Synthesis, characterization and application of N-Ti/13X/MCM-41 mesoporous molecular sieves

Article abstract of DOI:10.1166/jnn.2016.11048

Di-n-butyl phthalate (DBP) is a type of phthalate ester. In recent years, an increasing number of studies have examined the removal of DBP. In this study we use a composite material of N-Ti/13X/MCM-41, synthesized by nitrogen, molecular sieve 13X, tetrabutyl orthotitanate and tetraethyl orthosilicate as raw materials, CTAB as a structural template and tetrabutyl titanate and urea under hydrothermal conditions. The optimized experimental conditions, such as the amount of material, reaction time, pH value and initial concentration were tested. The surface areas of N-Ti/13X/MCM-41 were found to be 664 m²g^-1. TEM micrographs revealed N-Ti/13X/MCM-41 is consisting of aggregates of spherical particles, similar with standard synthesized MCM-41 (Mobil Composition of Matter No. 41). Through photocatalytic degradation experiments, the optimum degradation efficiency of DBP was more than 90% at a pH 6.0 with catalyst dosing of 0.15 g L^-1.

Full text of DOI:10.1166/jnn.2016.11048

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Vol. 16, 6567–6574, 2016
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Synthesis, Characterization and Application of
N-Ti/13X/MCM-41 Mesoporous Molecular Sieves
Hong Tao1, Nhat-Thien Nguyen2, Xiao-Hui Hei1, Nguyen Cong Nguyen2, Hsiao-Hsin Tsai3,
I-Cheng Chang3ꢀ∗, and Chang-Tang Chang3ꢀ∗
1Department of School of Environment and Architecture, University of Shanghai for Science and Technology,
Shang-Hai City, 100044, China
2Department of Institute of Environmental Engineering and Management, National Taipei University of Technology,
Taipei 106, Taiwan
3Department of Environmental Engineering, National I-Lan University, I-Lan City, 260, Taiwan
Di-n-butyl phthalate (DBP) is a type of phthalate ester. In recent years, an increasing num-
ber of studies have examined the removal of DBP. In this study we use a composite material
of N-Ti/13X/MCM-41, synthesized by nitrogen, molecular sieve 13X, tetrabutyl orthotitanate and
tetraethyl orthosilicate as raw materials, CTAB as a structural template and tetrabutyl titanate and
urea under hydrothermal conditions. The optimized experimental conditions, such as the amount
of material, reaction time, pH value and initial concentration were tested. The surface areas of
N-Ti/13X/MCM-41 were found to be 664 m2g−1. TEM micrographs revealed N-Ti/13X/MCM-41 is
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consisting of aggregates of spherical particles, similar with standard synthesized MCM-41 (Mobil
IP: 193.9.158.33 On: Tue, 10 May 2016 01:50:19
Copyright: American Scientific Publishers
Composition of Matter No. 41). Through photocatalytic degradation experiments, the optimum
degradation efficiency of DBP was more than 90% at a pH 6.0 with catalyst dosing of 0.15 g L−1
.
Keywords: MCM-41, 13X, Composite Materials, di-n-Butyl Phthalate.
1. INTRODUCTION
use mesoporous silica for the adsorption of metal ions,
excellent adsorption ability and selectivity towards Pb2+
(ca. 300 ꢁg mg−1).9 Wu et al. (2013) have been synthe-
sized benzene-bridged periodic mesoporous organosilicas
and use as adsorbents for the adsorption of methylene
blue, these adsorbents have very high adsorption capacities
and extremely rapid adsorption rates for methylene blue
removal.10 Whittaker et al. (2014) predicting the integral
heat of adsorption for gas physisorption on microporous
and mesoporous adsorbents.11
Mesoporous materials have great potential for use in
both macroscopic applications and nanotechnology. In
the study of Ariga et al. (2012) introduce examples
of recent developments in mesoporous materials involv-
ing innovations in their components. These examples
include syntheses of mesoporous silica, metal oxides,
semi conductive materials, metals, alloys, organic compos-
ites, biomaterial composites, carbon, carbon nitride, and
boron nitride, as innovative components.12 Jiang et al.
(2012) synthesized Mesoporous alumina films with large-
sized cage-type mesopores were prepared by using com-
mercially available diblock copolymer (PS-b-PEO) and
Engineered nanomaterials (ENMs), as an important con-
cept advance in nanotechnology environmental and health
(nano-EHS) is important for environmental health and
safety, it play a key role in human and environmental
issue, and hazard generation.1 Since scientists at Mobil
Oil Research and Development announced the success-
ful synthesis of mesoporous molecular sieves (M41S) in
1992, numerous studies on the synthesis, characterization
and application of M41S have been reported.2–4 Owing
to the amorphous pore walls and rich surface hydroxyl
groups,5ꢀ6 which facilitate the modification of skeleton
and surface properties, the functionalization of mesoporous
silica materials have attracted growing attention.7 Meso-
porous materials, having pore sizes that range from 2 to
50 nm, thanks to high surface areas of >1000 m2g−1, large
pore volumes and large nanoscale pores, readily absorb
gas and liquid.8 There are some articles on the application
of the mesoporous material, such as Shieh et al. (2013)
∗Authors to whom correspondence should be addressed.
J. Nanosci. Nanotechnol. 2016, Vol. 16, No. 6
1533-4880/2016/16/6567/008
doi:10.1166/jnn.2016.11048
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Synthesis, Characterization and Application of N-Ti/13X/MCM-41 Mesoporous Molecular Sieves
Tao et al.
economic inorganic salt (AlCl3) as aluminum source. The
obtained mesopore sizes drastically expand from 35 nm to
80 nm.13 More recently, Ariga et al. (2014) use the method
of Iler and Kirkland to preparation of layer-by-layer (LbL)
microcontainers, both studies report the buildup of inor-
ganic film based on negatively charged silica particles and
positively charged boehmite (alu-mina) fibrils. Preparation
of LbL microcontainers using a poly-(dimethylsiloxane)
mold with poly(vinyl alcohol) and sodium montmorillonite
clay nanoplatelets.14
adsorption/desorption BET isotherm analyzer and Trans-
mission Electron Microscope, X-ray powder diffraction
and Fourier transform infrared spectra.
2. MATERIALS AND METHODS
2.1. Chemicals and Starting Materials
Molecular sieve 13X (Na2O · Al2O3 · SiO2 · H2O), hexade-
cyl trimethyl ammonium bromide (C16H33(CH3ꢂ3N+Br−,
CTABr), tetraethyl orthosilicate (C8H20O4Si), tetrabutyl
orthotitanate (C16H36O4Ti), Urea (CH4N2O), hydrochloric
acid (HCl), nitrogen (N2ꢂ, anhydrous ethanol (C2H5OH),
dibutyl phthalate (C16H22O4ꢂ, sodium hydroxide (NaOH)
and di-n-butyl phthalate (DBP, C16H22O4ꢂ were all
obtained from Guo-Yao Group Chemistry Reagents
Co., Ltd.
The fabrication methods of mesoporous silica materials
mainly include skeleton doping and surface modification.
Surface modification of nanoparticles (NPs) is an efficient
method to control the contact between nanomaterials and
the biotics.15 Many kinds of metal ions, such as Al3+, Ti4+
,
Zr4+, Mn2+, Ni2+ and Ga3+ have been introduced to the
framework of mesoporous silica directly using hydrother-
mal processes and generating active sites such as acidic
sites and redox active sites.16–20 González et al. (2009)
synthesized a series of aluminium doped MCM-41 (Al-
MCM-41) with acidity, by changing the Si/Al molar ratios.
The Al-MCM-41 materials acted as acidic catalysts in the
hydro isomerization of n-heptane and the convention of
n-heptane increased with the enhanced acidity of the Al-
MCM-41 samples.21 Do et al. (2005) reported a series of
Ti-containing MCM-41 samples, such as Ti-MCM-41 with
2.2. Synthesis of N-Ti/13X/MCM-41
First, about 13X was dispersed into 10 mL of sodium
hydroxide (NaOH) aqueous solution and stirred 30 min.
Then, at room temperature, 5.2 mL of tetraethyl ortho-
silicate (C8H20O4Si) was added drop by drop to the homo-
geneous solution and continuously stirred for 30 min to
obtain solution A. Afterwords, B solution was obtained
by adding 2.5 g hexadecyl trimethyl ammonium bro-
mide (C16H33(CH3)3N+Br−, CTABr) to the A solution dur-
ing 30 min of continuous stirring. Afterwards, 0.05 g of
tetrabutyl orthotitanate (C16H36O4Ti) and requisite amount
variable Si/Ti ratios and Cr–Ti substituted TiO loaded
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2
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MCM-41 having different TiO2 loading. In the case of
nitrogen (N2) were added, again with stirring. The mix-
ture was continuously stirred overnight to carry out the
reaction.
Copyright: American Scientific Publishers
the Ti-MCM-41 samples with Si/Ti ratios higher than 20,
the framework incorporation of Ti into MCM-41 increased
with a decreasing Si/Ti ratio. On the contrary, the Ti-
MCM-41 with a lower Si/Ti ratio (Si/Ti = 10) showed low
structural integrity and formation of Ti-oxide species, lead-
ing to a considerable decrease in surface area. In a signif-
icant finding, TiO2 loaded on transition-metal-substituted
MCM-41 was found to have discernible photocatalytic
activity under visible light irradiation. However, the effect
of the amount of Ti in Ti-containing MCM-41 materials
on their photo catalytic activities is not clear.22
Once the reaction was complete, hydrochloric acid
(HCl) and sodium hydroxide (NaOH) were added to
achieve a desirable pH level. The suspension was then
transferred into a Teflon-lined stainless steel autoclave and
ꢀ
heated at 110 C for 48 h. The resulting white precipitate
was then filtered and washed consecutively with deionized
Di-n-butyl phthalate (DBP), part of the phthalic acid
esters family, and is one of the most widely used plasticiz-
ers. It is the most frequently identified phthalic acid ester,
found in diverse environmental samples including ground-
water, river water, drinking water, open ocean water, soil
humates, lake sediments and marine sediments. Due to
such widespread use and ubiquity in the environment, an
increasing amount of attention has been directed towards
DBP in recent years.23
The aim of the present study was to synthesize
N-Ti/13X/MCM-41 materials and DBP adsorption exper-
iment was carried out to compare the performance of
N-Ti/13X/MCM-41 (Include the catalyst dosage, reaction
time, pH, initial concentration and recycled). The catalyst
properties of calcined N-Ti/13X/MCM-41 samples were
investigated through various techniques such as nitrogen
Figure 1. N2
N-Ti/13X/MCM-41.
adsorption–desorption
isotherms
of
the
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Tao et al.
Synthesis, Characterization and Application of N-Ti/13X/MCM-41 Mesoporous Molecular Sieves
Table I. The surface characteristics of mesoporous materials synthe-
sized by others with the values obtained from this study.
Surface
Year
Researchers
Materials
area (m2 g−1
ꢂ
2015
2014
2014
2013
2012
This study
N-Ti/13X/MCM-41
MCM-41
Ti/MCM-41
Al/MCM-41
Ti/MCM-48 and
Ti/MCM-41
V/Mn/MCM-41
Mn/MCM-48
Al/MCM-41
Ni/MCM-36 and
Ni/MCM-22
664
193–608
204–1081
1005–1246
1106–1582
Paz et al.28
Opembe et al.29
Wang et al.30
Peng et al.31
2012
2012
2010
2008
Mahendiran et al.32
Park et al.33
Iwanami et al.34
Emil Dumitriu35
863
683–688
993
870
2006
2005
Souza et al.36
Batista et al.37
Al/MCM-41
Cu/Al/MCM-41
870
682–910
Figure 3. XRD patterns high-angle peaks of the N-Ti/13X/MCM-41.
water. Finally, the synthesized material was calcined in air
at 550 C for 5 h. All the chemicals used in this work
were analytical grade.
2.4. Adsorption and Photoactivity Measurement
ꢀ
0.05 mL of DBP were added to 500 mL of deionized
water and agitated for 30 minutes using an Ultrasonic
cleaner (Delta Co., 10L). Then, the solution was stirred
for 30 min at a rotation speed of 250 rpm by a Mag-
netic Mixer (Fargo Instruments Co., MS-211) to obtain a
100 mg L−1 solution. Adsorption and photoactivity degra-
dation experiments were carried out in 100 ml Erlenmeyer
flasks to which 0.15 g of N-Ti/13X/MCM-41 with 100 mL
2.3. Characterization of the Materials
In this experiment, the formation of a mesoporous struc-
ture was confirmed by X-ray diffraction (XRD). X-ray
powder diffraction patterns were recorded using a Rigaku
Minifiex Diffractometer with a CuKꢃ radiation wavelength
of the appropriate concentration of the test sample solu-
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of 0.1541838 nm. The surface area and pore size were
determined with a nitrogen adsorption/desorption isotherm
analyzer. Nitrogen adsorption/desorption isotherms of
adsorbent samples were carried out at 77 K on a
Micromeritics ASAP 2020 N volumetric adsorption ana-
lyzer. Fourier transform infrared (FTIR) spectra of sam-
ples were recorded at room temperature on a Perkin
Elmer Spectrometer. Each sample was scanned 20 times
at 4 cm−1 resolution over the range 4000–400 cm−1. The
morphology of the samples was characterized by transmis-
sion electron microscopy (TEM; JEOL inc., EM2100).
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tion were added. The samples were subsequently capped
Copyright: American Scientific Publishers
and shaken at 500 rpm in a constant tꢀemperature bath
(Deng Yng Co., DKW-20) shaker at 25 C under illumi-
nation of a 400 W halogen light source. After the phase
was filtrated using a membrane filter, the residual DBP in
aqueous solutions were determined using a UV-vis spec-
trophotometer (Hitachi Co., U-3900). The final DBP con-
Figure 2. XRD patterns low-angle peaks of the N-Ti/13X/MCM-41.
J. Nanosci. Nanotechnol. 16, 6567–6574, 2016
Figure 4. TEM of the N-Ti/13X/MCM-41.
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Tao et al.
100
90
80
70
60
50
40
30
20
0.30g L-1
0.20g L-1
0.15g L-1
0.10g L-1
0.05g L-1
20
40
60
80
100
120
140
160
180
200
Time (min)
Figure 7. The effect of the N-Ti/13X/MCM-41 dosage on performance.
Figure 5. FTIR spectra of the N-Ti/13X/MCM-41.
high relative pressures.24 There is a hysteresis loop, char-
acteristic of H2, resulting from pores having a narrow inlet
and wide hole as shown in Figure 1.25ꢀ26 The surface areas
and pore sizes of the N-Ti/13X/MCM-41 was 664 m2g−1
and 2.79 nm, respectively. For comparison, the specific
surface area values for the MCM mesoporous materials
synthesized, the type of composite material used for the
synthesis and the year in which they were reported in the
literature are summarized in Table I.
centrations were determined using ꢄmax of each DBP. DBP
solutions showed maximum absorbance at wavelengths of
229 nm.
The effect of contact time on the DBP removal of the
samples was studied by evaluating the removal efficiency,
removal efficiency of the DBP calculated as:
Removal efficiency ꢅ%ꢂ = ꢆꢅC0 −Cꢂ/C0ꢇ×100
(1)
The X-ray powder diffraction patterns of calcined mate-
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Where C0 is the initial concentration of the dye and C is
rials are shown in Figure 2 and Figure 3. They clearly indi-
IP: 193.9.158.33 On: Tue, 10 May 2016 01:50:19
the solution concentration after adsorption.
Copyright: American Scientific Publishers
cate characteristic low-angle peaks of composite materials,
showing that the adsorbent materials possess a hexagonal
mesophase structure with a clear (100) peak and weaker
reflections assignable to (110) and (200) reflections. The
reflection peaks for composite materials indicate a pore
structure similar to MCM-41, due to the smaller size of
periodic mesoporous areas, which is characteristic evi-
dence of the hexagonal mesoporous structure associated
with spherical particles.27 High-angle peaks of the com-
posite materials revealed only three reflection peaks at the
3. RESULTS AND DISCUSSION
3.1. Characterization Analysis
Isotherms of N-Ti/13X/MCM-41 composite materials were
measured with an N2 adsorption/desorption isotherm ana-
lyzer at a liquid nitrogen temperature (77 K). The
isotherms belong to Type IV in the definition of IUPAC
and indicate that the N2 is condensed with in the pores at
Figure 6. Adsorption properties of the N-Ti/13X/MCM-41.
Figure 8. The effect of reaction time.
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Tao et al.
Synthesis, Characterization and Application of N-Ti/13X/MCM-41 Mesoporous Molecular Sieves
Table II. DBP degradation adsorption kinetics equation.
Concentration (mg L−1
)
Formula
R2
5
y = −0ꢈ02532x +1ꢈ72994
y = −0ꢈ01392x +2ꢈ16259
y = −0ꢈ00893x +2ꢈ53442
y = −0ꢈ00709x +2ꢈ89247
y = −0ꢈ00592x +3ꢈ16117
0.96967
0.96157
0.98868
0.98439
0.98088
10
15
20
25
bands at 1635 cm−1 were caused by deformation vibra-
tions of adsorbed water molecules,40 several absorption
bands at around 1095–800 cm−1 could be assigned to
the Si–O–Si stretching41ꢀ42 and bands at 460 cm−1 were
due to the bending vibrations of surface Si–O− groups.43
Weak absorption bands near 960 cm−1 corresponded to
the replacement of Si by Ti and creation of an asym-
metric local framework, the framework vibration bands
associated with a Si–O–Ti bond. The absorption bands at
550∼400 cm−1 were the 13X molecular sieves.
Figure 9. The effect of pH.
vicinity of 20ꢀ, 23ꢀ and 26.5ꢀ, which are characteristic
peaks consistent with the 13X molecular sieve and can
be considered evidence of the presence of the micropore
structure in the composite materials.
TEM micrographs revealed the particle morphol-
ogy of composite materials after calcination. The
N-Ti/13X/MCM-41 consists of aggregates of spherical
particles, similar to the shapes for standard MCM-41 syn-
thesized under basic conditions.38 According to the TEM
3.2. Photocatalytic Degradation
3.2.1. Adsorption Properties of the N-Ti/13X/MCM-41
Adsorption efficiency experiments were conducted for
30 minutes, under no illumination, using a solution
made up of 10 mg L−1 of DBP and 0.15 g L−1 of
N-Ti/13X/MCM-41. Results are illustrated in Figure 6.
Adsorption efficiency increased with increasing reaction
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analysis (Fig. 4), the samples generally exhibited ordered
time and reached a maximum value at 20 minutes when
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hexagonal arrays of mesopores with a uniform pore size.
Although some areas of the samples were not highly
ordered, significant areas of the hexagonal order were
observed.
Figure 5 shows the FT-IR spectrum of N-Ti/13X/MCM-
41 over the range of 7800–350 cm−1. The bands near
3400 cm−1, can be attributed to the stretching vibrations
of the bulk silanol groups, molecular water OH− groups
and/or silanol group H ions.39 Moreover, the absorption
Copyright: American Scientific Publishers
adsorption efficiency of DBP was more than 50%. After
20 minutes, the adsorption efficiency remained unchanged
showing that that DBP adsorption into the composite mate-
rials is limited and once adsorption equilibrium is reached,
adsorption efficiency does not increase with additional
time.
3.2.2. Effect of N-Ti/13X/MCM-41 Concentration
Photocatalytic degradation experiments were carried out
using different amounts of N-Ti/13X/MCM-41 added to
100
Pure material
Recycle-1
Recycle-2
Recycle-3
80
60
40
20
0
20
40
60
80
100 120 140 160 180 200 220
Time (min)
Figure 10. The effect of initial DBP concentration.
Figure 11. Recycle experiments.
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Synthesis, Characterization and Application of N-Ti/13X/MCM-41 Mesoporous Molecular Sieves
Tao et al.
Table III. Intermediates of the reaction.
with increasing reaction time and obtained a degrada-
tion efficiency of more than 90% at a reaction time
of 180 min. After 180 min, the degradation efficiency
remained unchanged, likely due to a restriction in the num-
ber of active catalyst sites and increased illumination.
Time
(min)
Compound
names
Formula
structure
Samples
A
4ꢈ12
Benzoic acid
Methyl benzoate
Monobutyl phthalate
Dibutyl phthalate
COOH
B
C
D
4ꢈ28
COOCH3
3.2.4. Effect of pH
13ꢈ45
14ꢈ13
COOH
COOC4H9
Results show that the pH of the DBP solution had a sig-
nificant impact on photocatalytic degradation efficiency.
Degradation efficiency experiments were carried out on a
solution comprised of 10 mg L−1 DBP and 0.15 mg L−1 of
N-Ti/13X/MCM-41. The pH of the solution was adjusted
from 2 to 12 under an open light source. Figure 9 shows
the degradation behavior at the low pH value. Degrada-
tion efficiency increased with increasing pH value and the
best efficiency was found to be more than 90% at pH = 6.
On the contrary, the degradation efficiency decreased by
increasing pH value from 6 to 12. Under acidic condi-
tions, the DBP may undergo a certain degree of hydrolysis.
COOC4H9
COOC4H9
a 10 mg L−1 DBP solution having a pH = 6.0. Figure 7
shows how increases in concentration from 0.05 to
0.15 g L−1 caused increases in degradation efficiency. This
result is due to an increase in the amount of catalyst, which
produced a more active substance and sped up the rate of
degradation. When the concentration was increased from
0.15 to 0.30 g L−1, the degradation efficiency decreased.
Excessive catalyst dosage caused increased turbidity of the
solution, light transmittance was reduced, hindering the
penetration depth of light and thus inhibiting the compos-
ite material photocatalytic degradation efficiency of DBP.
The best efficiency occurred using a 0.15 g L−1 catalyst
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dosing combined with a 10 mg L−1 concentration of DBP
condition. The resulting degradation efficiency was 90%
at a reaction time of 150 min.
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Hydrolysis produced benzenedicarboxylic acid enhances
Copyright: American Scientific Publishers
solubility of DBP in water. The half-life of DBP is short
under such acidic conditions, which is conducive to pho-
tocatalytic degradation reactions. On other hand, when the
solution is in an alkaline state, degradation of DBP causes
the formation of CO2 and HCO3, and OH free radical scav-
enging effect, which ultimately reduces DBP degradation
rates.
3.2.3. Effect of Reaction Time
Figure 8 illustrates illumination time relative to removal of
DBP. Using a 10 mg L−1 solution of DBP, the pH of the
solution was adjusted to 6 and the photocatalytic degra-
dation efficiency of DBP was observed under different
reaction times. Degradation efficiency of DBP increased
3.2.5. Effect of Initial Concentration DBP
Figure 10 shows the effect of the initial concentration
on degradation of DBP at a pH = 6, using a solution of
0.15 mg L−1 of N-Ti/13X/MCM-41 and 180 min reaction
time. Initial concentrations of DBP ranged from 5, 10, 15,
20, 25 mg L−1. With increasing concentrations of DBP,
photocatalytic degradation efficiency showed a downward
trend. Under the same initial conditions, the catalyst sur-
face, once excited by light, generates a constant number
of hydroxyl free radicals. As the concentration of DBP
increased, the number of molecules needed to degrade
Figure 12. Degradation pathway of di-n-butyl phthalate.
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Synthesis, Characterization and Application of N-Ti/13X/MCM-41 Mesoporous Molecular Sieves
exceeds the number of hydroxyl free radicals, and degra-
dation efficiency was decreased.
References and Notes
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In this study composite materials were recycled by filter-
ꢀ
ing with ethanol and drying at 350 C for 2 hours. The
recycled form of the composite material was then used to
perform photocatalytic degradation of the DBP solution.
Results are shown in the Figure 11. In comparison with
new composite materials, degradation efficiency of recy-
cled material is lower. However, photocatalytic degrada-
tion efficiency is still significant, and was found to be as
high as 70%. But degradation efficiency of 3rd recycled
material only 35%. After several evidence recovered, and
its structure has been destroyed resulting in degradation is
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Results from analysis of the intermediates produced by the
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Table III. The main intermediate products of DBP pho-
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phthalate and benzoic acid. From this analysis, intermedi-
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mined and are shown in Figure 12.
4. CONCLUSIONS
In this study, the adsorption efficiency increased with
increasing reaction time. A maximum value was reached
at 20 min and adsorption efficiency was more than 50%.
Degradation efficiency increased with the amount of mate-
rial added and reached a maximum degradation efficiency
of 90%. Excessive catalyst dosage causes increased tur-
bidity of the solution and reduction of light transmittance
and penetration depth, thus inhibiting the composite mate-
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Degradation efficiency of DBP increased with increasing
reaction time and the best efficiency was found to be more
than 90% at a pH = 6. Degradation efficiency decreased
with increasing initial concentrations of DBP. The result
shows good compliance with the pseudo first order equa-
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Received: 31 January 2015. Accepted: 12 March 2015.
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6574
J. Nanosci. Nanotechnol. 16, 6567–6574, 2016