Article

pubs.acs.org/Langmuir

Kinetics of (3-Aminopropyl)triethoxylsilane (APTES) Silanization of

Superparamagnetic Iron Oxide Nanoparticles
Yue Liu,† Yueming Li,‡ Xue-Mei Li,*,† and Tao He*,†
†
Shanghai Advanced Research Institute, Chinese Academy of Sciences, Shanghai, China 201210
‡
State Key Laboratory of Metastable Materials Science and Technology, College of Materials Science and Engineering, Yanshan
University, Qinhuangdao 066004, China
*
S Supporting Information

ABSTRACT: Silanization of magnetic ironoxide nanoparticles with (3-aminopropyl)triethoxylsilane (APTES) is reported. The
kinetics of silanization toward saturation was investigated using different solvents including water, water/ethanol (1/1), and
toluene/methanol (1/1) at different reaction temperature with different APTES loading. The nanoparticles were characterized by
Fourier transform infrared spectroscopy, vibrating sample magnetometry, transmission electron microscopy, and thermal
gravimetric analysis (TGA). Grafting density data based on TGA were used for the kinetic modeling. It is shown that initial
silanization takes place very fast but the progress toward saturation is very slow, and the mechanism may involve adsorption,
chemical sorption, and chemical diffusion processes. The highest equilibrium grafting density of 301 mg/g was yielded when
using toluene/methanol mixture as the solvent at a reaction temperature of 70 °C.

■ INTRODUCTION
The (3-aminopropyl)triethoxylsilane (APTES) compound is an
important silane coupling agent and is a widely used grafting
agent to promote interfacial behavior of inorganic oxides
including silica,1,2 ceramics,3 titania,4 and magnetic iron oxide
nanoparticles (MNPs).5 APTES surface-functionalized MNPs
in particular found applications in many biological applications
including cell separation6 and enzyme separation, diagnosis as
MRI contrast agent,7−9 as magnetically controlled drug
carriers,10 and hyperthermia treatment media as illustrated in
many literature reports.2,11−19 The mechanism of surface
functionalization is the formation of Fe−O−Si bond between
the nanoparticles and silane ligand, very similar to the siloxane
layer formation on silica. However, accurate control of the layer
quality has been a difficult task.8,11,20−22 Silane attachment may
exist in physisorption, hydrogen bonding, or electrostatic
attachment besides covalent linkage.20 Even for covalently
linked ligands, complications may be present in monolayer and
multilayer formation.23
The general silanization sequence follows by the hydrolysis
of triethoxyl groups into trihydroxyl groups and then
polycondensation of the hydroxyl groups with the surface
hydroxyls groups from the MNP surface. However, several
reaction routes may be involved, which makes the grafting
density of the silane ligands highly dependent on the reaction
conditions as illustrated in Scheme 1. For example, after
hydrolysis the silanol groups may react with surface hydroxyl
groups leading to surface silanization. The surface-immobilized
ligands then condense with vicinal silanol groups forming either
a monolayer or highly branched polycondensed structure.
Overall, the kinetics of the silanization is critical for controlling
the layer formation process.11
Layer formation kinetics of octadecyltrichlorosilane (ODS)24
and octyltriethoxyl silane (OTS) has been studied widely.25−28
It is generally believed that the silanization is fast with that of
the reaction kinetics following the Langmuir model in the short
time range leading to a self-assembled monolayer and the
process toward saturation is of slow kinetics.27,29 For APTES
silanization process in particular, there have been many studies
on the molecular structure,20 type of bonding,21 and surface
Received: August 23, 2013
Revised: November 20, 2013
Published: November 20, 2013

© 2013 American Chemical Society 15275 dx.doi.org/10.1021/la403269u | Langmuir 2013, 29, 15275−15282
Langmuir Article

Scheme 1. Schematic Illustration of Possible Reaction Routes for APTES Silanization of Magnetic Nanoparticles

Table 1. The Silanization Operating Conditions for MNPs

entrya solvent T (°C) initial APTES conc. (g/L) reaction time (min) equilibrium grafting density (De, mg/g)b
MNPw30−2% H2O 30 20 60, 120, 300, 600, 1440 243.9
MNPw30−0.2% H2O 30 2 60, 120, 300, 600, 1440 96.6
MNPw70−2% H2O 70 20 60, 120, 300, 600, 1440 275.5
MNPw70−0.2% H2O 70 2 60, 600, 1440 248.1
MNPM30−2% MeOH/toluene 30 20 60, 600, 1440 259.1
MNPM30−0.2% MeOH/toluene 30 2 60, 600, 1440 198.8
MNPM70−2% MeOH/toluene 70 20 60, 600, 1440 301.2
MNPM70−0.2% MeOH/toluene 70 2 60, 600, 1440 278.6
MNPE30−2% EtOH/H2O 30 20 60, 600, 1440 243.9
MNPE30−0.2% EtOH/H2O 30 2 60, 600, 1440 209.6
MNPE70−2% EtOH/H2O 70 20 60, 600, 1440 281.7
MNPE70−0.2% EtOH/H2O 70 2 60, 600, 1440 263.2
a
The subscripts are denoted as the reaction conditions. For example, MNPw70−0.2% refers to aminated MNP prepared using water as the solvent at 70
°C reaction temperature and 0.2% (v/v) APTES loading. bResults from data fitting for the equilibrium grafting density (De) by the pseudo-second
order kinetics.

derivatization conditions30 but the layer formation kinetics has
not been reported to the authors’ knowledge. Moreover, the
surface coverage of APTES for MNP has not been reported,
nor the complete plot of reaction kinetics. The understanding
of the kinetics of APTES silanization would help to clarify
whether a monolayer is formed and eventually the quality
control of the layer.11,21
15276
In this report, surface functionalization of MNP with APTES
is investigated under different reaction conditions in order to
reveal the layer formation kinetics, especially the kinetics in the
process toward saturation. The maximum grafting density and
reaction constants are estimated based on the kinetic model.
The use of different solvents was carried out in order to assess
solvent effects on the reaction kinetics. The results may help
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Figure 1. TEM images of MNPs (left) and MNP-NH2 (right).
the quality control of the silane layer in terms of reaction time,
temperature, and solvent selection.
■
EXPERIMENTAL SECTION
Materials. FeCl3·6H2O and FeCl2·4H2O were both purchased
from Sigma-Aldrich. Sodium hydroxide was purchased from Longxi
Chemicals (Shantou), China. The (3-Aminopropyl)-triethoxysilane
(APTES) compound was purchased from Alfa Aesar. All the organic
solvents were of reagent grade and used as received unless stated
otherwise. Doubly distilled water was used throughout the experi-
ments.
Synthesis of MNP Iron Oxide Nanoparticles. Water was
deoxygenated by bubbling N2 for 30 min. A stock solution of NaOH
was prepared by dissolution of NaOH (23.08 g, 0.57 mol) in water (1
L). FeCl3·6H2O (5.4 g, 20 mmol) and FeCl2·4H2O (4.0 g, 20 mmol)
were dissolved in 80 and 120 mL distilled water, respectively. The
molar ratio of Fe3+/Fe2+ was 1:1. The two solutions were mixed
together and added into the alkaline solution prepared above slowly
under vigorous stirring. The mixture was heated to 80 °C and stirred
for 30 min under N2. The black precipitates were washed 3 times with
distilled water followed by magnetic decantation and dried under
vacuum.
Silanization of MNPs by APTES. For optimization of the surface
coating process of the silanization, different solvent and reaction
temperature were attempted as shown in Table 1. When water-based
solvent was used, the reaction procedure is as follows. Briefly, the
nanoparticles obtained from coprecipitation (0.5 g) were dispersed in
the solvent (100 mL) and then APTES (0.2 or 2 mL) was added into
the mixture under mechanical stirring. The reaction mixture was
heated up to 30 or 70 °C for a specified time then cooled down to
room temperature followed by magnetic decantation and thorough
washing with ethanol. The samples were then dried under rotary
evaporation and subsequently in an oven (60 °C) for 24 h.
When a mixture of methanol/toluene (volume ratio, 1:1) was used
as the solvent, the procedure is as follows. The nanoparticles were
dispersed in 100 mL of the solvent, sonicated for 30 min, and heated
up to 95 °C till 50 mL of the solvent was evaporated. Thereafter,
methanol (50 mL) was added. The operation was repeated three times
to ensure the solution was completely anhydrous. Subsequently, the
volume of reaction mixture was fixed to 100 mL by the addition of
methanol followed by APTES addition and stirred for a certain time at
30 or 70 °C under N2. The product was washed several times with
anhydrous ethanol and distilled water by magnetic decantation and
dried under vacuum.
Characterization. Infrared spectra of the nanoparticles were
recorded on an AVA TAR 360 Fourier transform infrared spectros-
copy (Thermo Nicolet) by pressing the MNPs into a KBr pellet. The
surface grafting density of the dry nanoparticles was determined by
thermal gravimetric analysis (TGA) (DSC204, NETSCH) under a N2
atmosphere at a heating rate of 10 K/min. The heating temperature
range was from room temperature to 800 °C. Morphology of the
nanoparticles was characterized by field emission scanning electron
microscopy (FESEM) (S4800, Hitachi) and transmission electron
microscopy (TEM) (JEM-2010UHR, Joel). Magnetic properties of the
MNP were recorded on a vibrating sample magnetometry (VSM, EV7,
ADE) and carried out at room temperature in magnetic fields up to 10
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kOe. Specific surface area was calculated via the Brunauer−Emmett−
Teller (BET) method according to nitrogen adsorption−desorption
measurements performed at 77 K on a Micromeritics ASAP 2020
adsorption analyzer.
■ RESULTS AND DISCUSSION
MNP Preparation and Silanization. Fe3O4 MNPs were
prepared via coprecipitation of Fe2+ and Fe3+ ions (molar ratio
1:1) with an average diameter of 9 nm (Figure 1) as
determined by TEM. The silanization of MNP with APTES
is schematically shown in Scheme 1 with ideal conditions being
that a monolayer is formed (route 1). The resulting MNP is
denoted as MNP-NH2. The reaction routes depicted in Scheme
1 include APTES hydrolysis and surface attachment by the
formation of Fe−O−Si bonds, leading to monolayer (route 1)
or multilayer formation (Route 2). Ionic bonding may also be
present which is not illustrated. Several (mixture) solvents were
investigated with respect to reaction temperature and APTES
loading as illustrated in the following paragraphs.
All the reaction conditions explored are shown in Table 1.
The subscripts in letters, numbers and percentage are referred
as the solvents (with W, M, and E representing water,
methanol/toluene mixture, and ethanol/water mixture, respec-
tively), reaction temperature, and initial APTES charging
percentage with respect to the solvent (v/v).
Water as the Solvent. Water was used as the solvent
because the MNPs are well dispersible in water. FT-IR was
used to verify the successful surface modification, where MNPs
after surface modification showed a similar spectrum to that of
APTES (Supporting Information Figure S1). Vibrating sample
magnetometry was used for the characterization of the
magnetization of the MNPs (Supporting Information Figure
S2). The saturation magnetization (Ms) of MNP was 50 emu/g
for uncoated MNPs and 40 emu/g for MNPw70−2% with no
remnant magnetization indicating that the both MNPS are
superparamagnetic. X-ray diffraction patterns of the MNPs
showed typical Fe3O4 diffraction peaks at 35.8° corresponding
to the (311) planes (Supporting Information Figure S3) before
and after surface modification indicating surface functionaliza-
tion did not change the crystal structure of nanoparticles.
Thermal gravimetric analysis was used to quantify and compare
the degree of silanization at different reaction time, temper-
ature, and APTES charging. Thermal gravimetric data were
converted to silane grafting densities (D g ) by using
independent calculation for molecular weight (Mw) of the
removed component (NH2C3H6) during TGA treatments. It
should be noted that TGA does not allow quantifying the
composition of the layer growing on the nanoparticles but
rather the amount of material grown on the particles. Because
no other silane ligands were present, TGA was used to quantify
the amount APTES grown on the MNPs. It is assumed that all
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the silane ligands were fully hydrolyzed because it would not be
possible to estimate the contribution of partially hydrolyzed
ones bearing ethoxyl (OEt) moieties. It should be noted that
the weight loss below 200 °C was not taken into consideration
for grafting density determination in order to minimize effects
of solvent and ligand incorporation or physisorption (Support-
ing Information Figure S4 shows a typical TGA curve).
APTES silanization of MNPs were carried out at 30 and 70
°C, each with two different APTES loadings (0.2 and 2%),
respectively at different reaction time. The Dg analyzed by
thermal gravimetric analysis was plotted against the reaction
time as illustrated in Figure 2. For all the reactions, Dg increased
Figure 2. Grafting density change of the MNP-NH2 nanoparticles
under different reaction conditions using water as the solvent. (□) 70
°C, 2% APTES; (○) 70 °C, 0.2% APTES; (△) 30 °C, 2% APTES;
(▽) 30 °C, 0.2% APTES.
significantly within the first hour of reaction time. For all
reactions, the initial 1 h of reaction contributed the most of the
grafting density increase, especially for the reactions carried out
at higher reaction temperatures (70 °C). This finding agrees
with literature in that silanization is a fast process and over 90%
of saturation is achieved within the first hour of reaction.29
However, it is observed that at lower reaction temperature, the
initial grafting density is highly dependent on the initial silane
concentration. For example, at 30 °C the initial APTES grafting
density was very low, only 64 mg/g at 0.2% of APTES loading;
even after 24 h of reaction, it was only 95 mg/g. However, at
2% APTES loading the initial grafting density was 224 mg/g
and reached to 247 mg/g indicating that initial silane
concentration is a key factor for the silanization reaction. On
the other hand, the reaction temperature plays also important
roles. At 0.2% APTES loading, 70 °C initial 1 h of reaction
yielded a Dg of 236 mg/g, much higher than that at 30 °C. It is
interesting though to compare the Dg change with time of
MNPw30−2% and MNPw70−0.2%. Although the initial Dg of
MNPw70−0.2% was higher than MNPw30−2%, the final Dg was
comparable to each other, indicating that temperature is overall
a more critical factor in the silanization processes.
The kinetics of the silanization reaction in water was assessed
on the basis of the amount of deposited silane (Dt, mg/g) as a
function of reaction time (t, min). Several kinetic models were
used to fit our experimental data including Lagergren pseudo-
first order (Supporting Information Figure S5), pseudo-second
order (Figure 3a), Elovich (Figure 3b) and intraparticle
diffusion (Supporting Information Figure S6) models.
Lagergren pseudo-first order model did not yield a linear
fitting and therefore was not considered further. Pseudo-second
order fitting (Figure 3a) gave results with correlation coefficient
(r2) in the range of 0.9973−0.9999. Pseudo second order
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Figure 3. The kinetics of MNP nanoparticles silanization with APTES
using water as the solvent as fitted by pseudo- second order model (a)
and Elovich model (b).
kinetics describes a chemical adsorption process. Elovich model
describes the second order kinetics by assuming the actual
surfaces are heterogeneous for chemical sorption, which gives
correlation coefficients ranged from 0.69 to 0.98. The
intraparticle diffusion model with Dt versus t1/2 resulted in
fittings with r2 lower than 0.95 (shown in Supporting
Information Figure S6). If intraparticle diffusion occurs, then
Dt versus t1/2 will be linear and the line will pass through the
origin when intraparticle diffusion is the only rate limiting
process. According to Supporting Information Figure S5, it
appears that the fitting indeed is linear but does not go through
the origin. This indicates that the silanization mechanism is
complex and that adsorption, chemical sorption, and intra-
particle diffusion models all contribute to the rate determining
steps.
The pseudo-second order and Elovich kinetic equations are
shown in Table 2, where Dt and De, are grafting density at
reaction time (t) and at equilibrium respectively. In every
regression, the sum of error squared (SSE) between the
predicted values (Dcalc) and the experimental results (Dexp) was
calculated according to
N
∑i = 1 (Dexp − Dcal )2
SSE =
N (1)
where N is the number of experiments. The pseudo second
order kinetic constant was calculated from the intercept and
slope of the plots of t/Dt versus t. The De was determined as
the inverse of the slope of the regression. The rate constant is
determined by slope2/intercept. The rate constants were very
low as seen in Table 2. For MNPw‑70−2%, the equilibrium
grafting density was 275 mg/g as the highest and 96.6 mg/g for
MNPw‑30−0.2% as the lowest, following the Pseudo-second order
model. Comparison of the experimental results with the data
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Table 2. Kinetic Parameters of Different Models for APTES Silanization

pseudo-second ordera Elovichb
t/(Dt) = [(1/k2De) + t/Dt] Dt = (1/β)ln(αβ) + (1/β)ln(t)
−1 −1 −1 −2)
MNP De (mg/g) k2 × 10 (g mg
4
min ) R 2
SSE α (mg g min β (g mg−1 min−1) R2 SSE
MNPw30−2% 244.0 13.22 0.9974 2.81 6.35 × 10 39
0.4018 0.9832 0.1351
MNPw30−0.2% 97.2 2.8 0.9999 1.18 140.51 0.1041 0.9975 0.2004
MNPw70−2% 274.9 4.16 0.9999 2.21 3.24 × 1014 0.1401 0.9424 0.7293
MNPw70−0.2% 247.9 8.54 0.9999 1.19 1.86 × 1012 0.1347 0.9747 0.6554
MNPM30−2% 259.1 1.62 0.9990 10.64 5.454 × 105 0.07092 0.8582 4.4358
MNPM30−0.2% 198.8 4.67 0.9996 2.27 5.90 × 105 0.091308 0.9968 0.4811
MNPM70−2% 301.2 3.19 0.9992 4.83 3.41 × 1010 0.097982 0.9543 2.4813
MNPM70−0.2% 278.6 10.70 0.9951 0.94 2.070 × 1017 0.1626 0.9934 1.2885
MNPE30−2% 243.9 14.0 0.9997 2.92 1.5107 × 1044 0.4451 0.937 0.4507
MNPE30−0.2% 209.6 12.1 0.9999 0.98 1.189 × 1023 0.2826 0.996 0.1742
MNPE70−2% 281.7 3.76 0.9999 6.78 1.3102 × 1021 0.1956 0.6931 2.632745
MNPE70−0.2% 263.2 6.8 0.9998 1.53 5.661 × 1022 0.2225 0.937 0.9015
a
Dt, De, t, and k2 represent grafting density at reaction time (t), grating density at equilibrium, reaction time, and the reaction rate constant. bα and β
represent the initial sorption rate (mg·g−1 min−2) and desorption constant (mg·g−1 min−1), respectively.

fitting showed surprisingly that the equilibrium grafting density subscript E) and methanol/toluene mixture (denoted with
was very close to the experimental results at 24 h of reaction subscript M) were also used as solvents for the silanization. The
time, indicating that the equilibrium grafting density may have grafting density change with time is plotted in Figure 4. The
been reached.
On the other hand, for MNPw‑70−2% it could be seen that
within the first hour of reaction time the grafting density had
reached 90% of De, but for MNPw‑30−0.2%, the grafting density
had only reached two-thirds of De. Moreover, due to kinetic
reasons even at 24 h of reaction time the Dg of MNPw‑30−0.2%
was still much lower than that of MNPw‑70−2%, a little more than
one-third. Therefore, it appeared that although both reaction
temperature and initial silane concentration were important
parameters in determining the equilibrium grafting density of
the nanoparticles, reaction temperature appeared more
important for silanization than the initial silane concentration.
The kinetics of silanization has been widely studied and
reports mainly focused on the growth of monolayer on flat
substrate including oxidized silicon, titania.23,31−36 Literature
results showed that the silanization follows a first order
Langmuir adsorption kinetics. For example, Balgar et al.28 used
atomic force microscopy to characterize the monolayer growth
and showed that the growth of octadecyltrichlorosilane
proceeds via the formation of islands with a sometimes
branched shape indicative for a DLA-type growth mechanism.
Garcia et al.24 characterized the surface silanization kinetics of
the TiO2 nanoparticles with octytriethoxysilane under com-
pressed CO2 and reported that the self-assembled monolayer
was formed in a short time (within 15 min) and the kinetic
equation resembled the Langmuir adsorption model for
monolayer formation. However, the kinetic data were based Figure 4. Grafting density of magnetic MNP-NH2 nanoparticles
prepared using water/ethanol (a) and toluene/methanol (b) as the
on a reaction time up to 120 min. There are few reports
solvent. (□) MNP70−2%; (○) MNP70−0.2%; (△) MNP30−2%; (▽)
exploring the entire layer formation mechanism for APTES to MNP30−0.2% .
the authors’ knowledge.
It is shown according to our results that when water is used
as the solvent the silanization follows a two-stage reaction initial grafting density increased rapidly for both solvents
kinetics with the first stage a fast increase in grafting density and system, similar to water as the solvent. Again, for both mixed
thereafter a process of slow saturation in silanization. Moreover, solvents within the first hour of reaction the growth of Dg is
the overall reaction kinetics appears to be a complex one fast, agreeing with literature results that silanization takes place
involving adsorption, chemical sorption, and intraparticle rapidly and the process toward saturation is a slow process. The
diffusion processes. difference in the Dg with different solvents is most probably
Other Solvents. In order to verify the silanization caused by the complicated solvent effects. Solvent effects might
mechanism, water/ethanol (1/1) mixture (denoted with be ascribed to the competition effects, differences in polarity
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and diffusivity of the solvent molecules, agreeing with literature
results.27,37,38 On the other hand, it appeared that the initial Dg
for water/ethanol mixture solvent is higher than the methanol/
toluene mixture, which may indicate the methanol/toluene
mixture is not suitable for silanization at ambient temperature
(around 30 °C) with a low initial silane concentration. Overall,
it can be seen that when methanol/toluene (1/1) mixture is
used, the highest grafting density is yielded at 70 °C using 2%
of APTES loading.
The kinetic fittings of silanization over longer time by the
pseudo-second order are shown in Figure 5a,b, respectively, for
Figure 5. The kinetics fitting of MNP nanoparticles silanization with
APTES using ethanol/water mixture (a) and methanol/toluene (b) as
the solvent as fitted by Pseudo- second order model. (▽) MNP30−0.2%;
(○) MNP30−2%; (△) MNP70−0.2%; (□) MNP70−2%.
ethanol/water mixture and methanol/toluene mixture as the
solvents. The data fitting with Elovich model is not shown, but
the reaction rate constants, r2 and SSE, are shown in Table 2.
All the reaction data fit well with the pseudo-second order
kinetics and Elovich models indicating that the solvent does not
change the reaction kinetics for the slow saturation silanization
process. The reaction constants are shown in Table 2. The
calculated equilibrium adsorption capacity is 301.2 mg/g using
toluene/methanol mixture as the solvent at a reaction
temperature of 70 °C and a reaction time of 24 h based on
pseudo-second order model. It should be noted that the data
fitted by the pseudo-second order kinetics model were
surprisingly close to the values obtained at 24 h of reaction
time. These results indicate that the silanization might have
reached an equilibrium state and longer reaction time may not
increase the degree of silanization.
In summary, the use of different solvents does not change the
kinetics of the silanization process. However, the degree of
silanization depends greatly on the reaction conditions. It may
indicate that to prepare a silane layer with suitable surface
coverage, the silanization temperature is a key parameter in
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contrast to the initial silane concentration. Nevertheless, it
should be pointed out that at a low reaction temperature and a
low silane concentration, the progress toward saturation may be
longer than 24 h with a low surface coverage.
Surface Coverage. If a monolayer of silane is formed on
the MNP surface, the maximum grafting density can be
calculated, according to the following equation
⎛ S ⎞⎛ M ⎞
Dg = ⎜ BET ⎟⎜⎜ W ⎟⎟
⎝ Ssi ⎠⎝ Na ⎠ (2)
where SBET is the specific surface area of the bare nanoparticle
(m2/g), Ssi is the occupied surface area of an silane ligand
(nm2), Mw is the molecular weight of APTES (221 g/mol), and
Na is the Avogadro constant (6.02 × 1023 /mol). The surface
area of the MNP was calculated via the BET method according
to nitrogen adsorption−desorption measurements with an
average value of 162 m2/g. Assuming that the occupied surface
area of a silane ligand is 0.2 nm2,39 a grafting density of 298
mg/g is expected according to eq 2. Interestingly, the
experimental result of Dg at 70 °C (301 mg/g) using
toluene/methanol mixture solvent is very close to the
theoretical prediction by BET calculation, assuming a
monolayer exists on the surface. Moreover, based on the
Pseudo-second order model the equilibrium Dg of 301.2 mg/g
was expected, which was also close to the data based on BET
calculation. Therefore, it can be seen that the pseudo-second
order kinetics can be used rationally to describe the kinetics of
APTES silanization of MNP. Moreover, these results indicate
that a monolayer (route 1) is most likely resulted during the
surface grafting process. Also, to prepare an APTES silane layer
with a good quality the reaction should be carried out at higher
temperature (70 °C) using methanol/toluene mixed solvents at
a large excess of APTES.
■ CONCLUSIONS
Kinetics of APTES silanization of supermagnetic iron oxide
nanoparticles was investigated with the use of different solvents
and under different reaction temperatures. The results show
that initial silanization takes place very fast and can account for
over 80% of the degree of grafting. The process toward
saturation is very slow and may take 24 h before reaching
equilibrium. Various kinetic models were used for the data
fitting, and it was found that the reaction mechanism may
involve pseudo-second order, Elovich, and intraparticle
diffusions models. Overall, this report clarified the kinetics of
APTES silanization toward saturation and may serve as a
guideline for the preparation of aminated MNPs with
controlled surface grafting density.
■
ASSOCIATED CONTENT
*
S Supporting Information
The FTIR spectra, VSM loops, XRD patterns, and a typical
TGA curve of the MNPs are shown in Figures S1−S4,
respectively. The kinetics data fitting by Lagergren pseudo-first
order and intraparticle diffusion models are shown in Figures
S5 and S6, respectively. Particle size distribution of the MNPs is
shown in Figure S7. This material is available free of charge via
the Internet at http://pubs.acs.org.
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■
AUTHOR INFORMATION
Corresponding Authors
*E-mail: lixm@sari.ac.cn. Tel: +86-21-20350881. Fax: +86-21-
20325112.
*E-mail: het@sari.ac.cn. Tel: +86-21-20325162.
Notes
The authors declare no competing financial interest.
■
ACKNOWLEDGMENTS
The authors would like to thank the partial financial support
from National Natural Science Fund China (Project nos.
21176119, 51202212), the National Key Basic Research
Program of China (973 Program with Project no.
2012CB932800), and Shanghai Ministry of Science and
Technology (Project no. 13DZ1205100).
■
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