CHEM. RES.

CHINESE UNIVERSITIES 2011, 27(3), 500502

Preparation and UV-light Absorption Property of Oleic

Acid Surface Modified ZnO Nanoparticles
KANG Jong-hun1,2, GUO Yu-peng2, CHEN Yue2 and WANG Zi-chen2*
1. Pyongyang Printing Industry University, Pyongyang, DPRK;
2. College of Chemistry, Jilin University, Changchun 130021, P. R. China
Abstract Syntheses of zince oxide(ZnO) nanoparticles by direct precipitation and surface modification with oleic
acid were reported. ZnO nanoparticles were characterized via X-ray diffractometry(XRD), transmission electron
microscopy(TEM), infrared spectroscopy(IR) and UV-Vis spectroscopy. The prepared ZnO nanoparticles were nearly
spherical and highly crystalline with an average size of 29 nm. In addition, high UV-light absorption properties of
oleic acid surface modified ZnO nanoparticles were successfully obtained for a dispersion of ZnO nanoparticles in
ethanol.
Keywords ZnO nanoparticle; Oleic acid; Modification; UV-light absorption; Dispersion
Article ID 1005-9040(2011)-03-500-03

Introduction

Zinc oxide(ZnO) nanoparticles have attracted much interest because they possess various remarkable physical and
chemical properties that are distinct from those of conventional
bulk materials. ZnO is widely used for cosmetic application
because it is a chemically stable and environmentally friendly
material that has good transparency and UV-blocking properties[13]. Different synthesis methods have been devised,
including sol-gel technique[4], microemulsion synthesis[5], mechanochemical processing[6], spray pyrolysis and drying[7,8],
thermal decomposition of organic precursor[9], RF plasma synthesis[10], supercritical-water processing[11], selfassembling[12],
hydrothermal processing[13], vapor transport process[14], sonochemical or microwave-assisted synthesis[15,16], direct precipitation[17] and homogeneous precipitation[18]. However, ZnO in
nanoparticles due to the existence of water molecules results in
hard agglomerates, which impede the application of ZnO
nanoparticles. Therefore, the removal of water moiety in the
nanoparticles is a key process for reducing hard agglomerates.
The modification of nanoparticles to enhance the surface
chemical and physical properties is the key for the successful
application of nanomaterials. Oleic acid is commonly used to
modify SiO2[19], TiO2[20], CaCO3[21], CuS[22], ZnO[23]. In particular, surface-modified ZnO particles received much attention
because of enhanced dispersability in fluids. In the present investigation, the precursor of ZnO nanoparticles was prepared
by precipitation from the solutions of zinc chloride and sodium
carbonate in the presence of surfactant and ZnO nanoparticles
were obtained after calcination. On one hand, the surface of
ZnO nanoparticles was modified with oleic acid to improve the
compatibility between inorganic nanoparticles and organic
matrix. Furthermore, the UV-light absorption property of a ZnO

nanoparticle-ethanol dispersion was also evaluated. The nanoparticles were characterized with infrared spectroscopy(IR),
transmission electron microscopy(TEM), X-ray photoelectron
spectrometry(XPS) and UV-Vis spectroscopy.

2
2.1

Experimental
Materials

Zinc chloride(ZnCl2), sodium carbonate(Na2CO3), sodium

dodecylbenzenesulfonate(SDBS), toluene, cyclohexane, dioctyl
phthalate(DOP), n-hexane and deionized-water were used in
the experiments. All the reagents used were analytical grade.

2.2

Synthesis of Nanosized ZnO

ZnO nanoparticles were synthesized by the reaction of

ZnCl2 with Na2CO3 aqueous solution. ZnCl2 and Na2CO3 were
dissolved in deionized-water to form solutions with certain
concentrations, the surfactant SDBS added into Na2CO3
aqueous solution, its concentration was 3 mmol/L. First of all,
100 mL of 0.8 mol/L ZnCl2 aqueous solution was added into a
three-neck flask, and then the temperature was raised to 80 C
in a water bath. Next, 100 mL of 0.67 mol/L Na2CO3 aqueous
solution including SDBS was added dropwise slowly to it
under continuous stirring. Last, the temperature was held at
80 C for 40 min. The precipitate was collected by filtration
and washed with distilled water and absolute ethanol for several times. Then the precipitate was dried at 80 C under vacuum
for 12 h to have the precursor ready. Afterwards the precursor
calcinated at 400 C for 2 h to obtain the ZnO nanoparticles.

2.3

Surface Modification with Oleic Acid

For the surface modification with oleic acid, the amount of

*Corresponding author. E-mail: wangzc@jlu.edu.cn

Received May 17, 2010; accepted June 13, 2010.
Supported by the Key Project of the National Eleventh Five-Year Research Programe of China(No.2008BAE66B00).

No.3

KANG Jong-hun et al.

oleic acid was varied in the experiments. Typically, oleic acid

of 0.05 g was dissolved in 100 mL of absolute ethanol in a
flask to form the solution, and the mass ratio of oleic acid to
ZnO is 5%. The above ZnO nanoparticles of 1 g were then
added to the solution to react for 2 h at 60 C under stirring.
The particles were collected by filtration and washed with distilled water and absolute ethanol for several times, then dried at
50 C for 24 h.

2.4

LD =

V
100%
V + 50

Particle Characterization

Fourier transform infrared(FTIR) analysis was performed

on FTIR-8400S(Shimadzu, Japan) with KBr method. X-ray
diffraction(XRD) analysis for powders was performed on
XRD-6000(Shimadzu, Japan). The size and shape of nanoparticles were determined under a transmission electron microscope JEM-1200EX(JEOL, Japan). UV-Vis absorption of ZnO
nanoparticles was measured on a UV-2550 spectrophotometer
(Shimadzu, Japan) by dispersing nanoparticles in ethanol.

3
3.1

half-maximum, and is the Bragg diffraction angle. The XRD

peak (101) gives an average diameter of about 29 nm for ZnO
nanoparticles.
Fig.2 illustrates the TEM images of ZnO nanoparticles
without surface modification. ZnO nanoparticles consist mainly
of nearly spherical particles of a size of about 29 nm.

Measurement of Lipophilic Degree

The lipophilic degree(LD) of ZnO nanoparticles was characterized by dispersing the nanoparticles of 0.5 g in water of
50 mL with the addition of methanol[16]. When ZnO nanoparticles were put into distilled water, the unmodified ZnO nanoparticles precipitated in water, while the modified ZnO nanoparticles which grafted with oleic acid, floated on the water
surface. When methanol was dropped into the water slowly
with continually stirring, the modified ZnO nanoparticles were
wetted and hence precipitated gradually. The volume of the
methanol(V) used was recorded and the LD was calculated
according to the following equation:

2.5

501

Results and Discussion

Fig.2

3.2

TEM image of ZnO nanoparticles

Surface Modification with Oleic Acid

The surface groups of ZnO nanoparticles before and after

modification were characterized by IR.
Fig.3 curves ac show the FTIR spectra of non-modified
ZnO nanoparticles, oleic acid modified ZnO nanoparticles
(OA-ZnO) and modification agent OA, respectively.
In Fig.3 curve a, the peak at 3438 cm1 shows that the
stretching vibration of the OH group is present in the
non-modified ZnO nanoparticles. In Fig.3 curve c, the peak at
1729 cm1 corresponds to COOH in OA. In Fig.3 curve b,
OA-ZnO corresponding to carboxylate appears, the strong
symmetric carboxylate stretching bands of oleate at 1402 and
1461 cm1, the asymmetric carboxylate stretching band of
oleate at 1551 cm1, and the peaks at 2926 and 2855 cm1 corresponding to long alkyl chain of OA were all found in the
FTIR spectrum of OA-ZnO. Thus, it can be concluded that the
OA-COOH has reacted with OH on the surface of ZnO, and
the product is carboxylate.

Characterization of ZnO Nanoparticles

The XRD pattern of ZnO nanoparticles is illustrated in

Fig.1. All the peaks can be well indexed to the zincite phase of
ZnO(International Center for Diffraction Data, JCPDS No. 361451). No peaks from other phase of ZnO and impurities were
observed, suggesting that high-purity ZnO was obtained.

Fig.3

Fig.1 XRD pattern for ZnO nanoparticles

The ZnO particle diameter D was calculated via the
Debye-Sherrer formula D=K/(cos), where K is Sherrer constant, is the X-ray wavelength, is the peak width of

IR spectra of non-coated ZnO nanoparticles(a),

oleic acid modified ZnO nanoparticles(b) and
modification agent OA(c)
The influence of the mass ratio of oleic acid to ZnO(%) on
lipophilic degree(LD) is illustrated in Fig.4.
As shown in Fig.4, the LD increases with increasing the
amount of OA when the amount of oleic acid is less than 4%;
when the amount increases above 4%, the LD decreases. This
indicates that OA reached the saturation of single-molecularlayer adsorption when the amount of OA was 4%, and higher
amount of OA have no effect on improving the LD. When the
amount of OA increases further, the long chain of OA entangles

502

CHEM. RES. CHINESE UNIVERSITIES

Fig.4 Influence of the amount of oleic acid on

modification effect
with each other, hindering the carboxyl group(COOH) of OA
to react with the hydroxide group on the surface of ZnO nanoparticles. The characteristics of oleic acid modified ZnO nanoparticles are shown in Table 1. The dispersabilities of T1 in
organic solvents were significantly improved compared with
that of non-modified ZnO nanoparticles.
Table 1
Run

Vol.27

Conclusions

Syntheses of zinc oxide nanomaterials by direct precipitation and surface modification with oleic acid have been reported. Furthermore, the UV absorption property of a ZnO
nanoparticle-ethanol dispersion was also evaluated. The following conclusions can be drawn from our experiments and
analyses: The ZnO nanoparticles obtained here were nearly
spherical particles with a size about 29 nm. The oleic acidmodified ZnO nanoparticles were obtained by the reaction between OH group on the nanoparticles and COOH of the
oleic acid. FTIR results confirm that an organic layer exists and
the linkage between inorganic nuclei and organic layer is
chemical bond. In addition, the LD of ZnO nanoparticles was
measured. A low-concentration dispersion of ZnO nanoparticles
in ethanol exhibited excellent UV shielding and transparency
properties.

Dispersibility of T0 and T1 in organic solvents*

Solvent

1
2

Toluene
Cyclohexane

Hexane

DOP

Sedimentation time/min
T0
<1
13

T1
40
125

150

52

380

5
Ethanol
5
890
* The amount of oleic acid is T0: 0%, T1: 5%; sedimentation time was
determined via a dispersed solution(10%, mass fraction) at room temperature.

The UV absorption property of the ZnO-ethanol dispersions was highly dependent on the ZnO nanoparticle concentration. The correlation between UV absorption property and
concentration in dispersion systems is well known. The
as-prepared ZnO nanoparticles exhibit high UV-blocking capacity, which makes the nanoparticles potentially useful in
cosmetic application.
For evaluation of UV absorption property, different concentrations of ZnO nanoparticles dispersions in ethanol were
prepared. The UV absorption spectra of the ZnO nanoparticleethanol dispersions with various mass fractions(0.005%
0.075%) are shown in Fig.5.

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