ZnO2 Nanoparticles Using Zinc(II) Isobutylcarbamate

Bull. Korean Chem. Soc. 2014, Vol. 35, No. 2 431

http://dx.doi.org/10.5012/bkcs.2014.35.2.431

Preparation of ZnO2 Nanoparticles Using Organometallic Zinc(II)

Isobutylcarbamate in Organic Solvent
Kyung-A Kim, Jae-Ryung Cha, Myoung-Seon Gong, and Jong-Gyu Kim*
Department of Chemistry, Dankook University, Cheonan, Chungnam 330-714, Korea. *E-mail: jkim16@dankook.ac.kr

Deparment of Nanobiomedical Science and WCU Research Center of Nanobiomedical Science,

Dankook University, Cheonan, Chungnam 330-714, Korea
Received September 16, 2013, Accepted November 12, 2013
Zinc peroxide nanoparticles (ZnO2 NPs) were prepared by reacting zinc(II) isobutylcarbamate, as an organometallic precursor, with hydrogen peroxide (H2O2) at 60 C. Polyethylene glycol and polyvinylpyrrolidone
were used as stabilizers, which suppressed aggregation of the ZnO2 NPs. Conditions such as concentrations of
H2O2 and the stabilizer were systemically controlled to determine their effect on the formation of nano-sized
ZnO2 NPs. The formation of stable ZnO2 NPs was confirmed by UV-vis, Raman spectroscopy, X-ray
photoelectron spectroscopy, transmission electron microscopy (TEM), scanning electron microscopy (SEM),
and X-ray diffraction. The TEM images revealed that polyvinylpyrrolidone-stabilized ZnO2 NPs (diameter,
1030 nm) were well dispersed in the organic solvent. Quite pure ZnO NPs were obtained from the peroxide
powder by simple heat treatment of ZnO2. The transition temperature of 170 oC was determined by differential
scanning calorimetry.
Key Words : Zinc peroxide, Zinc(II) isobutylcarbamate, ZnO-precursor, Hydrogen peroxide

Introduction
Interest in metal oxide nano-materials has increased due to
their potential applications. Of these oxides, zinc oxide is a
transparent electroconductive and piezoelectric material
with applications in electronic, photonic photo cells and
laser diodes devices. But, the shape and size of nano zinc
oxide govern its properties.1-3 In a wet chemical route, most
zinc oxide nanoparticles (NPs) of various morphologies
have been synthesized by decomposing zinc compounds
through decomposition/oxidation at different temperatures.
ZnO2 NPs are a semi-conductor with a wide band gap
energy of 4.20 eV.4,5 ZnO2 NPs can be applied to high-tech
plastic processing6,7 and the rubber industry.8 They can also
be used as an oxidant for explosives and pyrotechnic mixtures.9 ZnO2 NPs can additionally be used as precursors to
prepare ZnO NPs.10,11 ZnO2 is an odorless white stable solid
at ambient temperature, but it is decomposed by heating at
150 C to release oxygen.12 New methods of preparing ZnO2
powder use an aqueous system with various zinc salts.12-14
ZnO2 powder is mostly produced by adding one of the
followings: ZnO,15 Zn(OH)2,15 ZnR2,4 Zn(NO3)2,16 and
ZnCO315 to a solution of H2O2 with an additional source of
energy such as light. A variety of ways are available to prepare ZnO2 powder such as sol-gel synthesis, polyol synthesis, autoclaves, hydrothermal method, and laser ablation.12-21
The preparation of stabilized ZnO2 NPs has been reported
using zinc oxide as the precursor and phosphate acid or salt
derivatives as stabilizers.22 But, most methods require high
temperature and vacuum. Furthermore, the products obtained using these methods are poorly crystallized and may
contain impure phase precursors or reactants.

In this study, we demonstrate that ZnO2 NPs can be prepared via a thermal reaction of zinc(II) isobutylcarbamate as
new organic precursor with H2O2: (Zn(OCONHC4H9)2 +
H2O2 ZnO2 + 2 C4H9NH2 + 2 CO2) at 60 C within 30
min. The resulting products were characterized by X-ray
diffraction (XRD), Raman spectroscopy, X-ray photoelectron spectroscopy (XPS), field emission scanning electron
microscopy (FESEM), transmission electron microscopy
(TEM), high resolution TEM and selected area electron
diffraction (SAED).
Experimental
Materials and Instruments. Isobutylammonium isobutylcarbamate was synthesized from isobutylamine and
carbon dioxide. A ZnO2-precursor, zinc(II) isobutylcarbamate (Zn(IBC))2, was prepared by reacting zinc powder with
isobutylammonium isobutylcarbamate.23,24 Polyvinylpyrrolidone (PVP K15, Mw = 6,00015,000) and PVP K30 (Mw
= 40,00080,000) were purchased from Daejung Chem.
Metals Co. Ltd. and poly(ethylene glycol) (PEG 6000) was
purchased from Yakuri Pure Chem. Co. Ltd. Hydrogen peroxide, used as the oxidizing agent, was obtained from Dongwoo Fine Chem. Co. Ltd. The hydrogen peroxide solution in
2-methoxyethanol was dehydrated with anhydrous MgSO4.
TEM (JEM-2000EXII; JEOL, Tokyo, Japan), HR-TEM (JEM3010; JEOL, Tokyo, Japan) and UVvis (Shimadzu, UV1601PC, Tokyo, Japan) spectrometry were employed to
characterize the ZnO2 NPs. The XRD patterns of the ZnO2
NPs were measured using a Shimadzu XD-D1 X-ray diffractometer with CuK radiation ( = 1.54056 ) at a scanning rate of 2 C/second, in the 2 range from 1090. The 2-

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methoxyethanol solution used for dispersing the ZnO2 NPs

was dried slowly on amorphous carbon supported on a TEM
copper mesh grid. Raman spectra were taken by Senterra
Raman spectroscopy. Surface characterization was performed by XPS. The survey spectrum, Zn 2p, and O 1s lines were
recorded with an electron spectrometer (VG Microtech
ESCA2000) with an aluminum anode (K, 1486.6 eV).
Differential scanning calorimetry (DSC) measurements were
performed with a Sinco EvoSetaram DSC 131 instrument,
and the thermogravimetric analysis (TGA) was conducted
on a Shimadzu TGA 50 instrument at a heating rate of 10 oC/
min under a nitrogen atmosphere.
Preparation of the ZnO2 NPs. Nanometer-sized ZnO2
NPs were synthesized using an organometallic zinc carbamate precursor. Zn(IBC)2 (2.05 g) and PEG 6000 (2 g) were
dissolved in 2-methoxyethanol (30 mL) under vacuum at
room temperature for 30 min. Then, H2O2: 2-methoxyethanol
(3:97) (10 mL) was slowly injected into the Zn(IBC)2
solution, which was heated to 60 oC for 30 min. The reaction
mixture gradually formed a white dispersion to produce the
ZnO2 nanocolloid solution. The ZnO2 NPs were separated by
centrifugation and washed with distilled water and alcohol
several times. The precipitate was dried to a powder in air.
Other ZnO2 NPs were prepared in the presence of PVP
stabilizer using a similar procedure.
Results and Discussion
Zinc(II) isobutylcarbamate (Zn(IBC)2) is prepared by the
reaction of isobutylammonium isobutylcarbamate with zinc
metal powders. After 24 h, the reaction mixtures changed
from gray slurry to transparent solution, indicating formation
of Zn(IBC)2. The formation of Zn(IBC)2 was confirmed by
FT-IR, 1H NMR, 13C NMR and Raman spectra (Figure S1S4). The TGA curve showed no heat flow up to 200 oC and
the endothermic peak appeared at 125 oC, confirming that
the secession of decomposition of Zn(IBC)2 occurred in
succession, and that 2-methoxyethanol evaporated while
ZnO was formed, which matched well with the heat flow in
the DSC curve (Figure S5).
Zn(IBC)2 and H2O2 were used as the zinc precursor and
oxidizing agent, respectively, to prepare the ZnO2 nanocolloids. This is the first example of preparing a ZnO2 nanocolloidal solution in an organic solvent using a Zn(IBC)2
solution.
Several stabilizers were tested and the results indicated
that the nature and concentration of the stabilizers are crucial
parameters for yield of the colloidal solution and stability of
the particles. PVP was selected as the stabilizer to disperse
the nano-sized zinc peroxide in organic solvent. When the
oxidizing agent solution was poured into the Zn(IBC)2
solution at room temperature, the reaction did not proceed.
As the temperature was increased to 60 oC, the color of the
solution changed from transparent to white colloid. At this
time, the precursor was rapidly oxidized to produce ZnO2
NPs. The oxidation reaction of Zn(IBC)2 with H2O2 may be
represented as follows: Zn(OCONHC4H9)2 + H2O2 ZnO2

Kyung-A Kim et al.

+ 2 C4H9NH2 + 2 CO2.
Experiments were carried out to determine the optimum
conditions for preparing stable ZnO2 colloids of different
sizes, shapes, and particle size distributions, while varying
the concentrations of Zn(IBC)2, oxidizing agent, and stabilizer
in the mixture.
Figure 1 shows the UV-vis spectra of zinc peroxide colloidal solutions under different concentrations of oxidizing
agent (3%, 5%, and 7%), which was prepared by dispersing
ZnO2 NPs in 2-methoxyethanol. Maximum absorption occurred at 234 nm when the H2O2 concentration was 3% or 5%.
ZnO2 NPs prepared using 7% H2O2 exhibited a slight red
shifted absorption from 234 to 243 nm. Abrupt oxidation
and decomposition of Zn(IBC)2 at high concentration of
H2O2 caused aggregation of the ZnO2 NPs.
TEM studies were conducted to confirm the shape and
size of the ZnO2 NPs formed by reacting Zn(IBC)2 (1.5% in
2-methoxyethanol) and hydrogen peroxide (3% H2O2 in 10
mL of 2-methoxyethanol) without a stabilizer. The formation
of ZnO2 NPs was monitored by the concentration (3%, 5%,
and 7%) of H2O2 (Figure 2). No detectable difference in size
was observed when the H2O2 concentration was less than
5% (Figure 2(a) and (b)). The particles were particularly
multi-dispersed at higher H2O2 concentrations, with concomitant aggregation of the particles (Figure 2(c)).
Figure 3 shows the UV-vis absorption peak of ZnO2
colloids at 213 nm when PEG 6000, PVP K15 and PVP K30

Figure 1. UV-vis absorption spectra of ZnO2 colloid solutions

obtained from Zn(IBC)2 (1.5% in 2-methoxyethanol) at various
concentration of H2O2.

Figure 2. TEM images of ZnO2 NPs obtained from Zn(IBC)2 at a

concentration of (a) 3%, (b) 5% and (c) 7% hydrogen peroxide.

ZnO2 Nanoparticles Using Zinc(II) Isobutylcarbamate

Figure 3. UV-vis absorption spectra of ZnO2 colloid solutions

obtained from Zn(IBC)2 in the presence of PEG and PVP
stabilizers.

were used as stabilizers. A blue shift of the maximum absorption peak was observed by adding stabilizer. However, a
broad absorption peak in the spectrum extended from 300
400 nm, indicating the formation of larger NPs due to more
aggregation of the ZnO2 NPs. Moreover, the ZnO2 NPs exhibited a slight sharp absorption peak at 250400 nm when
the PVP concentration was increased.
Stabilized particles of various sizes and shapes formed en
masse at concentrations < 1.5% Zn(IBC)2, as shown in

Figure 4. TEM images of ZnO2 NPs obtained from Zn(IBC)2

oxidized with 3% H2O2 in the presence of 2 g of (a) PEG 6000;
inset figure, PEG 200, (b) PVP K15 as a stabilizer and (c) SEM
image of sample obtained from (b).

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Figure 4. Nevertheless, the ZnO2 NPs retained nano-range

sizes. All ZnO2 NP samples were spherically shaped with
sizes of 50200 nm. This result shows that the surfaces of
the ZnO2 NPs were hydrophobic due to the absorbed PEG or
PVP. However, the results shown in Figure 4 indicate that
stabilizer was required to disperse the ZnO2 NPs. Use of
PEG 6000 resulted in a large difference between agglomeration shapes, as shown in Figure 4. ZnO2PEG 6000 revealed quite dense polygon-type agglomerates with sizes of 30
100 nm, whereas ZnO2PEG 200 created large typical spherical
NPs (inset figure). Figure 4(b) shows a TEM image of the
ZnO2 NPs synthesized using PVP K15; the product obtained
was well-dispersed spherical NPs with sizes of 50200 nm.
The SEM image shows that nanospheres with a large size
distribution (50220 nm in diameter) were formed (Figure
4(c)). The SEM image revealed that the nanospheres were
structurally solid and their diameters were consistent with
the TEM result.
PVP K30, with a larger molecular weight, was employed
to obtain ZnO2 NPs < 100 nm. Spherical ZnO2 NPs with
particle sizes of 60150 nm were randomly formed in the
presence of PVP K30 (2 g) in Figure 5(a). When the amount
of PVP K30 was increased, spherical ZnO2 NPs with
particle sizes of 1030 nm were observed (Figure 5(b)). As a
result, the dispersion ability of PVP K30 was better than that
of PVP K15. Therefore, high molecular weight PVP K30
was useful to obtain nano-sized, spherical ZnO2 NPs. This is
because PVP K30 adsorbed on ZnO2 surfaces plays an
important role sterically stabilizing ZnO2 colloidal dispersions. Figure 5(c) shows a high resolution TEM image of

Figure 5. TEM images of ZnO2 NPs obtained from Zn(IBC)2 in

the presence of (a) 2 g and (b) 4 g of PVP K30, (c) HRTEM image
of ZnO2 sample of (a) or (b), and (d) the corresponding SAED
pattern.

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Figure 6. XPS spectrum of ZnO2 NPs obtained from Zn(IBC)2

and H2O2; inset figure is the O 1s changes between ZnO and ZnO2.

Kyung-A Kim et al.

Figure 8. TGA and DSC curves of the ZnO2 powders obtained

from Zn(IBC)2.

ZnO2 NPs with lattice spacing of about 0.28 nm for the (111)
plane in the cubic ZnO2. Figure 5(d) shows the corresponding selected area electron diffraction (SAED) pattern, confirming crystallinity of the product. These interval distances
of 0.28 nm correlate to the distances of (111) of ZnO2, which
has a cubic crystal.
Figure 6 presents the XPS survey spectrum of the ZnO
NPs. Note that no impurities, other than adventitious carbon,
were detected. The inset figure shows the O 1s regions of the
XPS spectrum. The highest peak in the O 1s spectrum was
531.23 eV, which is characteristic of oxygen species integrated in the material as hydroxide (OH) or peroxide (O22).
The oxygen in zinc peroxide compared with the oxygen in
zinc oxide (529.9 eV) was located at a higher binding energy
of 531.23 eV. The other broad peak at 528.87 eV was
attributed to poorly bound oxygen ions.
Figure 7 depicts the XRD spectra of ZnO (JCPDS card
No. 36-1451) and ZnO2 (JCPDS card No. 13-0351) synthesized in powder form by simple heating Zn(IBC)2 at 125 C
and heating at 60 C in the presence of H2O2, respectively.
The XRD spectra clearly show the crystalline structure and
the various peaks of the ZnO2 NPs. The dominant peaks of

ZnO2 were identified at 2 = 32.8, 37.18, 53.48, and 63.48

(ZnO for 2 = 31.38, 34.88, 36.48, 48.28, 57.08, 63.28, and
68.38), which was in agreement with the literature.25
ZnO2 can be used as a precursor to prepare ZnO. The
thermal behavior of the ZnO2 powder was investigated by
TGA and DSC analyses to confirm the transformation of
ZnO2 to ZnO. The TGA curve in Figure 8 shows that the
weight losses below 100 C were about 4.8%, indicating that
the powder samples adsorbed water.4 The small amount of
adsorbed water in the powder samples was possible to avoid
due to the preparation method using organic solvent such as
2-methoxyethanol. But the fine particle size and instability
of the material retains moisture. Weight losses were about
9.2% up to 170 C in the TGA curve. It drops from 91.8% to
76.8% in the temperature range from 170 to 210 C and then
remains almost constant up to 600 C. Based on the reaction
of 2 ZnO2 2 ZnO + O2, the calculated weight loss was
16.4%. The DSC curve in Figure 8 shows a sharp exothermic peak starting at 170 C, which is coincident with the
abrupt weight loss in TGA curve. It is known that the

Figure 7. X-ray diffraction patterns of ZnO2 and ZnO prepared by

reacting Zn(IBC)2 with H2O2 at 60 oC and simple heating at 125
o
C, respectively.

Figure 9. X-ray diffraction patterns of zinc peroxide (ZnO2) heated

at various temperatures for 30 min.

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size and shape of the ZnO2 NPs were confirmed by UV-vis,

SEM, TEM and HRTEM. The ZnO2 NPs were reduced to
ZnO by heating at 170 oC within 30 min. According to these
characteristics, this Zinc(II) isobutylcarbamate precursor has
sufficient potential for the preparation of ZnO2 and ZnO at
low temperature.
Acknowledgments. The present research was conducted
by the research fund of Dankook University in 2012.
References

Figure 10. The Raman spectra of ZnO prepared from annealing of

ZnO2 at 170 oC for 30 min and ZnO2 nanoparticles.

transition temperature of ZnO2 is about 200 C.26 The result

of isothermal aging (annealing) at 170 C for 30 min was not
coincident with that of the sample annealed with a 10 C/
min. Overall, the TGA/DSC results confirmed that the second
weight loss at around 170 C is indeed due to the decomposition of the ZnO2 cubic phase into the hexagonal ZnO.
ZnO2 powder was prepared by adding 3% H2O2 during the
thermal decomposition process, and the solution was heated
to various annealing temperatures of 120170 oC for 30 min
to investigate the effect of heating on the transformation of
ZnO2 into ZnO.
Zn(IBC)2 was directly transformed to ZnO by heating
Zn(IBC)2 in an H2O2 solution. The transparent solution of
Zn(IBC)2 and H2O2 changed into a white colored small
grain. Nanodimensional ZnO powders were obtained through
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Figure 10 shows the Raman spectra of the ZnO2 powder
after heating at 170 oC for 30 min, and the result was the
same as that of bulk ZnO sample. Four peaks were observed
at 331, 385, 438, and 578 cm1. The peaks at about 438 cm1
were assigned to the two nonpolar Raman active E2 vibrational modes of ZnO and are associated with the E2-low
mode and E2-high mode, respectively. The peaks at about
385 and 578 cm1 were attributed to the A1(TO) and A1(LO)
modes, and the 331 cm1 band was due to the 2-E2(M) mode
of ZnO, which is related to the multiphonon process.27
Conclusions
In summary, pure stabilized ZnO2 NPs were prepared by
reacting new organometallic precursor, zinc(II) isobutylcarbamate and hydrogen peroxide at 60 oC. Spherical and
nano-sized ZnO2 NPs with sizes of 1030 nm were obtained
using high molecular weight PVP K30 as the stabilizer. The

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