Atomic-Layer-Deposited ZnO on Carbon Black as High-Performance Catalysts for the Thermal Decomposition of Ammonium Perchlorate

Article abstract of DOI:10.1002/ejic.201700146

Hybrid materials with ZnO anchored on carbon black (CB) are fabricated by using the atomic-layer deposition (ALD) technique. The oxygen-containing functional groups on the surface of the CB act as the reactive sites to facilitate stable deposition of ZnO, and further create a unique hybrid structure with a C–O–Zn bond between CB and ZnO. The catalytic performance of the ZnO/CB hybrids for thermal decomposition of ammonium perchlorate (AP, NH₄ClO₄) is investigated, showing that two exothermic peaks are merged into one and the peak temperature decreases from 432 °C to 295 °C, even lower than that of ZnO (311 °C). The superior catalytic activity of ZnO/CB hybrids is attributed to the fast electron transfer from ZnO to CB and restricted electron recombination in the hybrids, which significantly benefits from the C–O–Zn bond fabricated by the ALD process. The present study provides a new insight into the catalytic mechanism of metal oxide/carbon hybrids, showing promise for catalyst and reaction accelerator applications.

Full text of DOI:10.1002/ejic.201700146

A Journal of
Accepted Article
Title: Atomic Layer Deposited ZnO on Carbon Black as High-
Performance Catalysts for the Thermal Decomposition of
Ammonium Perchlorate
Authors: Jingfeng Wang, Yang Li, Huanhuan Wang, Tian Tian, Shanxu
Zhu, Jia Zhou, Xiaohong Wu, and Wei Qin
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To be cited as: Eur. J. Inorg. Chem. 10.1002/ejic.201700146
Link to VoR: http://dx.doi.org/10.1002/ejic.201700146

10.1002/ejic.201700146
European Journal of Inorganic Chemistry
FULL PAPER
Atomic Layer Deposited ZnO on Carbon Black as High-
Performance Catalysts for the Thermal Decomposition of
Ammonium Perchlorate
Jingfeng Wang,[a] Yang Li,[a] Huanhuan Wang,[a] Tian Tian,[a] Shanxu Zhu,[a] Jia Zhou,[a] Xiaohong
Wu,*[a] Wei Qin [b]
Abstract: The ZnO anchored on carbon black (CB) hybrid materials
are fabricated by using atomic layer deposition (ALD) technique. The
oxygen-containing functional groups on the surface of CB act as the
reactive sites to facilitate stable deposition of ZnO, and further create
a unique hybrid structure with a C-O-Zn bond between CB and ZnO.
The catalytic performance of the ZnO/CB hybrids for thermal
decomposition of ammonium perchlorate (AP, NH4ClO4) is
investigated, showing that two exothermic peaks are merged into one
and the peak temperature decreased from 432℃ to 295℃, even lower
than that of ZnO (311℃). The superior catalytic activity of ZnO/CB
hybrids is attributed to the fast electron transfer from ZnO to CB and
restricted electron recombination in the hybrids, which significantly
benefits from the C-O-Zn bond fabricated by ALD process. The
present study provides a new insight into the catalytic mechanism of
metal oxides/carbon hybrids, showing promising for the applications
of catalyst and reaction accelerators.
address this issue, constructing a channel for electron transfer is
generally used to enhance the catalytic performance of ZnO, such
as introducing metal nanoparticles or carbon materials.[1d,
5]
Among these modified materials, carbon black is usually served
as a reactive template and a support to prepare metal or metal
oxide nanoparticles/carbon black hybrids, owing to its readiness,
lower cost, large surface area and excellent conductivity.[6]
Conventional methods to coat ZnO nanoparticles on carbon
black surface mainly include sol–gel, solution mixing, etc.[6a, 7] In
this work, atomic layer deposition (ALD) technique is employed to
fabricate ZnO nanoparticles, which is based on the surface-
controlled reactions from the gas phase.[8] And it is commonly
accepted that, due to the chemical inertness of carbon materials,
the gas precursor is favorable to react with oxygen-containing
functional groups, depositing ZnO NPs on the surface of carbon
materials.[9] As a result, ALD is ideally suited to generate stable
bonding interaction between ZnO and carbon black.
Herein, we demonstrate the fabrication of ZnO/CB hybrid
materials using ALD technique. The ALD ZnO nanoparticles with
average size of 10 nm are anchored on the surface of carbon
black with the stable C-O-Zn bond, constructed via capturing Zn2+
ion on functionalized carbon black with the bridge of oxygen atom.
The unique ZnO/CB hybrids, consequently, give rise to an
excellent catalytic effect for the thermal decomposition of AP,
showing that two peaks of the low-temperature decomposition
(LTD) and high-temperature decomposition (HTD) of AP are
merged into a single peak, and the peak temperature decreased
from 432 to 295℃, even lower than that of ZnO (311℃). Besides,
the exothermic heat in the catalytic decomposition of AP by the
hybrids is also significantly increases from 376 to 1692 J/g. The
present of C-O-Zn bond accelerates the electron transfer from
excited ZnO to carbon black, higher utilization percentage of the
electron than individual ZnO, resulting in the better catalytic
activity of ZnO/CB hybrids.
Introduction
ZnO, an important transition metal oxide semiconductor material,
has many favorable properties including wide band gap, strong
room-temperature luminescence, excellent reactivity, non-toxicity,
and most importantly, low cost, which has led to its widespread
application in optoelectronic devices, gas sensors, solar cells and
especially catalysis.[1] The photocatalytic activity of ZnO has
already been researched extensively both domestically and
abroad, while ZnO as catalyst to facilitate the thermal
decomposition of ammonium perchlorate (AP) is in its infancy.[2]
Here, AP is the most widely used oxidant in composite solid rocket
propellants and its thermal decomposition process has a great
impact on the combustion performance of the propellant.[3]
It has been proved that the catalytic activity is correlated
conduction-band electron from the excited ZnO, while the electron
of n-type ZnO semiconductor is dependent on excess zinc, acting
as the intrinsic donors in ZnO.[4] However, the low utilization
percentage of the electron, due to the quickly electron
recombination in ZnO, hinders the wide application of ZnO. To
Results and Discussion
Characterization of morphology and structure
It is commonly accepted that, due to the chemical inertness of
carbon materials, it is difficult for ALD to successfully deposit
nanoparticles atop.[8-9] Figure 1 schematically describes the
process of the ZnO/CB hybrids fabricated by ALD. First, a
prevenient activation is carried out by the acid treatment, resulting
in the formation of activated carbon surface with dense functional
groups, such as hydroxyl (–OH) and carboxyl (–COOH).[6b] Then,
the functional groups can be straightforwardly employed for the
[a]
[b]
School of Chemistry and Chemical Engineering, Harbin Institute of
Technology
Harbin, Heilongjiang,150001, China.
E-mail: wuxiaohong@hit.edu.cn
School of Materials Science and Engineering, Harbin Institute of
Technology
Harbin, Heilongjiang,150001, China.
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10.1002/ejic.201700146
European Journal of Inorganic Chemistry
FULL PAPER
at half maximum (HWFM) as much as 2.10° can be ascribed to
the (002) plane of the carbon black.[10] And, the diffraction peaks
of ZnO are marked with the red circularity, which is perfectly
corresponded to the hexagonal wurtzite structure for ZnO
(JCPDS No. 36-1451).[2d]
To obtain the microstructure of the ZnO/CB hybrids, the TEM
image is depicted in Figure 2b~2f. Figure 2b shows a typical TEM
image of the obtained ZnO/CB hybrid nanostructures, exhibiting
the ZnO nanoparticles successfully anchored onto the surface of
the carbon black as there are no extra ZnO particles found
agglomerated over the carbon black surface. Moreover, from the
elemental mapping image of Zn shown in Figure 2c, it can be
indicated that the zinc elements are not homogeneous distribution,
because the density of functional groups was not high enough to
allow the ALD precursors to react uniformly, and the island growth
mode is favored.[9c] Besides, the ZnO nanoparticles have an
average particle size of 10 nm as shown in the Figure 2d,
suggesting that the growth rate is slightly lower than the typical
result of 1.3 Å per cycle for the ZnO ALD.[11] From the high
resolution TEM (HRTEM) image shown in Figure2e, two kind of
the interplanar spacing are 0.28 nm and 0.34 nm, which are
matched well with the (100) plane of hexagonal wurtzite ZnO and
the gap between the two single graphene layer in CB,
respectively.[12] And the detailed analysis of the boundary in the
two kind regions, marked with yellow dotted circle in Figure 2e, is
shown in Figure 2f, indicating that some of the ZnO lattice sites
have been incorporated into the CB surface, resulting from the C-
O-Zn bond formed by the reaction between DEZn and the oxygen
functional groups of CB surface during the ALD process.[12a, 13]
To further identify the formation of C-O-Zn bond between the
ZnO and CB, the chemical state of ZnO, CB and ZnO/CB hybrids
Figure 1. Schematic representation of the proposed ALD growth of ZnO on
carbon black surface.
reactive sites to react with DEZn vapors to form C-O-Zn(Et)
species. Following by release of H2O causes the reaction
between H2O and Zn(Et) to yield Zn−OH species.[8] The two
sequential half-reactions are described by the following:
(A)
(B)
C -OH *Zn(Et)2  C -O - Zn(Et)*CH3CH3
Zn(Et)*H2O  ZnOH  CH3CH3
where the asterisks represent the surface species. Finally, by
repeating these reactions in an ABAB… sequence for 100 times,
the ZnO is successfully deposited on the surface of CB with the
mass percentage of 57.9% calculated from TG analysis (Figure
S1) and the C-O-Zn bond is locally created between CB and ZnO
by the ALD technique.
The X-ray diffraction (XRD) pattern of the as-achieved sample
of ZnO/CB hybrids shows in Figure 2a. From the XRD pattern,
simultaneous observation of Bragg peaks corresponding to the
ZnO and CB indicates that the ZnO/CB hybrid is successfully
synthesized. The first Bragg peak at 25.4° with a large full width
Figure 2. (a) XRD spectrum of the ZnO/CB hybrids; (b) Low-magnification TEM image, (c) Element mapping image of Zn and (d, e, f) The HRTEM images of
ZnO/CB hybrids.
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10.1002/ejic.201700146
European Journal of Inorganic Chemistry
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Figure 3. The XPS spectrum (color map for experimental data; solid line for Gaussian-resolved result) of (a) Zn 2p for ZnO; (b) O1s and (c) C 1s for CB; (d) Zn 2p,
(e) O1s and (f) C 1s for ZnO/CB hybrids.
is analysed by XPS spectroscopy. The chemical shifts, as shown
in Figure 3, are noticeably altered upon ZnO ALD deposited on
CB surface. From the Zn 2p spectra of ZnO and ZnO/CB hybrids
in Figure 3a and Figure 3d, the Zn 2p3/2 and Zn 2p1/2 binding
energy varies from 1020.8 to 1022.6 eV and from 1043.8 to
1045.6 eV, respectively. The shift of Zn 2p spectrum to higher
binding energy suggests that higher oxidized is formed, resulting
from the formation of covalent bonds between ZnO and other
elements on the surface CB, such as the Zn-O-C bond.[4b, 14]
In addition, Figure 3b shows a broad signal of the O 1s XPS
spectrum for CB, which is deconvoluted into three components
that can be ascribed to the contribution of C=O (530.8 eV), C-OH
(532.2 eV) and –COOH (533.6 eV).[15] Meanwhile, the O 1s peak
for ZnO/CB hybrids shown in Figure 3e shifts to the lower binding
energy side, and the peak is resolved into four components.
Generally, the two components located at 529.9 and 531.0 eV are
attributed to the Zn-O bond and VO in wurtzite ZnO structure,
respectively.[4a, 13b] Furthermore, the presence of two other peaks
appeared at 531.8 and 532.9 eV, the low binding energy
compared with C–OH and –COOH of CB, indicates that the
chemical environment of O is changed. This likely originated from
a reaction of DEZn with –OH occurred on both C–OH and –COOH
terminated CB surfaces to form C-O-Zn bond.[14a, 15b]
the C atom gets more electrons and the peak shifts to lower
binding energy at 285.7 eV.
In order to give further evidence for the establishment of C-O-
Zn covalent bond, the FTIR analysis is also performed. Figure 4
shows representative FTIR spectra taken of CB and ZnO/CB
hybrids. The characteristic ZnO peak is seen at 482 cm-1 for the
Zn-O stretching vibration.[17] The three peaks at 1050, 1089 and
1398 cm-1 assigned to C-O stretching vibration from alcohol
groups,[15b, 18] disappear after deposition, suggesting a reaction of
C-O with DEZn to form C-O-Zn bond, while the appearance of a
broad peak at 1199 cm-1, not seen on CB surface, is characteristic
of C-O-Zn bond, and the similar study of Ti-O-C bond has been
reported by Y. Lei and co-workers.[19] In addition, the peak of C=O
In Figure 3c, the peaks at 284.7 and 285.0 eV of C 1s spectrum
for CB can be ascribed to the skeletal C-C structure of sp2 and
sp3 carbon, respectively,[10] which are similar to C 1s spectrum for
ZnO/CB hybrids shown in Figure 3f. Consistent with O 1s spectra,
the peak at 286.1 eV contributed to C-OH also show a slightly
decrease in binding energy after ZnO deposition, demonstrating
the substitution of H atom at the tail end of C-OH by Zn atom.[14a,
16] Because the Zn atom has higher electron density than H atom,
Figure 4. The FTIR spectrum of CB and ZnO/CB hybrids.
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10.1002/ejic.201700146
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From the Figure 5a, all the DSC curves have the similar
endothermic peaks, indicating that the catalyst has nothing to do
with the crystallographic transition of AP. After involving the ZnO
and ZnO/CB hybrids, the significant difference for AP
decomposition is the disappearance of the HTD process, while
the catalytic properties of CB for AP decomposition is insignificant,
which exhibits the smaller reduction of HTD temperature from 432
to 374℃ and unchanged of LTD temperature (Figure S2). But in
the presence of ZnO/CB hybrids, the LTD temperature at 295℃
is lower than that of AP mixture with ZnO and pure AP. Consistent
with the DSC curves, the TG curves (Figure 5b) show that the
decomposition of AP with ZnO/CB hybrids starts at 260℃, which
is lower than AP with ZnO at 286℃ and pure AP at 281℃. Besides,
the exothermic heat is also an important parameter for the
application of AP. As shown in Figure 5c, when ZnO and ZnO/CB
hybrids are added, the heat release increases from 376 to 1047
and 1692 J/g, respectively.
Figure 5. (a) DSC curves, (b) TG curves, (c) the value of heat release and (d)
dependence of ln(β/Tp2) on 1/Tp for pure AP, AP mixture with ZnO and AP
mixture with ZnO/CB hybrids. Scatter points are experimental data and lines
denotes the linear fitting results.
To further study the catalytic role of ZnO and ZnO/CB hybrids
in AP thermal decomposition, the kinetic parameters of AP
decomposition can be calculated using the Kissinger correlation:

AR
ln( )  ln( ) 
Ea
Ea
stretching vibration at 1730 cm-1, shifted to the right side at 1645
cm-1 after deposition, demonstrates the changing carboxylic
species to metal carbonyls due to the existence of C-O-Zn
bond.[16a, 20] Meanwhile, the C-H features such as asymmetric CH3
stretching modes at 2973 and 2925 cm-1, symmetric stretching
mode at 2873 cm-1 and =C-H bending mode at 881 cm-1,[19]
significantly decrease in intensity, because the ALD ZnO is
successfully anchored on the CB surface, leading to the decrease
of CB surface area. At last, due to the effect of adsorbed H2O on
the FTIR spectra, unfortunately, it is difficult to discriminate the
broad bands of the O-H stretching mode and other groups that
contained C-O bands at 3400 and 3450 cm-1.[15b]
TP2
RTP
where β is the heating rate in degrees Celsius per minute, Tp is
the peak temperature, R is the ideal gas constant, Ea is the
activation energy, and A is the pre-exponential factor.[2b,
2d, 21]
According to this equation, there is a linear correlation exhibited
2
between the term ln(β/Tp ) and 1/Tp, and the kinetic parameter of
activation energy (Ea) can obtain from the slope of the fitting
straight line. Pure AP, AP mixture with ZnO and AP mixture with
ZnO/CB hybrids are investigated by DSC test at different heating
rates from 5 to 20 K/min, respectively, showing that the peak
temperature is dependent on the heating rate (Figure S3). And
2
the experimentally measured values of ln(β/Tp ) versus 1/Tp for
From the TEM, XPS and FTIR results, it can be concluded that
C-O-Zn bond is successfully established between CB surface and
ZnO nanoparticles by ALD. And the bond is hopeful to be a
channel for fast electron transfer, promoting the catalytic activity
for the thermal decomposition of ammonium perchlorate.
AP decomposition without and with catalyst are shown in Figure
5d. For pure AP, the Ea of HTD process is calculated to be 130.1
Catalytic activity of the hybrid materials
The catalytic effect of ZnO/CB hybrids in the thermal
decomposition of AP is investigated by TG-DSC measurement.
Compared with ZnO/CB hybrids, the thermal decomposition of AP
and AP mixture with ZnO are also carried out, shown in Figure 5.
For pure AP, three obvious peaks at 242, 313 and 432℃ are
assigned to the endothermic transformation of AP from
orthorhombic to cubic phase, the low-temperature decomposition
(LTD) and high-temperature decomposition (HTD), respectively.
The LTD process comprises a series of chemical reaction starting
with electron transfer in AP subsurface to yield NH3 and HClO4,
and the process ceases on NH3-covered surface that the
2d]
unreacted NH3 accumulates on the surface.[2a,
The HTD
process is contributed to the oxidation of NH3 by HClO4.[2e, 3a]
Figure 6. Room-temperature PL emission spectra of ZnO NPs and ZnO/CB
hybrids.
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10.1002/ejic.201700146
European Journal of Inorganic Chemistry
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Figure 7. FTIR spectra of decomposed gas products of pure AP (a) and mixtures of AP with ZnO/CB hybrids (b) at different temperatures until they are completely
decomposed.
±9.3 kJ/mol, which is close to the value previously reported by G.
Tang.[2d] In presence of ZnO and ZnO/CB hybrids catalyst, the
activation energy Ea of AP decomposition is decreased
significantly to 84.1 ± 5.7 kJ/mol and 58.8 ± 2.9 kJ/mol,
respectively. These results confirm that ZnO and ZnO/CB hybrids
exhibit an obvious catalytic activity for the thermal decomposition
of AP. Moreover, the catalytic activity of ZnO/CB hybrids is better
than that of ZnO, probably because of the existence C-O-Zn bond
between ZnO and CB interface.
(1430~1750 cm-1) and NO2 (1200~1430 cm-1)[21, 25]. Compared
with pure AP, the major differences are that large amounts of HCl
and more kinds of oxynitride are produced from the mixture of AP
with ZnO/CB hybrids. These results suggest that a chemical
+
-
reaction is in existence between ZnO/CB hybrids and NH4 ClO4
molecules.
The proposed catalytic mechanism of ZnO/CB hybrids is
schematically shows in Figure 8. Due to the excellent electronic
conductivity characteristic of CB, the electron from the excited
ZnO can travel long distances without being scattered.[18] Thus,
Catalytic mechanism of the hybrid materials
+
-
the electron transfer in the NH4 ClO4 molecules, the first step of
LTD process, can be greatly accelerated in the presence of the
additional electron from the ZnO/CB hybrids to form NH3(g) and
HClO4(g), as shown in Figure 8b. For pure AP decomposition, the
LTD process can be ceased on an NH3-covered surface, while the
LTD process can be continuous until the AP is completely
decomposed with the additive of ZnO/CB hybrids. From the
Figure 8c and Figure 8d, HClO4(g) is adsorbed on the catalyst
To understand the role of the C-O-Zn bond on promoting catalytic
effect for thermal decomposition of AP, the quenching effect of
emission intensity is measured by PL spectra. In Figure 6, it can
be seen that, compared to ZnO NPs, the ZnO/CB hybrids exhibits
large extent (90%) of quenching of emission intensity, suggesting
that the fast electron transfer process occurs in the interface
between excited ZnO and CB, acted as donor and acceptor,
respectively.[10, 22]
In the present experiments, the valence-band electrons of ZnO
can be excited by heating energy when the temperature overtop
250℃[2d, 23] and moved to conduction-band, leaving behind the
positive holes in the valence-band. Due to the energy gap, the
excited electron can be transfer to the carbon materials. While in
the presence of C-O-Zn bond, the electron will be fast transfer to
CB, making the excited electron has more possibility to be
efficiently separated and migrated.[24] Besides, the resistance is
reduced from 5.04 kΩ for ZnO to 0.14 kΩ at room temperature
(Figure S4). Therefore, the catalytic active of ZnO/CB hybrids for
AP decomposition is evidently improved, compared to the
individual ZnO nanoparticles.
For the purpose to investigate the catalytic mechanism of
ZnO/CB hybrids for AP decomposition, TGA-FTIR spectroscopy
is used to detect the thermolysis products of pure AP and AP
mixture with ZnO/CB hybrids. From Figure 7, it can be seen that
the gas products are identified as H2O (3400~3800 cm-1), HCl
(2830~3083 cm-1), N2O (2149~2416/1000~1200 cm-1), NO
Figure 8. Schematic of catalytic thermal decomposition process of AP by
ZnO/CB hybrids.
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10.1002/ejic.201700146
European Journal of Inorganic Chemistry
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ThermoScientific, USA). The ZnO/CB hybrids is furtherly characterized by
Fourier transform infrared (FT-IR) using Thermo Nicolet iS50 with a
resolution of 4 cm-1 in the range 400~4000 cm-1.The photoluminescence
(PL) spectra of ZnO and ZnO/CB hybrids is obtained at an excitation
wavelength of 305 nm on Horiba Fluoromax-4 setup but without the filter
on emission side.
surface, capturing the electron from ZnO/CB hybrids, yielding the
negative oxygen ions (O−) and HClOx(x=0, 1 3) species, and then
，
，
2
the O− with powerful oxidation ability will react with NH3(g) to
produce N2O(g) and H2O(g) species.[2d, 2e, 25] In this process, the
releasing electrons re-accepted by the catalyst help the further
dissociation of HClO4 species to produce more O−. Then, the
formation of the NH3-covered surface is inhibited, and the rate of
thermal decomposition of AP accelerates. It is also noticed that
the oxidation of NH3 is a strongly exothermic reaction,[18] resulting
in the fact that the total heat release of AP mixture with ZnO/CB
NPs is higher than ZnO and pure AP.
Catalytic activity measurement: To obtain the catalytic performance of
ZnO/CB hybrids in the thermal decomposition of AP, the Pure AP, AP
mixture with ZnO and ZnO/CB hybrids at a mass ratio of 99:1 respectively
are studied by differential scanning calorimetry (DSC) and
thermogravimetry (TG) analysis using a thermal analyzer (SDT-Q 600, TA
Instruments USA) under N2 atmospheres on the temperature range of
RT~500℃ with the heating rate of 10℃/min.
Conclusions
Acknowledgements
In summary, the C-O-Zn bonding interaction between ZnO
nanoparticle and carbon black has been generated by ALD
technique. The ALD method used here, which is based on
surface-controlled reactions from the gas phase, successfully
supports the formation of the unique hybrids structure. And a
better catalytic performance of AP thermal decomposition,
compared with dispersed ZnO nanoparticles, has been achieved
by this unique ZnO/CB hybrids structure, showing that two
exothermic peaks are merged into one and the peak temperature
decreased from 432 to 295℃, even lower than that of ZnO
(311℃). During the AP catalytic decomposition process, the fast
electron transfer characteristic from excited ZnO to CB, due to the
presence of C-O-Zn bond, gives an additional pathway for the
The financial supports of the National Natural Science Foundation
of China (Grant No. 51671074, 51572060 and 51602079) and the
Doctoral Foundation of Heilongjiang province (LBH-Z14103) are
gratefully acknowledged.
Keywords: Atomic layer deposition • Hybrid materials •
Supported catalysts • Electron transfer • C-O-Zn bond
[1]
a) V. Q. Dang, T. Q. Trung, L. T. Duy, B. Y. Kim, S. Siddiqui, W. Lee, N.
E. Lee, ACS Appl. Mater. Interfaces 2015, 7, 11032-11040; b) J. X. Wang,
X. W. Sun, Y. Yang, H. Huang, Y. C. Lee, O. K. Tan, L. Vayssieres,
Nanotechnology 2006, 17, 4995-4998; c) Y. F. Gao, M. Nagai, Langmuir
2006, 22, 3936-3940; d) Y. C. Chen, K. Katsumata, Y. H. Chiu, K. Okada,
N. Matsushita, Y. J. Hsu, Appl. Catal. A: Gen. 2015, 490, 1-9.
a) S. Q. Tian, N. Li, D. W. Zeng, H. T. Li, G. Tang, A. M. Pang, C. S. Xie,
X. J. Zhao, Crystengcomm 2015, 17, 8689-8696; b) Z. X. Zhou, S. Q.
Tian, D. W. Zeng, G. Tang, C. S. Xie, J. Alloy. Compd. 2012, 513, 213-
219; c) R. F. S, Nature 1961, 192 64-65; d) G. Tang, S. Q. Tian, Z. X.
Zhou, Y. W. Wen, A. M. Pang, Y. G. Zhang, D. W. Zeng, H. T. Li, B. Shan,
C. S. Xie, J. Phys. Chem. C 2014, 118, 11833-11841; e) X. F. Sun, X. Q.
Qiu, L. P. Li, G. S. Li, Inorg. Chem. 2008, 47, 4146-4152.
+
-
supplementation of electron to accelerate the NH4 ClO4
molecules forming NH3 and HClO4 and the oxidation of NH3 by
HClO4, corresponding to the LTD process and HTD process,
respectively.
[2]
Experimental Section
[3]
[4]
a) D. L. Reid, A. E. Russo, R. V. Carro, M. A. Stephens, A. R. LePage,
T. C. Spalding, E. L. Petersen, S. Seal, Nano Lett. 2007, 7, 2157-2161;
b) V. V. Boldyrev, Thermochim. Acta 2006, 443, 1-36.
Preparation of ZnO/CB hybrids: The ZnO/CB hybrids are synthesized in
an ALD reactor (TALD-150 Kemicro Jiaxing) under 0.15 Torr at 150℃. The
diethyl zinc (DEZn, Zn(Et)2, Fornano Suzhou) and HPLC grade water, as
the zinc and oxygen precursors, respectively, are alternately exposed on
carbon black (CB) surface for controlled ZnO deposition. Before depositing,
carbon black (Sigma-Aldrich) is treated by the mixture of H2SO4 and HNO3
aqueous solution, resulting in the formation of active sites for ZnO ALD
growth. Subsequently, a typical ALD cycle: a 0.02 s pulse of Zn(Et)2(g), a 5
s extended exposure of Zn(Et)2(g) to carbon black powder, a 40 s N2 purge,
a 0.02 s pulse of H2O(g), a 5 s extended exposure of H2O(g), a 40 s N2 purge,
is explored to deposit ZnO. In this work, 100 ALD cycles were performed.
a) J. W. Zhao, C. S. Xie, L. Yang, S. P. Zhang, G. Z. Zhang, Z. M.
CaiState, Appl. Surf. Sci. 2015, 330, 126-133; b) H. Moussa, E. Girot, K.
Mozet, H. Alem, G. Medjahdi, R. Schneider, Appl. Catal. B: Environ.2016,
185, 11-21.
[5]
[6]
X. He, H. Wang, Q. Zhang, Z. B. Li, X. C. Wang, Eur. J. Inorg. Chem.
2014, 2014, 2432-2439.
a) H. Qin, Q. L. Liao, G. J. Zhang, Y. H. Huang, Y. Zhang, Appl. Surf. Sci.
2013, 286, 7-11; b) S. S. Rich, J. J. Burk, C. S. Kong, C. D. Cooper, D.
E. Morse, S. K. Buratto, Carbon 2015, 81, 115-123.
[7]
R. D. C. Soltani, A. Rezaee, A. R. Khataee, M. Safari, J. Ind. Eng. Chem.
2014, 20, 1861-1868.
Characterization: The crystalline structure of the ZnO/CB hybrids is
obtained within the range of 2θ = 10°~90° using X-ray diffraction (XRD,
Rigaku D/max IIIA) with the Cu-Kα wavelength (λ=0.15406 nm).
Transmission electron microscopy (TEM) and high-resolution TEM
(HRTEM) are employed to manifest the microstructure of ZnO on CB
surface. The surface properties and chemical composition of the prepared
sample are investigated by X-ray photoelectron spectroscopy (XPS)
analysis on an X-ray photoelectron spectrometer (K-alpha,
[8]
[9]
M. Knez, K. Nielsch, L. Niinistö, Adv. Mater. 2007, 19, 3425-3438.
a) X. R. Wang, S. M. Tabakman, H. J. Dai, J. Am. Chem. Soc. 2008, 130,
8152-8153; b) S. M. George, Chem. Rev. 2010, 110, 111-131; c) X. Tong,
Y. Qin, X. Guo, O. Moutanabbir, X. Ao, E. Pippel, L. Zhang, M. Knez,
Small 2012, 8, 3390-3395.
[10] J. Shim, J. K. Kim, K. S. Lee, C.-L. Lee, M. Ma, W. K. Choi, J. Y. Hwang,
H. Y. Yang, B. Angadi, J. H. Park, K. Yu, D. I. Son, Nano Energy 2016,
25, 9-17.
This article is protected by copyright. All rights reserved.

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European Journal of Inorganic Chemistry
FULL PAPER
[11] D.J. Lee, K.J. Kim, S.H. Kim, J.Y. Kwon, J. Xu, K.B. Kim, J. Mater. Chem.
C 2013, 1, 4761.
[17] a) H. Li, Y. Wei, Y. Zhang, C. Zhang, G. Wang, Y. Zhao, F. Yin, Z.
Bakenov, Ceram. Int. 2016, 42, 12371-12377; b) T. N. Reddy, J.
Manna, R. K. Rana, ACS Appl. Mater. Interfaces 2015, 7, 19684-
19690.
[12] a) G. R. Dillip, A. N. Banerjee, V. C. Anitha, S. W. Joo, B. K. Min, S. Y.
Sawant, M. H. Cho, Chemphyschem 2015, 16, 3214-3232; b) X. Chen,
Y. Li, X. Pan, D. Cortie, X. Huang, Z. Yi, Nat. Commun. 2016, 7, 12273.
[13] a) J. Sun, G. Y. Zheng, H. W. Lee, N. Liu, H. T. Wang, H. B. Yao, W. S.
Yang, Y. Cui, Nano Lett. 2014, 14, 4573-4580; b) G. R. Dillip, A. N.
Banerjee, V. C. Anitha, B. Deva Prasad Raju, S. W. Joo, B. K. Min, ACS
Appl. Mater. Interfaces 2016, 8, 5025-5039.
[18] N. Li, Z. F. Geng, M. H. Cao, L. Ren, X. Y. Zhao, B. Liu, Y. Tian, C. W.
Hu, Carbon 2013, 54, 124-132.
[19] Y. Lei, B. Liu, J. L. Lu, J. A. Libera, J. P. Greeley, J. W. Elam, J. Phys.
Chem. C 2014, 118, 22611-22619.
[20] L. N. Yang, J. G. Hu, W. W. Wu, J. Tang, K. X. Ding, J. Li, Chem. Eng.
J. 2016, 306, 77-85.
[14] a) Z. W. Shi, A. V. Walker, J. Phys. Chem. C 2015, 119, 1091-1100; b)
Y. Liu, L. Si, Y. Du, X. Zhou, Z. Dai, J. Bao, J. Phys. Chem. C 2015, 119,
27316-27321.
[21] G. Tang, Y. W. Wen, A. M. Pang, D. W. Zeng, Y. G. Zhang, S. Q. Tian,
B. Shan, C. S. Xie, Crystengcomm 2014, 16, 570-574.
[22] a) W. T. Wu, L. Y. Zhan, W. Y. Fan, J. Z. Song, X. M. Li, Z. T. Li, R. Q.
Wang, J. Q. Zhang, J. T. Zheng, M. B. Wu, H. B. Zeng, Angew. Chem.
Int. Edit. 2015, 54, 6540-6544; b) G. Williams, P. V. Kamat, Langmuir
2009, 25, 13869-13873.
[15] a) L. F. Pena, C. E. Nanayakkara, A. Mallikarjunan, H. Chandra, M. C.
Xiao, X. J. Lei, R. M. Pearlstein, A. Derecskei-Kovacs, Y. J. Chabal, J.
Phys. Chem. C 2016, 120, 10927-10935; b) J.H. Zhou, Z.J. Sui, J. Zhu,
P. Li, D. Chen, Y.C. Dai, W.K. Yuan, Carbon 2007, 45, 785-796.
[16] a) A. Jaggernauth, R. M. Silva, M. A. Neto, M. J. Hortiguela, G.
Goncalves, M. K. Singh, F. J. Oliveira, R. F. Silva, M. Vila, J. Phys. Chem.
C 2016, 120, 24176-24186; b) R. M. Silva, M. C. Ferro, J. R. Araujo, C.
A. Achete, G. Cavel, R. F. Silva, N. Pinna, Langmuir 2016, 32, 7038-
7044; c) D. V. Lam, T. Gong, S. Won, J. H. Kim, H. J. Lee, C. Lee, S. M.
Lee, Chem. Commun. 2015, 51, 2671-2674.
[23] G. Korotcenkov, Mater. Sci. Eng., B 2007, 139, 1-23.
[24] a) Z. X. Zhou, F. He, Y. F. Shen, X. H. Chen, Y. R. Yang, S. Q. Liu, T.
Mori, Y. J. Zhang, Chem Commun 2017, 53, 2044-2047; b) J. H. Wang,
Y. L. Chen, Y. F. Shen, S. Q. Liu, Y. J. Zhang, Chem Commun 2017,
53, 2978-2981.
[25] Q. Li, Y. He, R. F. Peng, Eur. J. Inorg. Chem. 2015, 4062-4067.
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Entry for the Table of Contents
FULL PAPER
The present of C-O-Zn bond in the
boundary of ZnO/carbon black hybrids,
C-O-Zn bond; Electron transfer
Jingfeng Wang,[a] Yang Li,[a] Huanhuan
Wang,[a] Shanxu Zhu,[a] Jia Zhou,[a]
Xiaohong Wu,*[a] Wei Qin*[b]
generated
by
ALD
technique,
accelerates the electron transfer from
excited ZnO to carbon black, resulting
in the better catalytic activity for
thermal decomposition of ammonium
perchlorate.
Page 1. – Page 6.
Title: Atomic Layer Deposited ZnO on
Carbon Black as High-Performance
Catalysts for the Thermal
Decomposition of Ammonium
Perchlorate
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