Applied Surface Science 211 (2003) 315–320

Surface-modification of SiO2 nanoparticles

with oleic acid
Zongwei Li, Yongfa Zhu*
Department of Chemistry, Tsinghua University, Beijing 100084, PR China
Received 18 January 2003; received in revised form 24 February 2003; accepted 24 February 2003

Abstract

SiO2 nanoparticles modified by oleic acid (OA) were prepared using surface-modification method in this work. Infrared
spectroscopy (IR), transmission electron microscopy (TEM) and X-ray photoelectron spectra (XPS) were used to investigate the
structure of the modified SiO2 nanoparticles. Effects on coverage and dispersion in oil by OA concentration were also studied.
The results indicate that OA-modified SiO2 nanoparticles are capable of dispersing stably in mineral oil and the OA is bonded to
the surface of SiO2 nanoparticles through esterification. The optimal reaction temperature and the proportion of OA to SiO2 were
established.
# 2003 Elsevier Science B.V. All rights reserved.

Keywords: Surface-modification; Nanoparticles; SiO2; Coverage

1. Introduction [4]. If the surface-modification agent are high-weight

Nanoparticles have received considerable attention
because of their special physical and chemical proper-
ties [1]. A variety of method for preparing nanopar-
ticles and evaluating their properties have been
developed [2,3]. However, inorganic nanoparticles
are very easily to agglomerate in mediums and show
poor dispersion capacity in organic solvents and oil,
therefore the applications of many nano-sized parti-
cles are largely limited. Fortunately, this problem
could be resolved by using some special preparation
technique, for example, the preparation of nanoparti-
cles with surface-modification of organic compounds
*
Corresponding author. Tel.: þ86-10-62783586;
fax: þ86-10-62787601.
E-mail address: zhuyf@chem.tsinghua.edu.cn (Y. Zhu).
hydrocarbons, the nanoparticles thus prepared can be
dispersed stably in organic solvents and oil [5]. It has
been reported that organic compounds coating PbS,
TiO2, MnS have been synthesized successfully to
improve their dispersive capacity in organic solvents
and oil [4–6]. However, few of these papers studied
systemically the effects of cis-9-octadecenoic acid
(oleic acid, OA) concentration and reaction tem-
perature on the coverage and dispersion in organic
solvents and few of them established optimal synthetic
parameters.
Silicon dioxide (SiO2) is a useful catalyst and
semiconductive material, and has been widely used
in many fields. In the present work, OA surface-
modified SiO2 nanoparticles was synthesized using
surface-modification method [7,8], and the optimal
synthetic parameters were established. The structure
of the nanoparticles was investigated with infrared

0169-4332/03/$ – see front matter # 2003 Elsevier Science B.V. All rights reserved.
doi:10.1016/S0169-4332(03)00259-9
316 Z. Li, Y. Zhu / Applied Surface Science 211 (2003) 315–320

spectroscopy (IR), transmission electron microscopy

(TEM) and X-ray photoelectron spectra (XPS).

2. Experimental

2.1. Chemicals

The reagents in the experiments, such as OA,

n-hexane, etc., were analytical pure reagents (AR),
and were purchased and used without further treat-
ment. The SiO2 nanoparticle was A-380 with diameter
of 10–20 nm.

2.2. Equipments

IR analysis was carried out on a PE-2000 FT-IR

spectrometer. A H-800 TEM was used to examine the
morphology of the nanoparticles. XPS analysis was
conducted in PHI-5300 ESCA system at power 250 W,
with Al Ka radiation.
Fig. 1. IR spectra of (a) non-coated SiO2 nanoparticles, (b–f)
2.3. Preparation of surface-modified SiO2 OA-modified SiO2 nanoparticles and (g) modification agent OA.
nanoparticles
chain is present in the OA-modified nanoparticles. In
n-Hexane and OA were mixed with stirring, then an Fig. 1(g), the peak at 1729 cm1 correspond to –COOH
appropriate amount of SiO2 nanoparticles was added in OA. In Fig. 1(b–f), the –COOH vibration peak at
into them. The mixture was heated under vigorous 1729 cm1 disappears, while a new peak at 1590 cm1
stirring at 60 8C for 4 h. The solution was then filtered
and the precipitate was rinsed thoroughly with the
mixture solvent of alcohol and deionized water. The
precipitate was kept in a vacuum desiccator for 24 h.
A white powder was obtained, which was the surface-
modified nanoparticles of SiO2 with OA. By chang-
ing the proportion of OA to SiO2 nanoparticles and the
reaction temperature, a series of samples were prepared.

3. Results and discussion

3.1. Surface groups of SiO2 nanoparticles

The surface groups of SiO2 nanoparticles before

and after modification were characterized by IR and
XPS. Fig. 1 compares the IR spectra of non-coated
SiO2 nanoparticles and OA-modified SiO2 nanoparti-
cles and the modification agent OA. In Fig. 1(b–f), the
peaks at 2926 and 2855 cm1 show that long alkyl
Fig. 2. Effect of concentration of OA on the surface characters
of SiO2 nanoparticles. (a) ––OH-peak value of the surface of
nanoparticles—concentration of OA, (b) marked peak value of OA
bonded on surface of nanoparticles—concentration of OA, (c) (–OA)/
(–OH) on the surface of nanoparticles—concentration of OA.
 Z. Li, Y. Zhu / Applied Surface Science 211 (2003) 315–320 317

corresponding to carboxylate appears. Thus, it can be
concluded that the OA, –COOH has reacted with –OH
on the surface of SiO2, and the product is carboxylate.
However, in Fig. 1(b)–(f), the appearance of peak
3430 cm1 shows that –OH on the surface of the SiO2
nanoparticles has not reacted with OA completely. Thus,
the process of reaction can be described as following
SiO2 ðOHÞn þ yHOOCC17 H33
! SiO2 ðOHÞny ðOOCC17 H33 Þy þ yH2 O:
From Fig. 1(b)–(e), the strength of peak at
3430 cm1 corresponding to –OH on the surface of
the SiO2 nanoparticles decreases in turn, while the
strength of peak at 2926 and 2855 cm1 correspond-
ing to long alkyl chain of OA and the peak at
1590 cm1 corresponding to –COO increase in turn.
The strength of those peaks in Fig. 1(e) are almost the
same as which in Fig. 1(f), indicating that the super-
fluous OA did not combine with SiO2 nanoparticles
in samples E and F.

Fig. 3. XPS spectra of OA-modified SiO2 nanoparticles. (a) typical survey of modified SiO2 nanoparticles, (b) close-up survey at C1s, and
(c) close-up survey at O1s.
318 Z. Li, Y. Zhu / Applied Surface Science 211 (2003) 315–320
The effect of concentration of OA on the surface
characters of SiO2 nanoparticles is given in Fig. 2.
When the proportion between OA and SiO2 in the
reactants is about 15%, the marked peak value of –OH
on the surface of nanoparticles reaches a constant.
This indicates that the strong active sites on the surface
of nanoparticles have almost reacted with OA com-
pletely and the weak active sites are unlikely to react
with the OA. It is seen from Fig. 2 that from samples A
to F, (–OA)/(–OH) on the surface of nanoparticles
increased with the increase of the concentration of OA
in reactants within a certain extension and then
reaches a constant. Because the superfluous OA can-
not bind with SiO2 nanoparticles, the optimal propor-
tion of OA to SiO2 is about 20%, which is between
samples D and E.
The XPS spectra of OA-modified SiO2 nanoparti-
cles, C1s and O1s of the nanoparticles are shown in
Fig. 3. Since there are a large number CH2 groups in
the nanoparticles, the binding energy of C1s in long
alkyl chain is used as reference. The C1s spectra
consist of peaks at 284.5 eV (reference peak) and
288.3 eV, corresponding to alkyl and carboxylate car-
bon, respectively. The peak of Si2p is at 103.1 eV,
which is in agreement with Si2p in SiO2 (103.3 eV).
The O1s spectra measured consist of peaks at 530.5,
531.6 and 533.2 eV, corresponding to O1s in carbox-
ylate, –OH and SiO2, respectively. These results illus-
trate that the nanoparticles have a SiO2 core and an
organic acid surface layer. It can be concluded that the
OA is attached to SiO2 nanoparticles via physical
absorption or chemical bond. According to the results
of IR and XPS, we can affirm that the OA is bonded to
the surface of SiO2 nanoparticles.
Fig. 4 gives the relationship between the concentra-
tion of OA and the surface coverage of SiO2. It can be
seen that (–OA)/(–OH) on the surface of nanoparticles
is in direct proportion to the concentration of OA in the
reactants within a certain extension and then reaches a
constant. Thus, it indicates that the OA covers the
surface of nanoparticles equably instead of assembling
and the saturation of OA is about 20%.
3.2. Morphology of SiO2 nanoparticles
The morphology of SiO2 nanoparticles were carried
out by using TEM. Fig. 5 shows the TEM images of
OA-modified SiO2 nanoparticles and non-modified
Fig. 4. Relationship between the concentration of OA and surface
coverage of SiO2.
SiO2 nanoparticles. Fig. 5(a) and (c) are the TEM
images of nanoparticles which are magnified 10,000
times. It is founded from Fig. 5(a) that OA-modified
nanoparticles are dispersed well. It is seen from
Fig. 5(c) that non-modified particles are seriously
aggregated and the diameter of the aggregation is
about thousands of nanometers. Fig. 5(b) and (d)
are the TEM images of nanoparticles which are mag-
nified 100,000 times. It is found from Fig. 5(b) that
OA-modified nanoparticles are distinct and individual
particle can be distinguished. It is seen from Fig. 5(d)
that non-modified particles lap over and distinct par-
ticles can hardly be observed. These results confirm
that the phenomena of nanoparticles agglomeration
are decreased effectively because the nanoparticles
cores are kept apart by the surface-modification layer
and the repulsion between the particles is increased.
3.3. Dispersive capacity in organic solvents
The OA-modified SiO2 nanoparticles can be disper-
sed in some organic solvents, such as n-hexane, alcohol,
plasticizer, but it cannot be dispersed in water. The
non-modified SiO2 nanoparticles cannot be dispersed
in non-polar organic solvents, while it has good dis-
persive capacity in water. These experimental phenom-
ena indicate that a hydrophobic modified layer exists
on the surface of the OA-modified SiO2 nanoparticles.
Because SiO2 nanoparticles are very active and apt
to absorb –OH, the groups of –OH on the surface
of the nanoparticles can’t react with OA completely.
Thus, the structure of the OA-modified SiO2 is SiO2-
(OH)ny(OOCC17H33)y. It is seen from the structure
 Z. Li, Y. Zhu / Applied Surface Science 211 (2003) 315–320 319

Fig. 5. TEM image of OA-modified SiO2 nanoparticles (a and b) and non-modified SiO2 nanoparticles (c and d).

that the hydrophobic long alkyl chain on the surface of
particles improve the dispersive capacity of nanopar-
ticles in non-polar organic solvents and the –OH on
the surface of nanoparticles make them easy to dis-
perse in polar alcohol.
Table 1 shows the effect of OA/SiO2 on dispersive
capacity of nanoparticles. It is seen from Table 1 that
samples A–C are hard to disperse in non-polar organic
solvents, and samples D–F have good dispersive capa-
city in those solvents. The stability order of samples

Table 1
Effect of OA/SiO2 on dispersion of nanoparticles

Sample OA/SiO2 in the Dispersiona in different solvents

reactants (%)
n-Hexane Plasticizer CCl4 Alcohol Water

A 4.5 þ þ þ þþ þþþþ
B 9.1 þþ þþþ þþ þþþ þþþ
C 13.6 þþþ þþþþ þþ þþþþ þþþ
D 31.8 þþþþ þþþþ þþþ þþþþ þþ
E 68.2 þþþþ þþþþ þþþþ þþþþ þþ
a
Key: þ, un-disperse; þþ, partial-disperse; þþþ, disperse; and þþþþ, stable-disperse.
320 Z. Li, Y. Zhu / Applied Surface Science 211 (2003) 315–320

Table 2
Effect of reaction temperature on dispersion of nanoparticles

Sample Reaction Dispersiona in different solvents

temperature (8C)
n-Hexane Plasticizer CCl4 Alcohol Water
I 80 þ þ þ þ þþþ
II 70 þþ þþþ þþ þþþ þþþ
III 60 þþþ þþþþ þþþ þþþþ þþ
IV 50 þþþ þþþ þþ þþþþ þþþ
a
Key: þ, un-disperse; þþ, partial-disperse; þþþ, disperse; and þþþþ, stable-disperse.

in plasticizer is following: 24 h < A < B < 48 h <
DF. That indicates that the OA is insufficient in
samples A–C but superfluous in samples E and F, so
the optimal proportion of OA to SiO2 in reactants is
about 20%.
Table 2 shows the effect of reaction temperature on
dispersive capacity of nanoparticles. It is found that
the optimal reaction temperature is 60 8C.
4. Conclusions
1. The OA-modified SiO2 nanoparticles have been
synthesized by a chemical surface-modification
method.
2. The mechanism of the reaction between SiO2
nanoparticles and OA is esterification.
3. The optimal synthetic parameters were established:
reaction temperature is 60 8C, optimal proportion
of OA to SiO2 in reactants is about 20%.
Acknowledgements
This work was partly supported by Chinese National
Science Foundation(20071021), Trans-Century Train-
ing Program Foundation for the Talents by the Ministry
of Education, P.R.C. and supported by the Excellent
Young Teacher Program of MOE, PR China.
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