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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
2.2 Characterization
(Fe3+)2(OH)4(O2)2], Finally MnFe2O4 was generated
by aging [16, 17] in aqueous solution. The crystal nu-
The crystal structure and composition of the cleus grew and the lattice improved gradually under
samples were characterized by Bruker’s D8 Advance certain conditions, which results a high crystallinity
X-ray diffraction (using Cu-target, KĮ, 1.5406×1010 m, and regular arrangement of the internal particles. So
2ș, 15°70°). The morphological analysis was per- the intensity of crystal diffraction peak in curve 1 is
formed with Tecnai-12 transmission electron micro- higher and the peak shape is sharp and symmetrical.
scope (Philips). The thermal stability was tested by Homogeneous dry gel was first formed using cit-
TG-DTA-50 thermo gravimetric differential thermal ric acid and metal nitrate by the low temperature
analysis (Shimadzu, Japan, heating rate 20 °C·min1 combustion method, then the dry gel was ignited and
and temperature from 50 °C to 1000 °C) and the FT-IR combusted quickly to get MnFe2O4. The particle size
features was characterized by FTIR-8400S Fourier of the synthesized sample is small and in narrow dis-
transform infrared spectrometer (Shimadzu, Japan). tribution because of the good homogeneity of mixture
of raw materials. However, the sample prepared by
2.3 Catalytic performance to thermal decomposi- low temperature combustion method has a low crys-
tion of AP tallinity, and crystal dislocations and defects exist in
the crystal of the sample, because of the relatively
AP and the prepared samples were taken in mass short reaction time. Therefore, the intensity of crystal
ratio of 97Ή3, and then blended and grinded in a cer- diffraction peak in curve 2 is weaker and the peak
tain amount of ethanol. After the volatilization of shape is relatively broad.
ethanol, the thermal decomposition analysis was car-
ried out by DSC-823e (Mettler Toledo, Swiss). The 3.2 Morphology analysis
temperature ranges from 50 to 500 °C with the heating
rate 20 °C·min1 and the flow rate of N2 20 ml·min1, The TEM images of sample A and B are pre-
the catalytic activity of samples was measured by the sented in Fig. 2. The particles are cube-shaped corre-
changes of decomposition temperature and the appar- sponding to the cubic crystal system and they have
ent decomposition heat of AP. regular morphology, uniform size and good dispersion.
The average particle size of samples A and B is about
3 RESULTS AND DISCUSSION 30 and 20 nm respectively.
3.1 Phase analysis
3.3 FT-IR analysis
XRD patterns of samples A and B are presented
as curves 1 and 2 in Fig. 1. It can be found that dif- The FT-IR spectra of sample A and B correspond
fraction peaks appear at (111), (220), (311), (400), respectively to curves 1 and 2 as presented in Fig. 3. It
(511) and (440) planes in both curves 1 and 2. Com- is clear that there is no large difference in the infrared
pared with the standard PDF (Portable Document spectra between two samples. According to the struc-
Format) card, they are recognized as the diffraction ture analysis of spinel MnFe2O4, M2+ (such as Mg2+,
peaks of spinel MnFe2O4 (Joint Committee on Powder Mn2+, Ni2+) occupies the Td symmetrical position, Fe3+
Diffraction Standards No. 10-0319), indicating that and O2 occupy the molecular position of D3d and C3v
single phase spinel MnFe2O4 can be prepared by the respectively. There are a total of 13 vibration freedom
above two methods. degrees in the molecule, of which four are infrared
Using the co-precipitation phase inversion active and all of them are represented as F1u. More-
method, Fe(OH)3 was first formed, then į-FeOOH over, two high-frequency (ȣ1, ȣ2) IR absorption peaks
was generated [15], and part of Fe3+ in į-FeOOH appear at 600400 cm1 [18]. Hence the absorption
was easy to be replaced by Mn2+ to get [(Mn2+) peak about 420 and 574 cm1 of the two samples can
Chin. J. Chem. Eng., Vol. 19, No. 6, December 2011 1049
temperature. The characteristic peaks of Į-Fe2O3 and AP and are better than nano metal Ni [24], nano alloy
Į-Mn2O3 appear until 800 °C, indicating that the in- NiB [25] and nano metal oxide Fe2O3 [26]. MnFe2O4
tensive endothermic peak at about 793 °C is caused by prepared by low-temperature combustion method
the partial decomposition of MnFe2O4 to Į-Mn2O3 and shows better catalytic activity.
Į-Fe2O3. Therefore, it can be known that the prepared
MnFe2O4 shows a good thermal stability below 524 °C 3.5.2 Catalytic mechanism analysis
and it can be used as the catalyst to thermal decompo- A great deal of research on the thermal decompo-
sition of AP below that temperature. 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
3.5 Evaluation of catalytic performance aspects: Firstly, both transition metal ions Mn2+ and
3.5.1 Characterization of the catalytic performance Fe3+ in the structure of MnFe2O4 have outer d orbital
of the samples to AP with 3d5 electronic configurations, and the d orbitals
The thermal decomposition of pure AP can be di- are not filled with electrons and have hole conductiv-
vided into three stages [23]. The first stage corresponds ity. By accepting electrons transferred from the deg-
to the phase transition endothermic process of AP, radation process of ClO4, their own hole annihilation
which transforms from orthorhombic to cubic crystal is achieved, which objectively provides a useful space
with the temperature ranging from 240 to 250 °C. The to the electron transfer in the thermal decomposition
second stage corresponds to the low-temperature de- of AP, serves a bridge role and promotes the degrada-
composition exothermic process of AP with the tem- tion of ClO4. Secondly, owing to the high specific
perature ranging from 300 to 330 °C. The third stage surface area and large amount of surface active sites
corresponds to the higher temperature decomposition of nano-MnFe2O4 particle, it is easy to adsorb gas
exothermic process of AP with the temperature rang- phase redox reaction molecules to their surface, which
ing from 420 to 480 °C. promotes redox reactions between them.
Curves 1, 2 and 3 in Fig. 5 correspond to the dif- Nano-MnFe2O4 crystal shows good catalytic ef-
ferential scanning calorimetry (DSC) curves for pure fects by promoting the two key steps of AP thermal
AP, AP added sample A, and AP added sample B. It decomposition. Nano-MnFe2O4 prepared by low tem-
can be seen from the graph that the higher thermal perature combustion method shows better catalytic
decomposition temperature in curves 2 and 3 are activity due to its smaller particle size.
352.9 and 345.3 °C, respectively, decreased by 77.3
and 84.9 °C compared with pure AP (430.2 °C). The 4 CONCLUSIONS
low-temperature exothermic decomposition peaks
( 289.2 and 284.6 °C) overlap with the higher tem- Regular cube-shaped and single-phase spinel
perature exothermic decomposition peak, and are not MnFe2O4 samples were synthesized by co-precipitation
obvious in Fig. 5 owing to the large decreased tem- phase inversion method and low temperature combus-
perature of the higher temperature decomposition peak. tion method respectively, with the average particle
Moreover, the crystal transition temperatures locate at size of about 30 and 20 nm. In FTIR spectra, vibra-
near 247 °C with no significant change. The DSC re- tional absorption peaks appear at about 420 and 574
sults also show that the apparent decomposition heat cm1. The synthesized MnFe2O4 was thermally stable
of AP added samples A or B are 1071.9 or 1163.7 J·g1 below 524 °C. Nano-MnFe2O4 particles synthesized
respectively, increasing greatly by 482.5 or 574.3 J·g1 by the two methods decreased the higher thermal de-
compared with pure AP (589.4 J·g1). 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.
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