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Journal of Colloid and Interface Science 337 (2009) 7580

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Journal of Colloid and Interface Science


www.elsevier.com/locate/jcis

Surface modication of hydrophobic nanocrystals using short-chain carboxylic acids


Duc Quy Vo, Eui-Jung Kim, Sunwook Kim *
School of Chemical Engineering and Bioengineering, University of Ulsan, Ulsan 680-749, Republic of Korea

a r t i c l e

i n f o

Article history:
Received 8 March 2009
Accepted 23 April 2009
Available online 12 May 2009
Keywords:
Surface modication
Ligand exchange
Anti-solvent
Carboxylic acid
Fe3O4
TiO2

a b s t r a c t
Acrylic, acetic and methacrylic acids which are short-chain carboxylic acids have been applied to modify
the surface of oleic acid-coated TiO2 nanorods (NRs) and oleic acid/oleylamine-coated Fe3O4 nanoparticles (NPs). The short-chain carboxylic acids not only acted as modifying ligands but also as anti-solvents
during the ligand exchange processes. The prepared products have been characterized using TEM, HRTEM
and FTIR spectroscopy. The results show that the acrylic acid-exchanged TiO2 and Fe3O4 solution remain
stable even after six months, showing no agglomeration. Such acrylic acid-exchanged nanocrystals (NCs)
prepared in this work could also be well-dispersed in other polar solvents such as ethanol and ethanol/
water mixtures. On the contrary acetic acid and methacrylic acid-exchanged TiO2 solutions were not stable due to the presence of remaining oleic acid on the TiO2 surface. This approach has been shown to be
effective in making hydrophilic TiO2 NRs and Fe3O4 NPs and can also be applied to other NCs covered by
different hydrophobic ligands.
2009 Elsevier Inc. All rights reserved.

1. Introduction
Recently, lots of research works have been carried out in order
to synthesize nanocrystals (NCs) possessing excellent characteristics in term of narrow particle size distribution, high crystallinity
and uniform surface reconstruction [115]. The key strategy of recent investigations involves the use of surfactant which acts as a
stabilizing agent to prevent agglomeration and ensures a slow
growth rate of the particles [1618]. And the organometallic compounds have been commonly utilized as precursors for the preparation of NCs [1719]. The synthesis of NCs could be nely
controlled to produce materials with different shapes such as
sphere [1,4,68], cube [2,12], rod [5,2124], star [25,26], disk
[27], multi-branch [3] and so forth [3,25]. In addition to the shape
of materials the synthesized products showed various characteristics of semiconductors [6,2124], magnetic [1,4,68], and metals
[2,6]. Even the hybrid NCs which are composed of two or more
inorganic materials have been produced mainly in organic/surfactant mixtures [3,18,2834]. The surfactants used for the synthesis
of NCs can be amines [1,3,7,8,15], carboxylic [1,4,68,10,12,2123],
phosphonic acids [3], phosphine oxides [3,9,13] and others [11,24].
Among the above-mentioned surfactants oleic acid and/or oleylamine have been intensively employed because they can form a
dense protective monolayer producing highly uniform and monodisperse particles [35].
The NCs synthesized in organic/surfactant systems have a
drawback that they are only dispersible in nonpolar solvents such
* Corresponding author. Fax: +82 52 259 1689.
E-mail address: swkim@ulsan.ac.kr (S. Kim).
0021-9797/$ - see front matter 2009 Elsevier Inc. All rights reserved.
doi:10.1016/j.jcis.2009.04.078

as hexane and toluene [35]. Meanwhile, in some technological


elds such as biochemistry, nanocomposite and thin lm fabrication, NCs should be dispersible in polar solvents like water or alcohols [36]. To overcome this detriment the surface properties of the
particles must be changed from hydrophobic to hydrophilic. These
changes are commonly conducted using the ligand exchange
processes.
Ligand exchange is a well-known versatile method to desirably
tune the surface properties of colloidal NCs [35]. The surface modier plays a signicant role for the properties of the modied NCs,
allowing them to disperse in desired solvents [3543], improving
their stability [21] and enhancing their electronic and optical properties [44]. The surface modication of NCs has been usually
accomplished by adding ligands to the solid forms of NCs
[37,39,43] or to the solid containing bulk solutions [35,42]. In a recent investigation by Frankamp et al. [38] new ligand exchange
process has been introduced. The ligand exchange occurred at
the interface between modier-containing aqueous phase and
NC-containing organic phase while stirring two-phase mixture
[38].
The ligand exchange process has been successfully applied to
produce polar solvent-dispersed NCs using various hydrophilic ligands, e.g. silanes [35], tetramethylammonium hydroxide [37],
silsesquioxane [38], carboxylic [39,40], phosphonic [41], mercaptoalkanoic [42] acids and cetyltrimethylammonium bromide [43].
Amphiphilic polymers such as poly-dimethylaminoethyl methacrylate and poly-aminoamine have been utilized for transferring
semiconductor NCs from organic solvent to aqueous solution
[44]. In these reports almost all of the modifying ligands should
be large molecules to stabilize colloidal NCs in polar solvent. Small

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D.Q. Vo et al. / Journal of Colloid and Interface Science 337 (2009) 7580

modifying ligands resulted in NCs with poor stability. As the size of


the modifying ligand increases the exchanged particle becomes
larger, which leads to an increased difculty in utilization or a decrease in the magnetization of magnetic materials [35]. Therefore,
the surface modication of hydrophobic NCs using short-chain ligand that can stabilize colloids in a polar solvent for several
months may be an exciting result.
In this work we report a method to make hydrophilic NCs dispersed in a polar media using short-chain carboxylic acids rst as
anti-solvents and then as modifying ligands. TiO2 nanorods (NRs)
and Fe3O4 nanoparticles (NPs), whose properties and application
areas can be referred to by many papers [7,8,13,2124,28,30,45
50], were chosen as representatives of the NCs. The surfaces of
oleic acid-coated TiO2 NRs were tried to transform into hydrophilic
using acrylic, acetic and methacrylic acids. To test the proposed
method in this work the surfaces of the Fe3O4 NPs were also modied through the exchange of oleylamine/oleic acid with acrylic
acid.
2. Materials and methods
2.1. Materials
Iron (III) acetylacetonate (Fe(acac)3, 99.9%), 1,2-hexadecanediol
(90%), phenyl ether (99%), oleylamine (OLA, 70%), methacrylic acid
(MAcA, 99%), acrylic acid (AcA, 99%), oleic acid (OA, 90%), titanium
(IV) isopropoxide (TTIP, 97%), tetramethylammonium hydroxide
(TMAH, 25 wt% in H2O), and hexane (mixture of isomers, 98.5%)
were purchased from SigmaAldrich. Acetic acid (AA, P99.0%)
was also obtained from Fluka. High purity water (18 MX cm) was
prepared by a Millipore Q-guard 2 purication system and used
in the hydrolysis reaction of TTIP. Ethanol (Daejung Company, Korea, 95%) was used as an anti-solvent in the recovery and separation
of the NCs. All chemicals were used as received.
2.2. Synthesis of hydrophobic TiO2 NRs
TiO2 NRs were prepared according to the procedure described
by Cozzoli et al. [21] with a small modication. OA (35 g) was
dried at 100 C for 1 h with vigorous stirring in a 100 mL threeneck ask connected to a reux condenser under nitrogen atmosphere. TTIP (4 g) was added to the ask and stirred for 5 min to
form a Tioleic complex. After loaded into a 5 mL syringe, 2 M
aqueous TMAH solution (3 mL) was injected rapidly into the ask.
The solution was maintained at 100 C and stirred under mild reux over 48 h to promote further hydrolysis and crystallization.
After cooling down to room temperature TiO2 NRs were readily
precipitated by the addition of excess ethanol to the reaction
mixture. The resulting precipitate was isolated by centrifugation
and then redispersed in 40 mL hexane to give pale yellow solution. The pale yellow color of TiO2 solution is caused by the formation of complex between carboxylic group and Ti atom on
the solid surface [51].

2.4. Synthesis of hydrophilic NCs through ligand exchange


In this work the experimental conditions such as temperature,
amounts of organic and inorganic materials as well as the size of
the vessel have been xed at the same values during the ligand exchange processes. For the synthesis of AcA-exchanged TiO2 NRs
3.6 mL of AcA and 0.4 mL of water were rst injected into a
10 mL vessel and stirred for 5 min. Then 4 mL of TiO2hexane solution (0.1 g of TiO2 NRs) was loaded into a 5 mL syringe and slowly
added to the vessel without stirring. Within 5 min white precipitate formed and was suspended in the interface. After TiO2 NRs
started slowly transferring into the AcA solution side, the process
was completed within 8 h. A transparent yellow AcA solution
was collected and used for characterization without centrifugation.
To obtain an AcA solution containing higher TiO2 content the addition of the TiO2hexane solution was repeated several times. The
maximal concentration of TiO2 was up to 0.1 g TiO2/mL (AcA and
H2O). The OA-coated TiO2 NRs were also modied by AA and MAcA
using the procedure similar to that of AcA.
To check the versatility of the method proposed in this work we
tried to modify oleic acid/oleylamine-coated Fe3O4 NPs using AcA
as a modifying ligand. The ligand exchange of Fe3O4 NPs was also
performed utilizing the same method for TiO2 NRs. It was observed
that Fe3O4 NPs were transferred completely into the aqueous AcA
solution after 12 h.
2.5. Characterization
The characterization of the synthesized products was performed by transmission electron microscopy (TEM) and Fourier
transform infrared (FTIR) spectroscopy. The TEM and high resolution TEM (HRTEM) images were obtained using a JEM 2011 Hitachi
S-4200 operating at 200 kV. All TEM samples were prepared by
dropping 0.5 lL NC (1 lg/mL) solution onto a carbon-coated copper grid followed by evaporation at 40 C in 10 min. The FTIR spectra were measured by a Nicolet 380 spectrometer with a spectral
resolution of 1 cm1. The OA-coated TiO2 NRs and the OA/OLAcoated Fe3O4 NPs for FTIR analyses were prepared by adding excess
ethanol to their solutions to remove residual surfactant. After centrifugation the collected solid samples were dried in a vacuum
oven for 5 h at 80 C. Ligand-exchanged NCs for FTIR analysis were
prepared by using a rotary evaporator to obtain solid forms. These
solids were dried in vacuum oven for 20 h at 80 C in order to separate residual ligands that would not attach on the NC surface. The
FTIR spectra of ligand-exchanged TiO2 NRs and Fe3O4 NPs were
measured using the pellets prepared by mixing their solids with
KBr. In order to get the FTIR spectra of the ligand an appropriate
amount of ligand solution was dropped on the KBr pellet prior to
analysis. For the FTIR analyses of solid samples the mass ratio of
the sample/KBr has been xed at 2 mg/200 mg.
3. Results and discussion
3.1. Ligand exchange of OA-coated TiO2 with AcA, AA and MAcA

2.3. Synthesis of hydrophobic Fe3O4 NPs


The synthesis of Fe3O4 NPs utilized the procedure reported by
Sun et al. [7,8]. Fe(acac)3 (0.706 g), 1,2-hexadecanediol (2.585 g),
OA (1.695 g), OLA (1.605 g) and phenyl ether (20 mL) were mixed
under nitrogen atmosphere and stirred vigorously. The mixture
was heated up to 200 C for 30 min, and then reuxed at 265 C
for another 30 min. After the reaction mixture was cooled to room
temperature, 80 mL ethanol was added into the solution. A darkbrown precipitate was separated by centrifugation and then redispersed in 20 mL hexane.

3.1.1. Ligand-exchanged TiO2 NRs and efciencies of the process


Titanium dioxide NRs were selected as the rst representative
of NCs in this work. As one of the most studied oxides TiO2 NRs
possess interesting and exciting prospects that come from a low
dimensionality, anisotropic features and quantum connement effects [2124]. With high aspect ratio and high surface area TiO2
NRs have a high density of sites available for surface reaction as
well as high charge carrier transfer rates, which are important in
photocatalysis and solar cell [2124]. For the synthesis of TiO2
NRs many methods such as templating [52], hydrothermal [53],

D.Q. Vo et al. / Journal of Colloid and Interface Science 337 (2009) 7580

non-hydrolytic [2224] and hydrolytic [21] solgel methods have


been developed. Among the various methods the approach utilizing surfactant has several advantages, e.g. solubility in solvent,
high crystallinity and tunable aspect ratio [2124]. Surface modication to produce stable and well-dispersed TiO2 NRs in polar solvent might be a subsequent step for their practical utilization [24].
As illustrated in Fig. 1 the surface modication of hydrophobic
TiO2 NRs was performed using AcA, AA, and MAcA as exchanging
ligands. When a yellow TiO2hexane solution (4 mL) was added
into 4 mL of aqueous AcA (or AA, MAcA), the phase was separated
showing TiO2hexane solution at the top and aqueous AcA solution
at the bottom (Fig. 2a). TiO2 NRs were then precipitated and suspended in the interface (in the red elliptic curve, Fig. 2b) because
the polarity of the hexane solution was changed due to the diffusion of carboxylic acids into an upper phase. This phenomenon
can be easily understood since these three ligands can be miscible
with hexane so that they act as anti-solvents towards OA. At the
interface the ligand exchange process took place and then TiO2
NRs gradually came to aqueous ligand solutions. This process
was completed after 8 h, which has been realized by the disappearance of a white suspension and the appearance of a yellow color of
AcA solution (Fig. 2c). The pale yellow color of AcA-exchanged TiO2
solution indicates that the COO group of AcA binds towards the Ti
atom on the solid surface [51]. The resulting AcA-exchanged TiO2

Fig. 1. Ligand exchange of oleic acid-coated TiO2 NRs with short-chain carboxylic
acids in which COO groups towards the surface of NRs. (a) Oleic acid, (b) acrylic
acid, (c) acetic acid and (d) methacrylic acid.

Fig. 2. Process of ligand exchange of OA-coated TiO2 NRs with AcA. Photographs of
TiO2 NRs (a) dispersed in hexane, (b) suspended in the interface and (c) dispersed in
aqueous AcA. TiO2 NR solutions give pale yellow color. (For interpretation of the
references to color in this gure legend, the reader is referred to the web version of
this paper.)

77

solution has been maintained stable even after six months without
agglomeration at room temperature. However, the AA and MAcAexchanged TiO2 solutions were not stable to show the agglomeration of particles. This agglomeration even occurred while TiO2 NRs
moved from the interface into the aqueous AA (or MAcA) solution.
In this research one of the keys to the successful surface modication of TiO2 NRs was the use of two phases formed by the introduction of water. In the absence of water the modifying ligands
and hexane were completely mixed to form a homogeneous solution. Due to a polarity change in solution TiO2 NRs were precipitated as ne solid particles that could not be dispersed in any
polar solvents. According to our experimental results the time
completing ligand exchange strongly depended on the relative
amount of water in the aqueous phase. In the presence of 10%
water (v/v in AcA and H2O) the ligand exchange has been completed after 8 h. If the concentration of water was 50%, the ligand
exchange process took several days to complete. The difference
of time required to complete the ligand exchange processes can
be explained by the competitive chemisorption. At high water content the chemisorption probability of modifying ligands towards
the OA-coated TiO2 NR surface decreases since the ligand exchange
process is a competitive chemisorption between the original and
the modifying ligands.
Fig. 3 shows a representative TEM image of colloidal TiO2 NRs
dispersed in an aqueous AcA solution (Fig. 2c). The TiO2 NRs are
crystalline particles with 23 nm in diameter and 2530 nm in
length. The TEM image indicates that there is no agglomerated
TiO2 NRs in an aqueous AcA solution because the surface of particle
has been changed to hydrophilic through the ligand-exchange process. In addition to the TEM analysis for the lower aqueous phase
the UVVis technique has been utilized to check the upper organic
phase. The UVVis spectrum of the upper organic phase, even
though it is not shown in this report, reveals that TiO2 absorption
peak at 258.6 nm does not exist. This indicates that there is no TiO2
NRs remained in the upper organic phase after the ligand exchange
processes. A clear interface as well as the non-existence of agglomerated particles in the lower aqueous phase further supports the
conclusion that the OA-coated TiO2 NRs are modied using AcA
with recovery efciency of 100% in this work.
3.1.2. Chemisorption of the modifying ligands
The FTIR spectroscopy was used to demonstrate the chemisorptions of the modifying ligands onto TiO2 surface. The FTIR spectra
of the OA-coated TiO2 NRs, ligand-exchanged TiO2 NRs and pure ligands were compared by varying ligands such as AcA, AA and
MAcA.

Fig. 3. (a) TEM image of TiO2 NRs, (b) HRTEM image and (c) FFT image of single TiO2
NR dispersed in aqueous AcA solution.

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D.Q. Vo et al. / Journal of Colloid and Interface Science 337 (2009) 7580

Fig. 4. FTIR spectra of (a) OA-coated TiO2 NRs, (b) AcA-exchanged TiO2 NRs and (c)
pure AcA.

Fig. 4 illustrates the FTIR spectra of OA-coated TiO2 NRs, AcAexchanged TiO2 NRs and pure AcA. The OA-coated TiO2 NRs
(Fig. 4a) show strong peaks at 2922, 2850 and 1459 cm1, which
are known as the characteristic peaks of CH2 chain vibrations
[21,5456]. And the peaks at 1525 and 1420 cm1 are the asymmetric and symmetric stretches of a COO group on the TiO2 surface, respectively [21]. After OA-coated TiO2 NRs were exchanged
with AcA, the asymmetric and symmetric stretching vibrations of
the COO group were shifted to 1529 and 1433 cm1 (Fig. 4b).
And it is interesting to note that the bands belong to CH2 chain
vibrations disappear in the AcA-exchanged TiO2 NRs as shown in
Fig. 4b. The disappearance of CH2 chain vibrations also reveals that
OA on the TiO2 surface has been completely replaced by AcA. In the
spectra of OA-coated TiO2 NRs and AcA-exchanged TiO2 NRs we
cannot nd a peak around 1700 cm1 (1709 cm1 for OA and
1721 cm1 for AcA) belonging to the vibration of free carboxylic
group. Based on this observation it may be said that there are no
residual ligands (OA and AcA) in the samples and the carboxylic
groups are anchored onto the TiO2 surface. The wavenumber separations, D, between mas(COO) and ms(COO) can be used to distinguish the types of the interaction between a carboxylic group and a
metal atom [21,5456]. In this work the bindings of OA and AcA
with the TiO2 surface (DOA = 105 cm1 and DAcA = 96 cm1) are
attributed to chelating bidentates. Below a wavenumber of
900 cm1 the characteristic bands of a TiOTi network can be
found in Fig. 4a and b [21].
The FTIR spectra of OA-coated TiO2 NRs, AA-exchanged TiO2
NRs and pure AA are presented in Fig. 5. The peaks at 2924 and
2852 cm1 in AA-exchanged TiO2 NRs (Fig. 5b) are ascribed to
the vibrations of a CH2 chain belonging to OA because the FTIR
spectrum of pure AA has no peaks in the range of 3000
2800 cm1. Therefore, it is clear that OA on the TiO2 surface was
not completely replaced by AA through the ligand exchange process. After the OA-coated TiO2 NRs were modied by AA, the asymmetric and symmetric stretching vibrations of the COO group on
the TiO2 surface were shifted to 1512 and 1428 cm1, respectively
(Fig. 5b). It is difcult to determine the exact amount of chemisorbed AA on the TiO2 surface; however, the chemisorption of
the AA ligands can be easily recognized through the signicant increase in the vibration intensity ratio between COO group and
CH2 chain after the exchange with AA.
The FTIR spectra of OA-coated TiO2 NRs, MAcA-exchanged TiO2
NRs and pure MAcA are illustrated in Fig. 6. The main features of
FTIR spectrum of MAcA-exchanged TiO2 NRs are similar to those
of AA-exchanged TiO2 NRs. For instance, the bands belonging to
CH2 chain vibration still exist even after the ligand exchange with

Fig. 5. FTIR spectra of (a) OA-coated TiO2 NRs, (b) AA-exchanged TiO2 NRs and (c)
pure AA.

Fig. 6. FTIR spectra of (a) OA-coated TiO2 NRs, (b) MAcA-exchanged TiO2 NRs and
(c) pure MAcA.

MAcA as shown in Fig. 6b. In addition to the AA-exchanged TiO2


NRs we may also conclude that OA on the TiO2 surface was not
completely replaced by MAcA in MAcA-exchanged TiO2 NRs. The
remaining OA in AA and MAcA-exchanged TiO2 NRs may be the
main reason to make them unstable since the surfaces of such
TiO2 NRs become less hydrophilic. However, the amount of OA in
MAcA-exchanged TiO2 NRs is slightly higher than the amount in
AA-exchanged TiO2 NRs. This observation has been deduced from
the intensities of CH2 vibration in their FTIR spectra (Figs. 5b and
6b). Since the ratio of sample/KBr is xed in this work, the CH2
vibration belonging to OA may be utilized to compare the relative
amount of exchanged carboxylic acids even though it is not so
quantitative. Based on the wavenumber separations, D, between
mas(COO) and ms(COO), the bindings of AA and MAcA with the
TiO2 surface (DAA = 84 cm1 and DMAcA = 95 cm1) are attributed
to chelating bidentates [21,5456].
The intrinsic differences of chemisorption ability of these three
ligands towards the TiO2 surface are not fully understood. However, based on the FTIR spectra it may be concluded that OA on
the TiO2 surface is completely replaced by AcA. Whereas, some
portion of OA is still remaining on the TiO2 surface after exchanging with AA and MAcA. Based on the FTIR intensities of OA remaining in the samples it may be said that the chemisorption abilities of
three ligands towards the surface of OA-coated TiO2 are in the
descending order such as AcA > AA > MAcA. It may be a big challenge to elucidate the reason why some ligands can stabilize the

D.Q. Vo et al. / Journal of Colloid and Interface Science 337 (2009) 7580

79

particles while others cannot although they are so similar. The detail knowledge from theoretical calculations about selective surface-adhesion energies on nanocrystals as well as sophisticated
experiments such as synchrotron-based analysis would be benecial to explain stability differences [5].
3.2. Ligand exchange of OA/OLA-coated Fe3O4 NPs with AcA
In order to further test the chemisorption ability of AcA on NCs
as well as the ligand exchange method proposed in this work,
hydrophobic Fe3O4 NPs were chosen as the second representative
material. The procedure to convert hydrophobic Fe3O4 NPs into
hydrophilic ones is very similar to the method used to treat the
OA-coated TiO2 NRs. When the hexane solution containing magnetite NPs was added into the aqueous AcA solution, the Fe3O4 NPs
were precipitated and suspended in the interface. And then NPs
were gradually transferred into the bottom phase. Fig. 7 shows a
typical TEM image of Fe3O4 NPs dispersed in aqueous AcA solution.
From the TEM and HRTEM images it can be inferred that Fe3O4 NPs
are highly crystalline uniform particles with 45 nm in diameter.
The TEM image also indicates that there is no agglomeration of
Fe3O4 NPs through the ligand exchange process. The AcA-exchanged magnetic NPs may have potential applications particularly in biotechnology due to their high stability, low cost and
high magnetism as well as low toxicity [57].
The FTIR spectra of OA, OLA and OA/OLA-coated Fe3O4 NPs are
shown in Fig. 8. The spectra of OA and OLA match with the previous reports [5456,58]. The peaks around 28503000 cm1 indicate the vibrations of CH2 chain present in OA and OLA. The peak
at 1709 cm1 is the vibration of free COO group of OA (Fig. 8b),
and those at 3329 and 1569 cm1 are the vibrations of NH2 group
in OLA (Fig. 8c). If the FTIR spectra of three materials are compared,
it can be said that the spectrum of OA/OLA-coated Fe3O4 NPs
(Fig. 8a) does not seem to resemble a combination of OA and
OLA [58]. For instance, the spectrum of OA/OLA-coated Fe3O4 NPs
does not show the characteristic peaks of OA (1709 cm1) and
OLA (3329 and 1569 cm1), but show new strong peaks at 1552
and 1405 cm1. The disappearance of the peaks at 3329 and
1569 cm1 may be due to the interaction of COO and NH
3 ions
[58]. The new peaks at 1552 and 1405 cm1 are ascribed to the
asymmetric and symmetric COO stretches with the surface Fe
center, respectively [5456,58]. The wavenumber difference, D, between mas(COO) and ms(COO), indicates that the binding of COO

Fig. 7. (a) TEM image of Fe3O4 NPs and (b) HRTEM image of single Fe3O4 NP
dispersed in aqueous AcA solution.

Fig. 8. FTIR spectra of (a) OA/OLA-coated Fe3O4 NPs, (b) pure OA and (c) pure OLA.

group onto the Fe3O4 surface is mainly chelating bidentate [35,54


56].
The FTIR spectra of OA/OLA-coated Fe3O4 NPs, AcA-exchanged
Fe3O4 NPs and pure AcA are illustrated in Fig. 9. Considering the
disappearance of CH2 chain vibrations in AcA-exchanged Fe3O4
NPs as shown in Fig. 9b, the OA and OLA on the Fe3O4 surface are
completely replaced by AcA through the ligand exchange process.
The peaks between 2900 and 3300 cm1 of AcA-exchanged Fe3O4
NPs can be interpreted as OH group on the Fe3O4 surface [35].
Such OH groups have been originated from H2O molecules that
existed during the experimental steps. New peaks at 1536 and
1447 cm1 could be the asymmetric and symmetric vibrations of
the COO group of AcA coordinating towards the Fe center, respectively [35,5456]. Based on the coordination modes of carboxylic
anion and metal site (D = 89 cm1), the binding of AcA with the
Fe3O4 surface is also ascribed to chelating bidentate [5456].
In this work the original ligands on the surface of TiO2 NRs and
Fe3O4 NPs were completely replaced by AcA after the ligand exchange processes. However, the times to complete the ligand exchange processes are different, e.g. 8 h for TiO2 NRs and 12 h for
Fe3O4 NPs. Since the binding strength of carboxylic acids with NC
oxides is weaker than that of amines [22], the chemisorption ability of AcA towards the OA-coated TiO2 surface is higher than that
towards the OA/OLA-coated Fe3O4 surface. This difference in
chemisorption abilities may be a reason why the time required
for the ligand exchange of TiO2 NRs is shorter than that of Fe3O4
NPs.

Fig. 9. FTIR spectra of (a) OA/OLA-coated Fe3O4 NPs, (b) AcA-exchanged Fe3O4 NPs
and (c) pure AcA.

80

D.Q. Vo et al. / Journal of Colloid and Interface Science 337 (2009) 7580

To the best of our knowledge it is the rst time that modifying


ligands worked as anti-solvents in the surface modication of colloidal NCs. The method proposed in this work possesses an advantage in that it utilizes a single step in order to complete the ligand
exchange process. In contrast to our method, previously reported
investigations required several steps such as reaction or ligand exchange, centrifugation and washing of precipitates [3544].
Even after the surface modication the original ligands on the
NC surface have not been completely eliminated as shown in our
AA- and MAcA-exchanged TiO2 NRs or in some of the previous
investigations [20,37]. That shortcoming may hamper the application of the obtained products since the original ligands are not usually compatible with a new environment in which the particles are
expected to be dispersed. In this work it has been demonstrated
that the hydrophobic NCs can be transformed into hydrophilic
ones with recovery efciency of 100% using acrylic acid as an
exchanging ligand. Moreover, chemisorbed AcA has a double bond
(C@C) at the end so that it can assist NCs in interconnecting with
target materials such as biomolecules or monomers.

[9]
[10]
[11]
[12]
[13]
[14]
[15]
[16]
[17]
[18]
[19]
[20]
[21]
[22]
[23]
[24]
[25]
[26]
[27]
[28]

4. Summary

[29]

We have introduced a novel way to modify the surface of


hydrophobic TiO2 NRs and Fe3O4 NPs using short-chain carboxylic
acids (AcA, AA and MAcA) rst as anti-solvents and then as modifying ligands. The surfaces of OA-coated TiO2 NRs and OLA/OAcoated Fe3O4 NPs were completely exchanged with AcA. And the
AcA-exchanged NCs showed excellent stability in polar media
without agglomeration. On the other hand, using AA and MAcA
as modifying ligands the OA on the TiO2 surface has not been completely exchanged with AA and MAcA. The remaining OA in AA and
MAcA-exchanged TiO2 NRs may be the main reason to make them
unstable since the surfaces of such TiO2 NRs become less hydrophilic. Based on the FTIR analyses it may be said that the chemisorption abilities of three ligands towards the surface of OAcoated TiO2 are in the descending order such as AcA > AA > MAcA.
Further analyses using TGA, XPS and UVVis will be benecial to
elucidate the mechanism of the ligand exchange process as well
as the properties of prepared NCs.

[30]

Acknowledgments

[45]

The authors acknowledge the nancial support from University


of Ulsan in 2004.

[46]
[47]
[48]

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