Applied Surface Science 328 (2015) 2633

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Applied Surface Science

journal homepage: www.elsevier.com/locate/apsusc

Excellent adsorption of ultraviolet lters using silylated MCM-41

mesoporous materials as adsorbent
Li Li a,c , Xuemei Wang a,b , Dongxia Zhang a,b , Ruibin Guo a , Xinzhen Du a,b,
a
b
c

College of Chemistry and Chemical Engineering, Northwest Normal University, Lanzhou 730070, PR China
Key Lab of Bioelectrochemistry & Environmental Analysis of Gansu, Lanzhou 730070, PR China
College of Science, Gansu Agriculture University, Lanzhou 730070, PR China

a r t i c l e

i n f o

Article history:
Received 2 August 2014
Received in revised form
18 November 2014
Accepted 20 November 2014
Available online 28 November 2014
Keywords:
MCM-41
Silylation
Adsorption
UV lters

a b s t r a c t
Silylated MCM-41 materials were examined to adsorb of ultraviolet (UV) lters from aqueous solution at
303 K. Compared to UV lters adsorbed on unsilylated MCM-41, a much higher adsorption capacity was
achieved by silylated MCM-41 materials. Surface modication offers a greater opportunity to adjust both
the pore size and surface properties of organic functionalized MCM-41 type materials. In the present
study, MCM-41, methyl functionalized MCM-41 (M-MCM-41) and chlorotrimethylsilane end-capped
(TMS-M-MCM-41) mesoporous materials were successfully synthesized using solgel technology. The
structures and properties before and after surface modication were systematically investigated through
N2 -adsorption desorption isotherms, scanning electron microscope (SEM) and transmission electron
microscopy (TEM), small angle X-ray powder diffraction analysis (SXRD), and infrared spectroscopy (FTIR). They together conrm that the methyl and trimethyl silyl (TMS) group is chemically bonded to the
internal surface of the mesopores. The sorption of UV lters obeys Langmuir and Freundlich sorption
isotherms, showing the suitability of silylated MCM-41 as adsorbent for enrichment of UV lters from
water.
2014 Elsevier B.V. All rights reserved.

1. Introduction
Ultraviolet (UV) lters are widely applied to sunscreen, cosmetics, personal care products and other pharmaceuticals in order to
protect the skin from solar radiation [1]. Most of UV lters are
organic substances, characterized by single or multiple aromatic
structures, often with attached hydrophobic groups [2]. However,
excessive use of UV lters would lead to environmental pollution
as well as accumulative negative effect on human beings [3]. Moreover, some UV lters can accumulate in biota and act as endocrine
disruptors which have estrogenic effects [4]. UV lter can be found
not only in personal care products [5] but also in environment
water [68], sludge [9], dust [10], organism [11] and serum [12].
Nowadays, UV lters have been included in the so-called emerging contaminants. Therefore, sample pre-treatment and effective
enrichment of UV lters were the key issues.
Since scientists in Mobil Oil Research and Development report
on the M41S family of silica based mesoporous materials in 1992

Corresponding author at: College of Chemistry and Chemical Engineering, Northwest Normal University, Lanzhou 730070, PR China. Tel.: +86 0931 7970796.
E-mail address: xinzhendu@yahoo.com (X. Du).
http://dx.doi.org/10.1016/j.apsusc.2014.11.116
0169-4332/ 2014 Elsevier B.V. All rights reserved.

[1315], MCM-41 has been widely used as adsorbent for the

removal of organic pollutants such as dyes [16], phenolic compounds [17], aromatics [18], and inorganic pollutants such as heavy
metals [19]. Numerous studies have been performed dealing with
their synthesis and surface modication which aimed to a further
improvement of the bulk properties. MCM-41 can be tailored by
in situ synthesis or post-synthesis modication in order to control the porosity and pore size. Such surface functional materials
have more advantages with the introduction of organic functional
groups. It is possible to match the special needs required by a proper
choice of the organic components. Studies have shown that silylation was a commonly used method for mesoporous materials
surface modication. The control of pore size, morphology, and
surface coverage represent important issues. Many studies focus
on surface hydrophobic modication of MCM-41 to enhance its
adsorption ability for selective adsorption of certain pollutants.
Zhao and Lu [20] modied siliceous MCM-41 by silylation using
trimethylchlorosilane, and studied the adsorption behaviors of the
modied samples systematically. Trouv et al. [21] synthesized
functionalized MCM-41 and HMS mesoporous silica with hexamethyldisilazane. The hydrophobic samples exhibited a considerably
higher adsorption capacity for N,N-diethyl-m-toluamide in aqueous solution than the unmodied ones. Zhu et al. [22] studied amine

L. Li et al. / Applied Surface Science 328 (2015) 2633

grafted MCM-41 mesoporous materials and have been approved

as a type of good candidates for CO2 capture by many experimental results. Javadian and Taghavi [23] showed the adsorption
characteristics of polypyrrole/thiol-functionalized Beta/MCM-41
(PPy/SH-Beta/MCM-41) for the removal of Hg2+ ions from aqueous solutions. Up to now, the adsorption of real water samples is
the focus [24,25]. In connection with the former area of application,
functionalized mesoporous MCM-41 materials of tunable pore size
provide a better adsorption effect applied to the sample pretreatment [26,27] and stationary phases for chromatography analysis
[28,29].
On the one hand, surface modied MCM-41 can greatly reduce
surface hydroxyl groups of MCM-41 mesoporous materials and
adjust the pore size within a certain range by changing the load
of organic functional groups. The surface chemistry can be altered
by surface functionalization, and the activity and selectivity can be
greatly promoted via the surface hydrophobicity of the materials.
On the other hand, surface modication is in imparting structural
stability against moisture and shrinkage, and the hydrothermal stability of the materials was greatly improved.
In the present study, MCM-41 was synthesized with solgel
technology and the methyl functionalized MCM-41 was synthesized with a co-condensation in one pot. It replaces the surface
OH groups with hydrophobic methyl groups, making the initially
hydrophilic surface hydrophobic. However, a lot of silanol groups
still existed on the surface of mesoporous materials after silylation,
which is prone to swelling behavior and affects the surface property and their selectivity. For this reason, chlorotrimethylsilane
was used to end-cap methyl silylation mesoporous materials using
post-synthesis. It is satisfying that the materials were well synthesized to meet with the nature of typical MCM-41 mesoporous
materials and maintained the basic pore structure after silylation.
Thus, silylated MCM-41 can be a good adsorbent for less polar or
non-polar organic compounds, which is subsequently used as an
adsorbent for UV lters (Their structure and relevant properties
are summarized in Table 1.) from aqueous solution. In this regard,
the equilibrium adsorption isotherms were investigated to explore
the effective enrichment and separation of UV lters from water.
2. Experimental
2.1. Chemicals

27

and a Waters 2695 empower workstation. Waters HT-340K HPLC

column oven was required for samples on constant temperature. The mobile phase was methanol/water (88/12, v/v) and the
wavelength was set at 310 nm. A WE-3 water-bathing constant
temperature shaker was used to assist the adsorption process.
FT-IR spectra were recorded on a Digilab FTS3000 FT-IR spectrometer. TGA was performed using Perkin Elmer PE6300 series
instrument in the temperature ranging from 25 to 800 C with
a heating rate of 10 C/min under nitrogen. XRD patterns were
obtained with a D/Max-2400 Powder X-ray diffractometer. N2
adsorptiondesorption isotherms were measured on a Tristar II
3020 surface area analyzer. The sample was rst degassed at 150 C
for 10 h before adsorption measurements. The surface area was
calculated according to the BET equation at the relative pressure ranging from 0.05 to 0.20 and the pore size distribution was
obtained from the desorption branch of isotherms using the BJH
approach. The pore volume was obtained by the amount adsorbed
at saturated pressure. The morphology of the samples was observed
by eld emission scanning electron microscope of JSM-6701(F).
TEM images of the samples deposited on carboncopper grids were
taken on Tecnai G2-F20 microscope.
2.3. Synthesis of MCM-41 material
MCM-41 was synthesized with solgel method. CTAB was dissolved in a certain volume of ultrapure water as a template. The
required amount of NaOH was added, stirring after it is completely
dissolved, TEOS was slowly added dropwise into the mixture by
a pressure equalizing addition funnel. The molar composition was
CTAB:TEOS = 0.2:1. After stirring for 6 h, a lot of white solid was generated and the solution present emulsion, the resulting mixture was
transferred into a teon-lined stainless steel autoclave reactor and
synthesized at 80 C for 24 h under autogenous pressure. Thereafter
the mixture was cooled to room temperature. The solid product
was ltered and rinsed completely with ultrapure water to neutral, and then dried in a vacuum oven at 80 C for 12 h. The sample
was denoted as CTAB-MCM-41. In order to remove template agent,
the sample was calcined in the mufe furnace by heating from room
temperature to 550 C at 5 C/min and keeping at 550 C for 6 h. By
this way, MCM-41 was obtained.
2.4. Synthesis of M-MCM-41 material

2-Ethylhexyl-4-methoxycinnamate (EHMC, purity 98%, Lot

No. 18565) and 2-ethylhexyl 4-(N,N-dimethylamino) benzoate
(OD-PABA, purity 97%, Lot No. 23111) were purchased from AccuStandard (New Haven, USA). Tetraethyl orthosilicate (TEOS purity:
98%) was purchased from Shanghai Chemical Reagents Company (China). Cetyl trimethylammonium bromide (CTAB) were
obtained from Sinopharm Chemical Reagent Co., Ltd. Methyl
trimethoxysilane (MTMS, 98%), trimethylchlorosilane (TMCS, 98%)
were purchased from Fluka. Sodium hydroxide (NaOH, AR), HPLCgrade methanol was obtained from Yuwang Chemical Company
(Shandong, China). Hydrochloric acid (HCl, 37%) was obtained from
Baiyin Chemical Company (China). Toluene (AR) was redistilled for
removal of water before use. Unless otherwise stated, all other
chemicals were of analytical grade. Ultrapure water was obtained
from Aquapro Water Purication System (Chongqing, China) and
was used in all experiments.

M-MCM-41 was synthesized via co-condensation of TEOS with

MTMS. CTAB as template agent was dissolved ultrapure water.
The required amount of NaOH was added, stirring after the solid
was completely dissolved, the mixture of TEOS and MTMS were
slowly added dropwise into the reactor via a dropping funnel. The molar composition was CTAB: (TEOS + MTMS) = 0.2:1.2,
n(MTMS)/[n(TEOS) + n(MTMS)] = 15%. After stirring for 6 h at 25 C,
the resulting mixture was transferred into a teon-lined stainless
steel autoclave reactor and synthesized at 100 C for 24 h under
autogenous pressure. Thereafter the mixture was cooled to room
temperature. The sample was denoted as CTAB-M-MCM-41.
In order to remove the template agent, CTAB-M-MCM-41 was
put into a 250 mL round bottom ask, the required amount of
ethanol and hydrochloric acid was added, the template agent was
removed by heating reux at 70 C for 6 h. The synthesized sample was ltered and dried at 40 C for 8 h, which was denoted as
M-MCM-41.

2.2. Apparatus

2.5. Synthesis of TMS-M-MCM-41

All separations were performed on a Waters 1515 system (Milford, MA, USA) equipped with a Waters 2487 dual  absorbance
detector, a Waters Sunre C18 column (150 mm 4.6 mm, 5 m)

TMCS end-capped M-MCM-41 was synthesized using post grafting method. Using toluene as medium, M-MCM-41 was put into a
50 mL round bottom ask and a certain amount TMCS was added

28

L. Li et al. / Applied Surface Science 328 (2015) 2633

Table 1
Structure and physicochemical properties of UV lters.
Molecular mass (g/mol)

Water solubilitya (mg/L)

max (nm)

OD-PABA

290.41

0.155

310

EHMC

165.19

0.0053

310

UV lters

Water solubility at 25 C.

(0.1 g 2.0 mL). This sample was magnetic stirring for 6 h at room
temperature, the product was ltered and rinsed with ether and
acetone in turn, and then dried in a vacuum oven at 40 C for 8 h.
This sample was denoted as TMS-M-MCM-41. The silylation reaction was shown below:
Si OH + Cl Si(CH3 )3 Si O Si(CH3 )3 + HCl
The silylated surface is terminated by a TMS group.
2.6. Adsorption of UV lters by silylated MCM-41
The time to reach equilibrium adsorption was investigated. Typically 20 mg of MCM-41 and silylated MCM-41 powder was taken
in an air-tight vial. 10 mL of freshly prepared aqueous solution of
UV lters was added to the vial. The mixture was kept in a waterbathing constant temperature shaker for certain time at 30 C to
reach equilibrium adsorption, then the powder was ltered and
detected using HPLC.
The adsorption amount qe (mg/g) was calculated using following
expression:
qe =

(c0 ce )V
m

(1)

where c0 (mg/L) and ce (mg/L) are UV lters concentrations before

and after adsorption, respectively; V (L) is the volume of aqueous solution containing UV lters, and m (g) is the weight of the
adsorbent.

600
M-MCM-41

500
TMS-M-MCM-41

Volume adsorbed (mL/g)

Chemical structure

MCM-41

400
300
200
100
0
0.0

0.2

0.4

0.6

0.8

1.0

Ralative pressure (p/p0)

Fig. 1. Nitrogen sorption isotherms of MCM-41, M-MCM-41 and TMS-M-MCM-41
materials.

because methyl and TMS groups are protruded into the pores and
occupy the space of the MCM-41 channels.
The textural properties are summarized in Table 2. Furthermore,
the specic surface area, total pore volume and pore size of MCM41, M-MCM-41 and TMS-M-MCM-41 materials were decreased
successively to a certain extent, emphasizing that functional groups
modied has grafted within the pore channels. The actual values
depend on its functionality and surface coverage.

3. Results and discussion

3.2. Scanning electron microscopy
3.1. Nitrogen sorption studies
Nitrogen sorption experiments were used to determine the
textural properties and surface features of mesoporous materials.
The nitrogen sorption isotherms for the unmodied and modied
materials are shown in Fig. 1. The overall appearance of the BET
isotherms is very similar and shows type IV adsorption behavior. The well-known sharp inection of the adsorptiondesorption
isotherms is evidence of a narrow mesopore size distribution, suggesting a uniform mesopore size of the ordered materials. This type
of hysteresis loop is commonly associated with capillary condensation in the mesopores, and is characteristic for a mesoporous
structure. Surface modication kept the overall appearance of these
type IV isotherms practically unchanged, indicating that the textural characteristics are not altered by surface modication with
MTMS and TMCS. For the surface modied samples, the adsorption plateau values, reecting the total surface area, are lowered

The surface morphology and distribution of particle size of the

mesoporous materials have been investigated using SEM. Fig. 2
shows the images of MCM-41 (Fig. 2A), M-MCM-41 (Fig. 2B) and
TMS-M-MCM-41 (Fig. 2C) samples. The images clearly demonstrate
that the surface morphology maintained during the synthesis of
M-MCM-41 and TMS-M-MCM-41. Samples have a regular spherical shape and uniform size of about 100 nm. It can be observed
that the mentioned materials above display similar agglomeration
Table 2
Structural properties of synthesized materials.
Material

SBET (m2 /g)

Vp (cm3 /g)

BJH Dpore (nm)

MCM-41
M-MCM-41
TMS-M-MCM-41

1053
979
843

0.91
0.81
0.57

3.45
3.30
2.68

L. Li et al. / Applied Surface Science 328 (2015) 2633

29

Fig. 2. SEM micrographs for MCM-41 (A), M-MCM-41 (B) and TMS-M-MCM-41 (C).

Fig. 3. TEM images of MCM-41 (A), M-MCM-41 (B) and TMS-M-MCM-41 (C).

3.3. Transmission electron microscopy (TEM)

TEM images provide further evidence of the stability of the
mesostructure after functionalization of methyl group. As can be
seen from Fig. 3, a periodic hexagonal structure and uniform pore
size distribution can be clearly observed for MCM-41 (Fig. 3A and
B), M-MCM-41 (Fig. 3C) and TMS-M-MCM-41 (Fig. 3D) materials.
It is noteworthy to mention that modied nanostructured materials are very stable polymerized walls without loss of long-range
uniform channel pore framework by using our synthetic strategy.
The TEM images of modied M-MCM-41 and TMS-M-MCM-41 are
similar to MCM-41 and their pore size are between 2.0 and 4.0 nm.

intensity of the (1 1 0) and the (2 0 0) peaks was slightly weaker

and broadened for M-MCM-41 and TMS-M-MCM-41 materials.
This observation refers to a lower long-range order because high
amount of methyl and TMS groups were grafted into MCM-41,
100

Intensity(a.u.)

to some extent. However, it is noticeable that the agglomeration

increases after modication.

TMS-M-MCM-41
M-MCM-41

3.4. Small angle X-ray diffraction

The SAXRD patterns of MCM-41, M-MCM-41 and TMS-M-MCM41 mesoporous materials are compared in Fig. 4. These patterns
feature distinct Bragg peaks at low angles, a strong (1 0 0) as well
as (1 1 0) and (2 0 0) reections of lower intensity, which characterize the highly ordered hexagonal pore structure. The relative

110
1

200
4

MCM-41
5

2 Thete (degree)
Fig. 4. SAXRD patterns for MCM-41, M-MCM-41 and TMS-M-MCM-41.

30

L. Li et al. / Applied Surface Science 328 (2015) 2633

100
1630
3470

Weight loss / %

96

2900

960
1090 800

480

TMS-M-MCM-41
M-MCM-41

MCM-41

MCM-41

92
M-MCM-41

88
T-M-MCM-41

84

4000

3500

3000

2500

2000

1500

1000

500

-1

Wavenumber [cm ]
80

100

200

300

400

500

600

700

800

Fig. 6. FI-IR spectra for MCM-41, M-MCM-41 and TMS-M-MCM-41 materials.

Temperature / C

however, the sharp peak of (1 0 0) diffraction is still clearly

observed. Nevertheless, it is clearly indicated that the basic MCM41 pore structure remains unchanged after surface modication. In
addition, there is no apparent shrinkage of the cell dimensions of
the materials with the solvent extraction treatment, which indicate
the material has a good structural rigidity.
3.5. TGA
Thermogravimetric analysis (TGA) was employed to investigate
the thermal stability of MCM-41, M-MCM-41 and TMS-M-MCM41 materials by temperature heating up from 30 C to 800 C. As
was shown in Fig. 5, the weight losses were 4.4%, 3.8% and 0.2%
separately for MCM-41, M-MCM-41 and TMS-M-MCM-41 showing successively decreasing trend as temperature rises from 30 C
to 105 C, which were mainly due to the removal of adsorbed water.
MCM-41 showed strong adsorption capacity of water molecules
and can easily absorb moisture from the air just because of its
large specic surface area and porosity. Moreover, the pore became
polar channel because it was covered with great amount uncondensed hydroxyl groups. It is obvious that the hydrophobicity for
T-M-MCM-41 was enhanced much more than that of M-MCM41 because more TMS groups were grafted onto the surface of
materials. From 150 C to about 500 C, the loss of 2.5% for unmodied MCM-41 was might be attributed to surface silanol groups
condensation formation of Si O Si bonds and residual surfactants. At a temperature about 480 C, there was a sudden decrease
weight loss about 12.7% for T-M-MCM-41 while 6.6% for M-MCM41, which were caused by the decomposition of the methyl and TMS
groups. Moreover, the thermal stability of TMS-M-MCM-41 materials was enhanced within 300 C comparing with M-MCM-41 and
MCM-41.
3.6. The infrared spectra
The infrared spectra were shown in Fig. 6. The strong broaden
peak near 3470 cm1 belongs to adsorbed water molecules and
surface hydroxyl ( OH) asymmetric stretching vibration absorption, and 960 cm1 for the surface hydroxyl groups of OH plane
bending vibration. 1090 cm1 absorption peak corresponds to the
Si O Si bond symmetric stretching vibration of MCM-41 skeleton.
1630 cm1 absorption peak corresponds to the bending vibration
of adsorbed water (because OH groups are hydrophilic in nature),
while in the vicinity of 480 cm1 and 800 cm1 attributable to Si O
stretching vibration and bending vibration of Si O tetrahedron.

After MTMS and TMCS reacting with Si OH, a corresponding

stretching vibration for C H bond near 2900 cm1 appeared and
the intensity for TMS-M-MCM-41 was stronger than M-MCM-41,
implying that more quantity of TMS groups bonding in. At the same
time, the absorption peak intensity at 3470 cm1 and 1630 cm1
reduced successively, 960 cm1 hydroxyl bending vibration peak
decreased in M-MCM-41 until it disappeared for TMS-M-MCM-41,
indicating that the hydrophobicity was enhanced because of considerable amount of the surface hydroxyl groups are substituted
with methyl and TMS after silylated reaction, which is quite corresponding to the previous conclusions in TG analysis.

3.7. UV lters dispersive solid-phase extraction isotherm for

silylated MCM-41
3.7.1. Effect of pH
The adjustment of pH is an important factor that affects the sorption behavior at water solid interfaces. Thus, the knowledge of pH
study is very important since pH not only affects the surface charge
of sorbent, but also affects the speciation of sorbent in solution [30].
To evaluate the pH effect, the pH of solution was examined from 2.0
to 10.0 (shown in Fig. 7). The adsorption quantity at pH 7.0 is much
higher than those obtained at other pH values for both OD-PABA
and EHMC. Consequently, pH 7.0 is employed in the whole sorption
procedure.

MCM-41for OD-PABA
MCM-41 for EHMC
M-MCM-41 for OD-PABA
M-MCM-41 for EHMC
T-M-MCM-41 for OD-PABA
T-M-MCM-41 for EHMC

140
120
100

qe(mg/g)

Fig. 5. TG for MCM-41, M-MCM-41 and TMS-M-MCM-41 materials.

80
60
40
20
0

pH
Fig. 7. Effect of pH.

10

L. Li et al. / Applied Surface Science 328 (2015) 2633

UV lters equilibrium adsorption in MCM-41, M-MCM-41 and TMSM-MCM-41 in water. The pseudo-second-order kinetic model and
intra-particle diffusion model have been widely used to t the
kinetic process of adsorption at the solid/water interfaces [30].

-1

20mg MCM-41, 10mLsolution c0=35mg L

-1
20mg M-MCM-41, 10mLsolution c0=25mg L
-1
20mg T-M-MCM-41, 10mLsolution c0=20mg L

qe(mg/g)

120

3.7.3. Langmuir isotherm

The Langmuir isotherm [31] describes a monolayer adsorption process on a homogeneous surface. Therefore, the Langmuir
isotherm model was chosen for estimation of the maximum
adsorption capacity. The linearized Langmuir equation is shown
in Eq. (2):

80

MCM-41 for OD-PABA

MCM-41 for EHMC
M-MCM-41 for OD-PABA
M-MCM-41 for EHMC
T-M-MCM-41 for OD-PABA
T-M-MCM-41 for EHMC

40

20

40

31

60

qe =

80

100

t (min)
Fig. 8. Amount of UV lters adsorbed in MCM-41, M-MCM-41 and TMS-M-MCM-41
materials versus time at 303 K.

qm KL ce
1 + KL ce

(2)

In Eq. (2), ce and qe are as dened before in Eq. (1), qm is a constant

and reect a complete monolayer (mg/g), KL is adsorption equilibrium constant (L/mg) that is related to the apparent energy of
sorption. The Langmuir isotherm Eq. (2) can be linearized into the
following equation:
ce
1
ce
=
+
qe
qm
KL qm

3.7.2. Adsorption kinetics

Fig. 8 shows the temporal variation of the amount of UV lters
adsorbed on MCM-41 and silylated MCM-41, when the materials
was exposed to an aqueous solution having 35 mg/L, 25 mg/L and
20 mg/L UV lters. The initial adsorption rate is higher because of
larger number of available active sites, until it slows down and
becomes constant in about 60 min, 50 min and 40 min. It was indicated that the adsorption speeded up after surface modication.
Hence 60 min, 50 min and 40 min were used corresponding to the
8

EHMC

OD-PABA

A plot of ce /qe versus ce should indicate a straight line with slope

of 1/qm and an intercept of 1/(KL qm ).
It was noted from Fig. 9 that the adsorption of EHMC by
unsilylated and silylated MCM-41 obey Langmuir isotherm and
the maximum adsorption capacity were 7.54 mg/g for MCM-41,
101.50 mg/g for M-MCM-41and 130.21 mg/g for TMS-M-MCM-41,
respectively. The applicability of the linear form of Langmuir model
was proved by the high correlation coefcients R2 > 0.99. This
suggests that the Langmuir isotherms provide a good model of

EHMC
OD-PABA

100

80

qe(mg/g)

qe (mg/g)

(3)

4
3

60
40

20

1
0

10

15

20

25

30

35

ce (mg/L)

10

15

ce(mg/L)

EHMC

120

OD-PABA

qe(mg/g)

100
80
60
40
20
0

10

15

20

ce(mg/L)
Fig. 9. UV lters adsorption isotherms in MCM-41 (a), M-MCM-41 (b) and TMS-M-MCM-41 (c).

20

25

32

L. Li et al. / Applied Surface Science 328 (2015) 2633

Table 3
Adsorption isotherm parameters for EHMC.

Qm (mg/g)

KL

R2

3.7.4. The Freundlich isotherm

The Freundlich isotherm model [32] is the earliest known equation describing the adsorption process. It is an empirical equation
and can be used for non-ideal sorption that involves heterogeneous
adsorption. The Freundlich isotherm is commonly given by the following non-linear equation:

7.54
101.50
130.21

0.2665
0.7620
0.6224

0.9988
0.9997
0.9992

qe = KF ce

EHMC
Langmuir

MCM-41
M-MCM-41
T-M-MCM-41

1/n

the sorption, as is shown in Table 3. Besides, the adsorption of

OD-PABA by silylated MCM-41 also obey Langmuir isotherm
and the maximum adsorption capacity were 69.54 mg/g for MMCM-41and 75.36 mg/g for TMS-M-MCM-41, the parameters were
shown in Table 3.

0.8

where KF is a constant for the system, related to the bonding energy.

KF can be dened as the adsorption or distribution coefcient
and represents the quantity of UV lters adsorbed onto adsorbent
for unit equilibrium concentration. A value for 1/n indicates the
adsorption intensity of UV lters onto the adsorbent. It is favorable
adsorption as its value ranging from 0.1 to 0.5 and linear adsorption
while 1/n = 1. 1/n above 2 is unfavorable adsorption also indicates

OD-PABA

0.7

(4)

EHMC

0.6
4

0.5
0.3

ce/qe

lg qe

0.4
0.2
0.1
0.0

3
2
1

-0.1
-0.2
0.4

0.6

0.8

1.0

1.2

1.4

1.6

10

15

25

30

35

ce(mg/L)

lg ce

EHMC
OD-PABA

0.4

20

EHMC
OD-PABA

0.30
0.25

0.3

ce/qe

ce/qe

0.20

0.2

0.15
0.10

0.1
0.05

0.0

10

12

14

16

18

20

0.00

22

10 12 14 16 18 20 22

ce(mg/L)

ce(mg/L)

Fig. 10. Langmuir and Freundlich t of UV lters adsorption. (a) Freundlich t of OD-PABA adsorbed by MCM-41; (b) Langmuir t of EHMC adsorbed by MCM-41; (c) Langmuir
t of OD-PABA and EHMC adsorbed by M-MCM-41; (d) Langmuir t of OD-PABA and EHMC adsorbed by T-M-MCM-41.

Table 4
Adsorption isotherm parameters for OD-PABA.
OD-PABA
Langmuir

MCM-41
M-MCM-41
T-M-MCM-41

Freundlich

Qm (mg/g)

KL

R2

69.54
75.36

0.2259
0.7092

0.9986
0.9996

KF

n1

R2

0.4415

0.6228

0.9884

L. Li et al. / Applied Surface Science 328 (2015) 2633

a cooperative adsorption. Eq. (4) can be logarithmic linearized by

form Eq. (5) and the Freundlich constants can be determined:
log qe = log KF +

1
log ce
n

(5)

The applicability of the Freundlich adsorption isotherm was also

analyzed, using the same set of experimental data, by plotting
log(qe ) versus log(ce ).
The data obtained from linear Freundlich isotherm plot for the
adsorption of the OD-PABA onto MCM-41 is presented in Fig. 10a.
The correlation coefcient R2 value was over 0.98 indicating that
the sorption tted well on Freundlich isotherm. The value of
1/n = 0.6228 indicated that the adsorption was easier adsorption
and the parameters were shown in Table 4.
The data above conrmed that silylated MCM-41 materials were
possible to obtain even higher adsorption for UV lters, which
came to the conclusion that surface functionalization enhanced
the surface hydrophobicity of the materials and altered the surface
chemistry.
4. Conclusion
In this study, on the basis of synthesis MCM-41 material, methyl
functional materials M-MCM-41 and end-capped TMS-M-MCM-41
were obtained. The investigation showed that the mesoporosity
and pore symmetry of the material is retained after surface modication, these materials have excellent thermal stability, structural
rigidity, large specic surface area and pore volume, which is a
prerequisite for their potential applications of adsorption materials.
As expected, silylated MCM-41 materials were applied to absorb
two kind of UV lters from aqueous solution. The experimental data followed Freundlich isotherm and Langmuir adsorption
isotherm. The experimental adsorption capacity is successively
higher for silylated M-MCM-41 and TMS-M-MCM-41 compared to
unsilylated MCM-41, which attribute to alteration of pore size and
surface hydrophobicity of the materials. Therefore, silylated MCM41 materials can be applied for effective enrichment and separation
of UV lters from water.
Acknowledgment
We are grateful to the National Natural Foundation of China
(Grant No. 21265019) for supporting this research project.
References
[1] N. Serpone, D. Dondi, A. Albini, Inorganic and organic UV lters: their role
and efcacy in sunscreens and suncare products, Inorg. Chim. Acta 360 (2007)
794802.
[2] N.A. Shaath, The Encyclopedia of Ultraviolet Filters, Allured, Illinois, 2007, pp.
109110.
[3] K. Fent, A. Zenker, M. Rapp, Widespread occurrence of estrogenic UVlters in aquatic ecosystems in Switzerland, Environ. Pollut. 158 (2010)
18171824.
[4] H. Holbech, U. Norum, B. Korsgaard, P. Bjerregaard, The chemical UV-lter
3-benzylidene camphor causes an oestrogenic effect in an in vivo sh assay,
Pharmacol. Toxicol. 91 (2002) 204208.
[5] E. Manov, N.V. Goetz, U. Hauri, C. Bogdal, K. Hungerbhler, Organic UV lters
in personal care products in Switzerland: a survey of occurrence and concentrations, Int. J. Hyg. Environ. Health 216 (2013) 508514.
[6] J.L. Bened, A. Chisvert, A. Salvador, D. Snchez-Quiles, A. Tovar-Snchez,
Determination of UV lters in both soluble and particulate fractions
of seawaters by dispersive liquid-liquid microextraction followed by
gas chromatographymass spectrometry, Anal. Chim. Acta 812 (2014)
5058.

33

[7] I. Tarazona, A. Chisvert, Z. Len, A. Salvador, Determination of hydroxylated

benzophenone UV lters in sea water samples by dispersive liquidliquid
microextraction followed by gas chromatographymass spectrometry, J. Chromatogr. A 1217 (2010) 47714778.
[8] T. Poiger, H.R. Buser, M.E. Balmer, P.A. Bergqvist, M.D. Mller, Occurrence of UV
lter compounds from sunscreens in surface waters: regional mass balance in
two Swiss lakes, Chemosphere 55 (2004) 951963.
[9] F. Vela-Soria, O. Ballesteros, A. Zafra-Gmez, L. Ballesteros, A. Navaln, A
new method for the determination of benzophenone-UV lters in human
serum samples by dispersive liquidliquid microextraction with liquid
chromatographytandem mass spectrometry, Talanta 121 (2014) 97104.
[10] N. Negreira, I. Rodriguez, E. Rubi, R. Cela, Determination of selected UV lters in
indoor dust by matrix solid-phase dispersion and gas chromatographytandem
mass spectrometry, J. Chromatogr. A 1216 (2009) 58955902.
[11] M. Bachelot, Z. Li, D. Munaron, P.L. Gall, C. Casellas, H. Fenet, E. Gomez, Organic
UV lter concentrations in marine mussels from French coastal regions, Sci.
Total Environ. 420 (2012) 273279.
[12] N. Negreira, I. Rodrguez, E. Rub, R. Cela, Optimization of pressurized liquid
extraction and purication conditions for gas chromatographymass spectrometry determination of UV lters in sludge, J. Chromatogr. A 1218 (2011)
211217.
[13] M.E. Davis, Organizing for better synthesis, Nature 364 (1993) 391393.
[14] C.T. Kresge, M.E. Leonowicz, W.J. Roth, J.C. Vartuli, J.S. Beck, Ordered mesoporous molecular sieves synthesized by a liquid-crystal template mechanism,
Nature 359 (1992) 710712.
[15] J.S. Beck, J.C. Vartuli, W.J. Roth, M.E. Leonowicz, C.T. Kresge, K.D. Schmitt,
C.T.W. Chu, D.H. Olson, E.W. Sheppard, A new family of mesoporous molecular sieves prepared with liquid crystal templates, J. Am. Chem. Soc. 114 (1992)
1083410843.
[16] C.K. Lee, S.S. Liu, L.C. Juang, C.C. Wang, K.S. Lin, M.D. Lyu, Application of MCM-41
for dyes removal from wastewater, J. Hazard. Mater. 147 (2007) 9971005.
[17] Y. Zhou, Y.F. Tao, J. Yang, W.G. Lin, et al., Novel phenol capturer derived from
the as-synthesized MCM-41, J. Hazard. Mater. 190 (2011) 8793.
[18] Y. Hu, Y.Y. He, X.W. Wang, C.H. Wei, Efcient adsorption of phenanthrene by
simply synthesized hydrophobic MCM-41 molecular sieves, Appl. Surf. Sci. 311
(2014) 825830.
[19] S.A. Idris a, C.M. Davidsona, C. McManamon, M.A. Morris, Large pore diameter
MCM-41 and its application for lead removal from aqueous media, J. Hazard.
Mater. 185 (2011) 898904.
[20] X.S. Zhao, G.Q. Lu, Modication of MCM-41 by surface silylation with
trimethylchlorosilane and adsorption study, J. Phys. Chem. B 102 (1998)
15561561.
[21] A. Trouv, I. Batonneau-Gener, S. Valange, M. Bonne, S. Mignard, Tuning the
hydrophobicity of mesoporous silica materials for the adsorption of organic
pollutant in aqueous solution, J. Hazard. Mater. 201 (2012) 107114.
[22] Y.J. Zhu, J.H. Zhou, J. Hu, H.L. Liu, The effect of grafted amine group on the
adsorption of CO2 in MCM-41: a molecular simulation, Catal. Today 194 (2012)
5359.
[23] H. Javadian, M. Taghavi, Application of novel polypyrrole/thiol-functionalized
zeolite beta/MCM-41 type mesoporous silica nanocomposite for adsorption of
Hg2+ from aqueous solution and industrial wastewater: kinetic, isotherm and
thermodynamic studies, Appl. Surf. Sci. 289 (2014) 487494.
[24] G.D. Sheng, H.P. Dong, Y.M. Li, Characterization of diatomite and its application
for the retention of radiocobalt: role of environmental parameters, J. Environ.
Radioactivity 113 (2012) 108115.
[25] G.D. Sheng, R.P. Shen, H.P. Dong, Y.M. Li, Colloidal diatomite, radionickel and
humic substance interaction: a combined batch, XPS and EXAFS investigation,
Environ. Sci. Pollut. Res. 20 (2013) 37083717.
[26] X.M. Wang, H.H. Rao, X.Q. Lu, X.Z. Du, Application of solgel based
octyl-functionalized mesoporous materials coated ber for solid-phase
microextraction, Talanta 105 (2013) 204210.
[27] D.X. Zhang, L.K. Xue, Q. Zhu, X.Z. Du, A novel ber with phenyl-functionalized
MSU (michigan state university) coating for solid-phase microextraction combined with high performance liquid chromatography for preconcentration and
determination of trace polychlorinated biphenyls in environmental water samples, Anal. Lett. 46 (2013) 22902301.
[28] T. Yasmin, K. Mller, Synthesis and surface modication of mesoporous MCM41 silica materials, J. Chromatogr. A 1217 (2010) 33623374.
[29] A. Galarneau, J. Lapichella, D. Brunel, F. Fajula, Z. Bayram-Hahn, K. Unger, G.
Puy, C. Demesmay, J.L. Rocca, Spherical ordered mesoporous silicas and silica
monoliths as stationary phases for liquid chromatography, J. Sep. Sci. 29 (2006)
844855.
[30] G.D. Sheng, Y.M. Li, X. Yang, X.M. Ren, et al., Efcient removal of arsenate by a versatile magnetic graphene oxide composites, RSC Adv. 2 (2012)
1240012407.
[31] I. Langmuir, The constitution and fundamental properties of solids and liquids,
J. Am. Chem. Soc. 38 (1916) 22212295.
[32] H. Freundlich, Colloid and Capillary Chemistry, Methuen, London, 1926, pp.
8385.