction molecules to their surface, which
promotes redox reactions between them.
Nano-MnFe2O4 crystal shows good catalytic ef-
fects by promoting the two key steps of AP thermal
decomposition. Nano-MnFe2O4 prepared by low tem-
perature combustion method shows better catalytic
activity due to its smaller particle size.
4 CONCLUSIONS
Regular cube-shaped and single-phase spinel
MnFe2O4 samples were synthesized by co-precipitation
phase inversion method and low temperature combus-
tion method respectively, with the average particle
size of about 30 and 20 nm. In FTIR spectra, vibra-
tional absorption peaks appear at about 420 and 574
cm1. The synthesized MnFe2O4 was thermally stable
below 524 °C. Nano-MnFe2O4 particles synthesized
by the two methods decreased the higher thermal de-
composition temperature of AP by 77.3 and 84.9 °C
and increased the exothermic quantity of decomposi-
tion by 482.5 and 574.3 J·g1 respectively, showing
good catalytic effect on AP decomposition. MnFe2O4
synthesized by low temperature combustion method
showed better catalytic activity due to its smaller par-
ticle size.
REFERENCES
1 Chen, W.F., Li, F.S., Liu, J.X., “Preparation of nanocrystalline Co3O4
and its catalytic performance for thermal decomposition of ammonium
perchlorate”, J. Catal., 26 (12), 10731077 (2005). (in Chinese)
2 Ma, Z.Y., Li, F.S., Cui, P., Bai, H.P., “Preparation of nanocrystalline
Fe3O4 and its catalytic performance for thermal decomposition of
ammonium perchlorate”, J. Catal., 24 (10), 795798 (2003). (in Chi-
nese)
3 Zhu, J.W., Chen, H.Q., Xie, B., Yang, X.J., Lu, L.D., Wang, X.,
“Preparation of nano crystalline Cu2O and its catalytic performance
for thermal decomposition of ammonium perchlorate”, J. Catal., 25
 Chin. J. Chem. Eng., Vol. 19, No. 6, December 2011
(8), 637640 (2004). (in Chinese)
4 Wang, Y., Zhu, J., Yang, X., “Preparation of NiO nanoparticles and
their catalytic activity in the thermal decomposition of ammonium
perchlorate”, Thermochim. Acta, 437, 106109 (2005).
5 Luo, Y.X., Lu, L.D., Wang, X., “Study of catalytic activity of
nanocrystalline transition metal oxides on NH4ClO4”, J. Energ. Ma-
ter., 10 (4), 148152 (2002). (in Chinese)
6 Castiglioni, G., Minelli, G., Porta, P., Vaccari, A., “Synthesis and
properties of spinel-type Co-Cu-Mg-Zn-Cr mixed oxides”, Solid
State Chem., 152, 526532 (2000).
7 Zakharchenko, N., “Catalytic properties of the Fe2O3-MnO system
for ammonia oxidation”, Kinet. Catal, 42 (5), 747753 (2001).
8 Muroi, M., Street, R., McCormick, P., “Magnetic properties of ul-
trafine MnFe2O4 powders prepared by mechanochemical process-
ing”, Phys. Rev. B, 63, 184414 (2001).
9 Botta, P., Bercoff, P., Aglietti, E., “Magnetic and structural study of
mechano chemical reactions in the Al-Fe3O4 system”, J. Mater. Sci.,
37, 25632568 (2002).
10 Zhen, L., He, K., Xu, C., “Synthesis and characterization of sin-
gle-crystalline MnFe2O4 nanorods via a surfacetant free hydrother-
mal route”, J. Magn. Mater., 320, 26722675 (2008).
11 Gajbhiye, N., Balaji, G., “Synthesis, reactivity, and cations inversion
studies of nanocrystalline MnFe2O4 particles”, Thermochim. Acta,
85, 143151 (2002).
12 Yang, G.S., Shi, J.H., Li, J.H., Wang, P., Yao, S.J., “Phase behavior
and structural transitions in sodium dodecyl sulfonate microemul-
sions”, Chin. J. Chem. Eng., 10 (6), 670672 (2002).
13 Zhou, Y.S., Jiang, G.W., “Study on properties of composite oxides
TiO2/SiO2”, Chin. J. Chem. Eng., 10 (3), 349353 (2002).
14 Yin, Q.X., Zhang, M.J., Wang, J.K., “Analyses of multiplicity and
stability patterns of agglomeration controlled precipitation with both
primary and secondary nucleations”, Chin. J. Chem. Eng., 10 (2),
202207 (2002).
15 Dou, Q.S., Zhang, H., Wu, J.B., Yang, D.R., “Synthesis and charac-
terization of Fe2O3 and FeOOH nanostructures prepared by ethylene
glycol assisted hydrothermal proeess”, J. Inorg. Mater., 22 (2),
213218 (2007). (in Chinese)
16 Tatsuo, I., Wataru, S., Akemi, Y., Kazuhiko, K., “Pore structures of
the thermal decomposition products of FeOOH particles doped with
Ni (II), Co (II) and Cu (II)”, Colloids Surfaces, 136, 183190 (1998).
17 Jiménez Mateos, J.M., Macías, M., Morales, J., Tirado, J.L., “Mn
1051
and Co substitution į-FeOOH and its decomposition products”, J.
Mater. Sci., 25, 52075214 (1990).
18 Shi, X., Wang, G., Li, C., “Preparation of ferrite ultrafine particle
catalysts by sol-gelmethod”, Chem. Res. Appl., 14 (5), 531533
(2002). (in Chinese)
19 Bujoreanu, V., Segal, E., Brezeanu, M., “On the formation of man-
ganese ferrite from MnO2 and FeSO4·7H2O aqueous solutions
through coprecipitation”, Thermochim. Acta, 288, 221237 (1996).
20 Chen, J., Sorensen, C., Klabunde, J., “Size-dependent magnetic
properties of MnFe2O4 fine particles synthesized by coprecipitation”,
Phys. Rev. B, 54 (13), 92889296 (1996).
21 Bonsdorf, G., Deneckeb, M., Christen, S., “X-ray absorption spec-
troscopic and Mössbauer studies of redox and cation-ordering proc-
esses in manganese ferrite”, Solid State Ionics., 101, 351357 (1997).
22 Zhang, W., “Synthesis and properties research of spinel iron acid
manganese materials”, M.A. Thesis, School of Chemical Engineer-
ing, Nanjing University of Science and Technology, Nanjing (2010).
(in Chinese)
23 Boldyrev, V., “Thermal decomposition of ammonium perchlorate”,
Thermochim. Acta, 443, 136 (2006).
24 Li, R., Liu, X.X., Wang, X.J., “Preparation of Ni and Ni-P nanopar-
ticles and their catalytic effect on the decomposition of ammonium
perchlorate”, Initiators Pyro. Techn., 4, 1518 (2008). (in Chinese)
25 Yang, Y., Pan, Z.H., Li, L.X., Li, Y.B., Cao, X.F., “Preparation of
nanometer NiB/Al composite and its thermal catalysis effect on AP
decomposition”, Chinese Journal of Energetic Materials, 17 (4),
446450 (2009). (in Chinese)
26 Lin, B.L., Bu, J.J., Zheng, H.Y., Zhao, W.Z., “Preparation and catalytic
performance on ammonium perchlorate decomposition of Fe2O3
nanoparticles”, Chemical Defence on Ships, 4, 1215 (2009). (in
Chinese)
27 Duan, H.Z., Lin, X.Y., Liu, G.P., Xu, L., Li, F.S., “Synthesis of Co
nanoparticles and their catalytic effect on the decomposition of am-
monium perchlorate”, Chin. J. Chem. Eng., 16 (2), 325328 (2008).
28 Sergey, V., Charles, A.W., “Kinetics of thermal decomposition of
cubic ammonium perchlorate”, Chem. Mater., 11 (11), 33863393
(1999).
29 Fan, X.Z., Li, J.Z., Fu, X.L., Wang, H., “Thermal decompositions of
ammonium perchlorate of various granularities”, Acta Chim. Sinica,
67 (1), 3944 (2009).