Preparation and catalytic activity comparison of Porous NiO, Co3O4 and NiCo2O4 superstructures on the thermal decomposition of ammonium perchlorate

Article abstract of DOI:10.1166/jnn.2016.11635

Porous NiO, Co₃O₄ and NiCo2O4 superstructures were successfully prepared via a facile hydrothermal-annealing method. The products were characterized by powder X-ray diffraction (XRD), field-emission scanning electron microscopy (FESEM) and energy dispersive spectrometry (EDS). The Brunauer-Emmett-Teller surface area and pore volume of the products were measured by N₂ adsorption isotherms. The catalytic performance of the as-prepared porous NiO, Co₃O₄ and NiCo₂O₄ superstructures on the thermal decomposition of ammonium perchlorate (AP) was investigated by thermal gravimetric analysis and differential scanning calorimeter. The results showed Co₃O₄ superstructures were more effective than others for the thermal decomposition of AP and the thermal decomposition temperature of AP shifted downward about 136.2 °C. Furthermore, the catalytic mechanism of porous NiO, Co₃O₄ and NiCo2O4 superstructures on the thermal decomposition of AP was discussed.

Full text of DOI:10.1166/jnn.2016.11635

Article
Journal of
Nanoscience and Nanotechnology
Vol. 16, 8635–8639, 2016
Copyright © 2016 American Scientific Publishers
All rights reserved
Printed in the United States of America
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Preparation and Catalytic Activity Comparison of Porous
NiO, Co O and NiCo O Superstructures on the Thermal
3
4
2
4
Decomposition of Ammonium Perchlorate
1
1ꢀ∗
1
2ꢀ∗
Jian-Guo Wang , Li-Na Jin , Xin-Ye Qian , and Ming-Dong Dong
1Institute for Advanced Materials, and School of Materials Science and Engineering,
Jiangsu University, Zhenjiang 212013, China
Center for DNA Nanotechnology (CDNA), Interdisciplinary Nanoscience Center (iNANO),
2
Aarhus University, DK-8000 Aarhus, Denmark
Porous NiO, Co O and NiCo O superstructures were successfully prepared via a facile
3
4
2
4
hydrothermal-annealing method. The products were characterized by powder X-ray diffraction
(
(
XRD), field-emission scanning electron microscopy (FESEM) and energy dispersive spectrometry
EDS). The Brunauer-Emmett-Teller surface area and pore volume of the products were measured
by N adsorption isotherms. The catalytic performance of the as-prepared porous NiO, Co O and
2
3
4
NiCo O superstructures on the thermal decomposition of ammonium perchlorate (AP) was inves-
2
4
tigated by thermal gravimetric analysis and differential scanning calorimeter. The results showed
Delivered by Ingenta to: Adelaide Theological Library
Co O superstructures were more effective than others for the thermal decomposition of AP and
3
4
IP: 5.189.201.23 On: Thu, 17 Nov 2016 03:19:11
ꢀ
the thermal decomposition temperature of AP shifted downward about 136.2 C. Furthermore, the
Copyright: American Scientific Publishers
catalytic mechanism of porous NiO, Co O and NiCo O superstructures on the thermal decompo-
3
4
2
4
sition of AP was discussed.
Keywords: Metal Oxide, Nanostructures, Thermal Decomposition, Ammonium Perchlorate.
1
4
15
1
. INTRODUCTION
Co O nanoparticles, CuFe O nanoparticles etc. It is
3 4 2 4
Solid fueled rockets are widely used in the fields of
aerospace, universal exploration and satellite launching.
Ammonium perchlorate (AP) is an important oxidizer in
solid composite propellants for solid fueled rockets and its
content is about 60% ± 90% by weight. The combustion
behavior of propellants is highly relevant to the thermal
decomposition of AP. The lower temperature at which AP
begins to decompose, the higher the burning rate of pro-
pellants is.1 Therefore, catalyzed thermal decomposition
of AP has attracted a great deal of attention in the past
well known that the catalytic activity of metal oxides
and their compounds is closely related to their sur-
face area and pore volume. Superstructures with higher
BET and pore volume have been great interest in the
past decade due to their potential applications in many
1
6–21
fields.
According to the past literature, porous transi-
tion metal oxide superstructures could have better catalyst
2
2–25
effect for thermal decomposition of AP.
For exam-
–3
ple, Jia et al. prepared porous ZnCo O nanorods catalyst
2
4
which decreased the decomposition temperature (T ) of
d
decades.4
–7
ꢀ ꢀ ꢀ
AP from approximately 315 C and 450 C to 274.5 C
ꢀ
22
Recently, transition metal oxides and their compounds
nanomaterials with various morphologies have been used
as effective catalyst for thermal decomposition of AP,
and 290.9 C. Moreover, they produced porous CoFe O
2
4
ꢀ
superstructures which decreased T of AP to 290.3 C and
d
ꢀ
23
319.6 C. In addition, in our past works, we prepared
porous Co O and NiO superstructures using metal organic
8
9
including CoO nanocrystals, CuO nanorods, ꢀ-Fe O
2
3
3
4
naotubes,10 Fe O nanorods and micro-octahedrons,
11
frameworks (MOFs) as precursors and found that they
2
3
1
2
13
24ꢁ25
ꢀ
-MnO2 nanowires,
V O nanowires,
octahedral
had good catalytic effect for the decomposition of AP.
2
5
However, to the best of our knowledge, there are still
few reports on the comparative investigations of catalytic
∗
Authors to whom correspondence should be addressed.
J. Nanosci. Nanotechnol. 2016, Vol. 16, No. 8
1533-4880/2016/16/8635/005
doi:10.1166/jnn.2016.11635
8635

Preparation and Catalytic Activity Comparison of Porous NiO, Co O and NiCo O Superstructures
Wang et al.
3
4
2
4
ꢀ
behaviors of porous transition metal oxides and their
compounds superstructures for thermal decomposition
of AP.
(ꢂ = 0ꢃ15406 nm) at a step width of 0.02 . SEM images
and EDS of the products were obtained on a field emission
scanning electron micro analyzers (JSM-7001F), employ-
ing an accelerating voltage of 5 kV or 20 kV. Nitrogen
adsorption–desorption isotherms, pore size distributions
and surface areas of the samples were measured by the
In recent decades, the hydrothermal method has been
widely used for the synthesis of a variety of func-
tional nanomaterials with specific sizes and shapes and
it possesses many advantages, such as fast reaction
kinetics, short processing time, phase purity, and high
instrument of NOVA 2000e using N adsorption.
2
2
6ꢁ27
crystallinity.
In the present work, we successfully syn-
3
. RESULTS AND DISCUSSION
thesized NiO, Co O and NiCo O superstructures via
3
4
2
4
3
.1. Structure and Morphology of the
a facile and economical hydrothermal-annealing method
without the assistance of template or surfactant. The cat-
alytic effect of the prepared NiO, Co O and NiCo O
As-Prepared Samples
Figure 1 shows the XRD patterns of the products after
annealing treatment. All peaks in Figures 1(a)–(c) can
be indexed as the cubic NiO, the cubic Co O and the
cubic NiCo O phase by comparison with the JCPDS crad
files no. 78-0643, 78-1970 and 73-1702. No other impu-
rity peaks are detected, indicating that NiO, Co O and
3
4
2
4
superstructures on the thermal decomposition of AP was
studied by thermal gravimetric analysis (TGA) and differ-
ential scanning calorimeter (DSC) in detail.
3
4
2
4
3
4
2
. EXPERIMENTAL DETAILS
NiCo O can be successfully obtained and all products are
2 4
2
.1. Synthesis of Porous NiO, Co O and
pure. Figure 2 depicts the EDS analyses of the as-prepared
products. When the Ni/Co molar ratio in start materials
is 1:1, the peaks of Ni, Co and O in the product can be
easily found (Fig. 2(c)). The C, Si and Au peak can be
3
4
NiCo O Superstructures
2
4
All chemicals and solvents are of analytical grade and
were used as received without further purification. In a typ-
ical experiment, NiCl · 6H O, CoCl · 6H O and 3 mmol
attributed to CO adsorbed by the sample, the substrate
2
2
2
2
2
of urea was dissolved in 20 mL de-ionized water to form a
and the gold sputtering, respectively. Based on the calcu-
lation, the Co/Ni atomic ratio is 2.05, which is close to the
stoichiometric ratio of NiCo O .
solution, in which the total molar mass of NiCl ·6H O and
2
2
CoCl ·6H O is 1 mmol. The Ni/Co molar ratio is 1:0, 0:1
2
2
2
4
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IP: 5.189.201.23 On: Thu, 17 Nov 2016 03:19:11
and 1:2, respectively. Subsequently, the as-prepare solu-
The morphologies of all the products are characterized
tion was transferred into a 25 mL T Ce flo op ny - rl ii gn he dt : As t ma i ne lrei cs sa n S cb iye n Ft iEf i Sc EPMu b al i ns dh e trhs e images of the samples are shown
ꢀ
steel autoclave, and maintained at 120 C for 5 h. After
the autoclave was allowed to cool at room temperature, the
product was collected by centrifugation, and washed with
deionized water and alcohol for several times, and dried
in Figure 3. When the Ni/Co molar ratio is 1:0, the
results shown in Figure 3(a) reveal that NiO particles are
composed of sphere-like architectures. Figure 3(c) shows
the morphology of Co O prepared in the presence of
3
4
ꢀ
in oven at 60 C for 5 h. In addition, a calcination process
1 mmol of CoCl · 6H O. It was observed that Co O
2
2
3
4
ꢀ
ꢀ
−1
(
350 C for 2 h in air with a heating rate of 2 C min )
consists of flower-like superstructures with abundant of
nanorods. Figure 3(e) illustrates urchin-like superstructures
for NiCo O products. From the high-magnification SEM
was performed to transform precursor to NiO, Co O and
NiCo O crystals.
3
4
2
4
2
4
2
.2. Catalytic Activity Tests
The catalytic activities of porous NiO, Co O and
3
4
NiCo O4 superstructures in the thermal decomposition
2
of AP were studied by a differential scanning calorime-
ter (DSC) and thermogravimetric analysis (TGA) using
STA 449C thermal analyzer with a heating rate of
(
a)
ꢀ
−1
1
0
C min in N atmosphere over the temperature
2
ꢀ
range of 30–500 C. Before the experiments, the as-
prepared porous NiO, Co O and NiCo O products were
3
4
2
4
(b)
mixed with AP and ground at a mass ratio of 98:2
to prepare the target samples for thermal decomposition
analyses.
(c)
1
0
20
30
40
50
60
70
80
2
.3. Characterization
2θ/degree
The products were characterized by powder X-ray diffrac-
tion (XRD) on a Rigaku D/max 2500PC diffractome-
ter with graphite monochromator and Cu Kꢀ radiation
Figure 1. XRD patterns of the as-prepared (a) NiO, (b) Co O and
(c) NiCo O superstructures.
3
4
2
4
8636
J. Nanosci. Nanotechnol. 16, 8635–8639, 2016

Wang et al.
Preparation and Catalytic Activity Comparison of Porous NiO, Co O and NiCo O Superstructures
3 4 2 4
ꢀ
images (Figs. 3(b), (d) and (f)), it can be clearly seen that
a large number of cracks and pores exist on the surface of
the products.
endothermic phase transition at 240–250 C, the low-
ꢀ
temperature decomposition (LTD) at 300–330 C and the
high-temperature decomposition (HTD) at 410–450 C
ꢀ
1
0
(
Fig. 4(d)). When NiO, Co O and NiCo O superstruc-
3 4 2 4
tures as catalysts were added to AP, all samples have the
similar endothermic peaks at about 250 C, indicating that
3
.2. Catalytic Activity of Decomposing
Ammonium Perchlorate
ꢀ
the catalysts have little effect on the crystallographic tran-
sition temperature of AP. However, in the relatively high
temperature region, the samples containing catalysts have
dramatic changes in the exothermic peaks of AP decom-
position. When 2 wt% catalysts were added to AP, the
DSC curves for thermal decomposition of pure AP and
its mixture with NiO, Co O and NiCo O superstruc-
tures are shown in Figure 4. Generally, the thermal
decomposition of pure AP takes place in three steps: the
3
4
2
4
ꢀ
original exothermic peak of pure AP at 445.0 C dis-
appeared and only one exothermic peak was observed.
(
a)
Ni
The exothermic peak temperature was 331.2, 308.8 and
ꢀ
3
35.1 C for NiO, Co O and NiCo O superstructures,
3
4
2
4
respectively (Figs. 4(a)–(c)).
The weight loss of AP is determined from the TG curves
of different catalysts (Fig. 5). Figure 5(d) exhibits two
weight loss steps while Figures 5(a)–(c) show only one
weight loss step. Obviously, when catalysts were added
to AP, the final decomposition temperature is decreased
O
Ni
ꢀ
ꢀ
ꢀ
from 450.4 C (pure AP) to 352.8 C (NiO), 313.8 C
Si
C
Ni
ꢀ
(
Co O ) and 338.6 C (NiCo O ), respectively. The results
3
4
2
4
are in agreement with those of the DSC curves shown
in Figure 4. From the above experimental results, it was
found that NiO and Co O , and NiCo O superstructures
0
2
4
6
8
10
KeV
3
4
2
4
(
b)
had good catalytic properties and Co O superstructures
3
4
O
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had the most effective catalytic activity for the thermal
IP: 5.189.201.23 On: Thu, 17 Nov 2016 03:19:11
decomposition of AP. The catalytic activity of Co O
3
4
Co
Copyright: American Scientific Publishers
superstructures was higher than that of Co O nanoparti-
3
4
1
4ꢁ24ꢁ28
cles, nanosheets and cubes.
Co
3
.3. Catalytic Mechanism of Decomposing
Ammonium Perchlorate
Up to now, the mechanism of the thermal decomposition
of AP is still unclear because the decomposition process
is a complex hetero-phase process involving coupled reac-
Si
Au
2
Co
C
2
2
tions in the solid, absorbed and gaseous phases. Accord-
ing to the traditional electron-transfer theory, the presence
0
4
6
8
10
2
+
3+
KeV
of partially filled 3d orbit in Ni or Co provides help in
an electro-transfer process. Positive hole in p-type semi-
conductor oxides like NiO, Co O and NiCo O , which
(
c)
O
3
4
2
4
can accept electrons from AP ion and its intermediate
products, enhance the thermal decomposition of AP.
Co
Ni
29ꢁ30
Generally, there are many factors influencing the catalytic
effect of the p-type semiconductor oxides on the thermal
decomposition of AP, such as chemical nature, particle
2
4ꢁ31–33
Co
size, morphology and surface area.
In our present
work, the BET surface areas and pore volumes of NiO,
Si
2
−1
O and NiCo O superstructures are 54 m g and
3 4 2 4
Au
Co
−1
21.6 mm g , 26 m g and 106.2 mm g , 69 m g
C
Ni
3
−1
2
−1
3
−1
2
1
3
−1
and 157.2 mm g , respectively. The average particle
sizes of NiO, Co O and NiCo O superstructures are cal-
0
2
4
6
8
10
3
4
2
4
KeV
culated by the Debye-Scherrer formula to be about 6.9 nm,
4.4 nm and 22.3 nm, respectively. However, Co O super-
2
Figure 2. EDS spectra of the as-prepared (a) NiO, (b) Co O and
3
4
3
4
(
c) NiCo O superstructures.
structures with smaller surface area and larger particle size
2
4
J. Nanosci. Nanotechnol. 16, 8635–8639, 2016
8637

Preparation and Catalytic Activity Comparison of Porous NiO, Co O and NiCo O Superstructures
Wang et al.
3
4
2
4
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IP: 5.189.201.23 On: Thu, 17 Nov 2016 03:19:11
Copyright: American Scientific Publishers
Figure 3. SEM images of (a), (b) NiO, (c), (d) Co O and (e), (f) NiCo O superstructures.
3
4
2
4
were more effective than others for the thermal decomposi-
tion of AP. In addition, Co O superstructures had a higher
This indicates that the catalytic ability of the as-prepared
products for decreasing the decomposition of AP depend
on not only their surface area, particle size and mor-
phology but also their chemical nature. Thus, the high
3
4
catalytic activity than NiCo O superstructures which
2
4
had the similar morphology with Co O superstructures.
3
4
331.2
(a)
352.8
308.8
(a)
(b)
313.8
(
(
b)
c)
335.1
(c)
338.6
445.0
317.7
(d)
450.4
(d)
500
100
200
300
400
100
200
300
400
500
Temperature (ºC)
Temperature (ºC)
Figure 4. DSC curves of the AP samples after addition of (a) 2 wt% NiO,
Figure 5. TG curves of the AP samples after addition of (a) 2 wt% NiO,
(
b) 2 wt% Co O , (c) 2 wt% NiCo O superstructures and (d) pure AP.
(b) 2 wt% Co O , (c) 2 wt% NiCo O superstructures and (d) pure AP.
3
4
2
4
3
4
2
4
8638
J. Nanosci. Nanotechnol. 16, 8635–8639, 2016

Wang et al.
Preparation and Catalytic Activity Comparison of Porous NiO, Co O and NiCo O Superstructures
3 4 2 4
catalytic performance of porous Co O superstructures
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4
(
may be explained as that in the decomposition process of
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. CONCLUSION
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In summary, we synthesized porous NiO, Co O and
NiCo O4 superstructures via a facile and economical
hydrothermal-annealing method without the assistance of
template or surfactant. The as-prepared porous NiO, Co O
and NiCo O superstructures have good catalytic proper-
ties for the thermal decomposition of AP due to their large
BET surface area and pore volume. Co O superstructures
show better catalytic activity than others and shifted the AP
3
4
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(
Acknowledgments: We acknowledge the financially
supported by National Natural Science Foundation of
China (No. 21401081), China Postdoctoral Science
Foundation (No. 2014M560397), Jiangsu Natural Sci-
ence Funds for Distinguished Young Scholars (No.
2
(
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1
Received: 1 March 2015. Accepted: 23 April 2015.
J. Nanosci. Nanotechnol. 16, 8635–8639, 2016
8639