Controllable synthesis of mesoporous titanosilicates for styrene oxidization using a nanocellulose template strategy

Article abstract of DOI:10.1039/c7ra01598d

In this work, mesoporous titanosilicates with tunable pore size were successfully synthesized using green and cheap bio-templates (nanocellulose). A series of samples was systematically prepared, characterized and used as catalysts for styrene oxidation by H₂O₂. The results demonstrated that the nanocellulose template strategy reported here was a feasible and effective method. The as-prepared titanosilicates presented high specific surface areas (450-500 m² g^?1) and their mesopore sizes could be tuned from 2 to 8 nm by varying the addition amount of templates in the synthesis process. Active tetrahedral Ti species were efficiently incorporated in the mesoporous silica. Meanwhile, strong acid sites of the samples were confirmed using NH₃-TPD. The catalytic results revealed that the optimal catalysts (Si/Ti = 20 mol ratio) showed high catalytic activity and product selectivity can be adjusted through changing the mesopore size of the catalysts. The recycling tests indicated that as-prepared catalysts exhibited low catalytic deactivation. In addition, the oxidation mechanism over this catalyst was proposed. Thus, the present novel, sustainable and controllable method showed potential practical applications.

Full text of DOI:10.1039/c7ra01598d

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Controllable synthesis of mesoporous
titanosilicates for styrene oxidization using
Cite this: RSC Adv., 2017, 7, 19237
a nanocellulose template strategy†
*
*
Lihui Gan, Naizhong Huang and Minnan Long
Dazhi Shen, Jian Liu,
In this work, mesoporous titanosilicates with tunable pore size were successfully synthesized using green
and cheap bio-templates (nanocellulose). A series of samples was systematically prepared, characterized
and used as catalysts for styrene oxidation by H2O2. The results demonstrated that the nanocellulose
template strategy reported here was a feasible and effective method. The as-prepared titanosilicates
presented high specific surface areas (450–500 m2 ꢀ1) and their mesopore sizes could be tuned from 2
g
to 8 nm by varying the addition amount of templates in the synthesis process. Active tetrahedral Ti
species were efficiently incorporated in the mesoporous silica. Meanwhile, strong acid sites of the
samples were confirmed using NH3-TPD. The catalytic results revealed that the optimal catalysts (Si/Ti ¼
20 mol ratio) showed high catalytic activity and product selectivity can be adjusted through changing the
mesopore size of the catalysts. The recycling tests indicated that as-prepared catalysts exhibited low
catalytic deactivation. In addition, the oxidation mechanism over this catalyst was proposed. Thus, the
present novel, sustainable and controllable method showed potential practical applications.
Received 8th February 2017
Accepted 25th March 2017
DOI: 10.1039/c7ra01598d
rsc.li/rsc-advances
pluronic triblock copolymer and 1-aminododecanelaurylamine,
are all from nonrenewable petroleum-based feed stocks and
1. Introduction
high cost which limited their large-scale application. Therefore,
it is still of great signicance to develop a simple, green and
cost-effective method by using renewable template materials as
an environmentally benign alternative. In this respect, bioma-
terials, in particular cellulose, attracts special attention as
a renewable, inexpensive “green” template.19–21
Since the discovery of titanosilicate-1 (Ts-1) in 1983, Ti incor-
porated zeolitic materials have received much attention due to
their remarkable catalytic activity, and created an environ-
mentally friendly route for the oxidation of organic compounds
using hydrogen peroxide in mild conditions.1,2 However, owing
to the fact that the pore sizes of conventional microporous
titanosilicate zeolites (Ts-1, Ts-2 or other microporous titano-
silicates) are smaller than 1 nm,3 large organic molecules
cannot assess the active sites located inside the cavities which
limits the utilization of microporous titanosilicates. To over-
come this drawback, mesoporous titanosilicates have been
developed and proved to be potential catalysts in a wide range of
oxidation reactions, especially for bulky organic molecules
oxidation. In recently years, many researches have been con-
ducted on synthesis of Ti containing mesoporous silica, such
as, Ti-MCM-type,4–7 Ti-HMS-type,8–11 Ti-SBA-type,12–16 etc., and
these catalysts have shown excellent catalytic properties in
oxidization reaction including hydroxylation of aromatics,3
oxidative desulfurization,17 oxidation of alkenes18 and so on.
Nevertheless, these catalysts suffer from cumbersome synthesis
procedures and high cost of templates. Especially for latter, the
template agents, such as cetyltrimethyl ammonium bromide,
Cellulose is one of the most abundant nature material on the
earth, which is sustainable, biodegradable and inexpensive
sources.22,23 When cellulose bers are subjected to acid hydro-
lysis, stable suspensions of nanocellulose are obtained. Nano-
cellulose is rod-like or ribbon-like object with a length typically
ranging from 50 to 1000 nm and a width varying from 3 to
50 nm.24–26 Due to possessing nanoscale dimension, high
specic strength, high surface area, unique nanosize and
accessible industrially in large scale, nanocellulose has been
considered as a most promising renewable nanomaterials.27–29
Recently, nanocellulose has been attracted people's interests in
synthesizing mesoporous materials.30–32 As a kind of nature
biological materials, nanocellulose is different from traditional
template agents. In addition, it has high aspect ratio, low
density and active surface of hydroxyl groups. Thus it possesses
the advantages of traditional so template and hard template at
the same time.33
In present work, we demonstrate a facile and sustainable
method for the synthesis of titanosilicates with tunable meso-
pore sizes and high specic surface areas by using nano-
cellulose as the template for the rst time. The characterization
College of Energy, Xiamen University, Xiamen, 36105, China. E-mail: jianliu@xmu.
edu.cn; longmn@xmu.edu.cn; Fax: +86-592-2188053; Tel: +86-592-5952787
† Electronic supplementary information (ESI) available. See DOI:
10.1039/c7ra01598d
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results revealed that active framework Ti species have effectively calculated by BET model. The pore size distribution curves were
incorporated in the mesoporous silicate. Further research obtained by the BJH (Barrett–Joyner–Halenda) method based on
illustrated that the pore size of as-synthesized mesoporous the adsorption branch of isotherm. The diffuse reectance UV-
titanosilicates was controllable. Finally, oxidation of styrene vis spectra were recorded on a VARIAN Cary 5000 spectrometer
was adopted as a probe reaction to evaluate the catalysts prop- equipped with a diffuse reectance attachment and using
erties of obtained titanosilicates.
BaSO4 as a reference. FT-IR spectra were recorded on a Nicolet
iS5 spectrometer. NH3-TPD was measured by using a Micro-
meritics AutoChem II 2920 equipped with a thermal conduc-
tivity detector (TCD).
2. Experimental
2.1. Chemical and materials
Cellulose from absorbent cotton, sulphuric acid, tetraethylor-
thosilicate (TEOS), tetrabutyl orthotitanate (TBOT), acetylace-
tone, styrene, hydrogen peroxide (30% w/v), acetonitrile. All
reagents was purchased from Shanghai Chemical Reagent Co.
Ltd. (Shanghai, China) and used as received without further
purication.
2.4. Catalytic activity
The catalytic tests were performed in a sealed round bottom
ask in which vigorous stirring at 80 C. Typically, the reactor
ꢁ
was charged with 200 ml styrene, 2 ml of acetonitrile as solvent,
specied hydrogen peroxide and 0.08 g catalyst loading. The
oxidation products were analyzed by gas chromatography on
Agilent 7890. Aer the reactions, the catalyst was separated by
centrifugation, washed with acetonitrile for three times and
dried at 100 ꢁC for 6 h to be reused.
2.2. Synthesis of titanosilicates
Suspensions of nanocellulose (NCC) were prepared as the
previous literature,34 with slight modication. In typical, ten
gram of cotton was treated with 100 ml of 65% (w/w) H2SO4 at
45 ꢁC for 120 min under vigorous stirring. Aer that, the ob-
tained nanocellulose suspension was diluted for 5-fold with
deionized water to terminate the hydrolysis. The nal aqueous
suspensions were sonicated for 20 min. The nal aqueous
suspensions were approximately 1.2% NCC concentration by
weight.
3. Results and discussion
3.1. Catalyst characteristics
Fig. 1 shows the XRD spectra of the samples with different Si/Ti
molar ratio. As seen, all the curves show a relatively weak
diffraction band at the 2q range of 15–35ꢁ, which is associated
with the amorphous silica materials.15,35 Additional peaks
characteristic of TiO2 are not detected in all samples. The result
indicates that the separate TiO2 phase is absent in the samples.
UV-vis diffuse reectance spectroscopy has been used to
study the environment of titanium in amorphous silica in the
wavelength range of 200 nm to 800 nm. As seen in Fig. 2, the
maxima of absorption band of all samples center at 220 nm
together with a weak shoulder band at 270 nm. The band at
220 nm can be attributed to tetrahedral Ti species and the
shoulder band at 270 nm indicate the presence of titanium in
an octahedral coordination environment.6 Absorbance value of
two bands suggests that a major of titanium species presents in
tetrahedral and accompanies by a less fraction in octahedral
coordination.3 Moreover, the absorption bands are not detected
in the range of 350–400 nm indicating that the presence of a free
TiO2 clusters or extra-framework anatase TiO2 species in all
One-pot synthesized titanium-silicate with various Ti loading
and pore size. In typically, 20 ml of ethanol, 10 ml TEOS,
specied mixture of acetylacetone and TBOT (molar ratio of
acetylacetone/TBOT ¼ 1/1) were thoroughly mixed at room
temperature. The molar composition of the mixture was 1
TEOS: 0.01–0.1 TBOT: 0.01–0.1 acetylacetone: 7.2 ethanol. To
this solution, specied volume of as-prepared nanocellulose
suspensions (1.2% wt) were added with vigorous stirring. The
nal solution was further stirred at room temperature for 2 h,
and the resulting mixture formed a gel in an oven at 100 ꢁC for
10 h. Finally, the product obtained was washed with deionized
ꢁ
water and calcined at 550 C for 5 h in air to remove the bio-
template incorporated in the composites. Aer that, the ob-
tained samples were crushed in an agate mortar. As a result, the
samples obtained were denoted as Ts-X(Y), where X ¼ 10, 20, 60
or 100 corresponding to the Si/Ti molar ratio and Y ¼ 0.5, 1.5 or
3.0 corresponding to the volume ratio of nanocellulose
suspensions to TEOS.
2.3. Characterization
Transmission electron microscopy (TEM) images were obtained
on Zeiss Libra200FE operated at 200 kV. XRD spectra of cata-
lysts were acquired on a Rigaku Ultima IV X-ray diffractometer
with Ni-ltered Cu Ka radiation operated at 40 kV and 30 mA.
The data was collected from 2q ¼ 10ꢁ to 90ꢁ at a scan rate of 10ꢁ
minꢀ1. The nitrogen adsorption and desorption isotherms were
measured on an ASAP 2020 system in static measurement
ꢁ
mode. The samples were degassed at 300 C for 4 h before the
Fig. 1 XRD patterns of titanosilicates synthesized with different Si/Ti
measurement. The specic surface area of sample was molar ratio.
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Ti ratios. As can be seen, all products show type-IV curves37 with
a narrow distribution of mesoporous diameters centering at
about 7.5 nm. Specic surface areas and pore volume change
slight at Si/Ti ¼ 100, 60 and 20 while they decrease prominently
at Si/Ti ¼ 10. These changes could be observed clearly in Table 1
(entry 1–4). This result indicates that titanium incorporated in
SiO2 framework has little effect on the mesoporous structure at
high Si/Ti ratio. However, excessive-loading of titanium (Si/Ti ¼
10) in the sample could also induce a reduction in BET surface
area and pore volume.
Fig. 2 (a) UV-vis spectra and (b) FT-IR spectra of titanosilicates with
different Si/Ti mole ratios.
The inuence of templates ratio on the morphology and pore
structure has been investigated. The results are showed in
Fig. 3c and d, and the corresponding parameters are listed in
Table 1 (entry 5–7). The pore diameter and pore volume
signicantly increase with the addition amount of nano-
cellulose templates in precursor solution. Subsequently, the
specic surface areas of the samples slightly decrease. These
results conrm that the pore size of the catalysts can be
systematically adjusted by varying the amounts of bio-template
(nanocellulose) in the synthesis system.
Fig. 4 gives the TEM images of as-prepared samples with the
NCC/TEOS ratio at 0.5, 1.5 and 3, respectively. The synthesized
samples show the patterns characteristic of disorder wormhole-
like meso-structure. The similar structure was also observed by
previously reports.38,39
The property of acid sites is determined by NH3-TPD (Fig. 5).
Two major desorption peaks are observed at 150–250 ꢁC and
300–800 ꢁC in Fig. 5. The former can be attributed to ammonia
desorbed from weaker acid centers, and the latter was from
relatively stronger acid centers. The acidic sites of the samples
can be attributed the unsaturated Ti4+ species at surface defect
sites of the catalysts.15,40
samples can be ruled out,17 which are in good agreement with
the XRD results.
The FT-IR spectra of the samples are shown in Fig. 2b. All
samples appear a band at 960 cmꢀ1 which can be associated
with the framework Si–O–Ti vibrations.2 The existence of Si–O–
Ti indicates that the Ti species are incorporation into the
framework which would supply active sites on catalyst. The
result further conrms that active framework Ti species have
efficiently incorporated in the mesoporous silica.
In this work, the samples have been synthesized under acidic
precursor solution conditions which is from the acidic nano-
cellulose suspension solution. The pH of the synthesis
precursor solutions are in the range of 0.2–0.4. The silica/Ti
precursor will hydrolysis under the action of acid catalyst.36
However, it is well known that the hydrolysis of silica precursor
(TEOS) is slower than that of titanium precursor (TBOT). To
avoid the incongruous hydrolysis rates, acetylacetone has been
used as a chelating agent to ensure active framework Ti species
efficiently incorporating into the framework of silica rather than
separate TiO2 crystals.
Fig. 3a and b show the N2 adsorption–desorption isotherms
and the pore size distribution for the samples with different Si/
3.2. Catalytic performances of catalysts
3.2.1 Effect of Si/Ti ratio. Finally, the catalytic performance
of as-synthesized samples are evaluated through oxidation of
styrene by using 30 wt% H2O2 as an oxidant. The main products
of the reaction are benzaldehyde, 1-phenyl-1,2-ethanediol and
benzoic acid. The effect of catalysts in different Si/Ti mole ratio
catalysts is investigated and the results are presented in Fig. 6a.
Obviously, the catalytic activity (styrene conversion) increases
rstly with the increasing of Ti content but then drop. The
optimum result is at Si/Ti ¼ 20 with the highest conversion of
71.3%. It is reasonable that the activity site increase with the Ti
content. However, the catalytic activity does not increase at Si/Ti
¼ 10. The result may be mainly due to the decreased specic
surface areas of the sample (Table 1, entry 1), which reduce the
activity sites on the surface of the catalysts.
3.2.2 Effect of pore size. Catalysts with three different pore
sizes at the Si/Ti ¼ 20 were evaluated and the results are shown
in Fig. 6b. The catalysts Ts-20(0.5) and Ts-20(1.5) exhibit almost
the same conversions (73.5% and 74.4%, respectively) which
can be attributed to their similar specic surface areas. Owing
to the relative low specic surface areas of Ts-20(3.0) compared
with the Ts-20(0.5) and Ts-20(1.5), the conversion correspond-
ingly decrease to 71.3%. As for the effects of pore size on
Fig. 3 N2 adsorption and desorption isotherms of mesoporous tita-
nosilicates with different Si/Ti ratio (a), corresponding pore size
distribution (b), different CNC/TEOS ratio (c) and corresponding pore
size distribution (d). The isotherms for products Ts-20(1.5) and Ts-
20(30) were vertically offset by 70 and 200 cm3 gꢀ1, respectively in part
(c).
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Table 1 Textural characterization of as-prepared titanosilicates
Si/Ti
(mole ratio)
NCC/TEOS
(v/v)
S
DBJHa
(nm)
Vp
b
Entry
Cat.
(m2 gꢀ1
)
(cm3 gꢀ1
)
1
2
3
4
5
6
7
Ts-10(3.0)
Ts-20(3.0)
Ts-60(3.0)
Ts-100(3.0)
Ts-20(0.5)
Ts-20(1.5)
Ts-20(3.0)
10
20
60
100
20
20
20
3
3
3
3
0.5
1.5
3
425.1
463.9
462.6
466.2
516.9
500.5
463.9
7.6
7.5
7.5
7.4
2.1
3.9
7.5
0.93
1.05
1.09
1.08
0.32
0.55
1.05
a
b
Pore diameter (obtained from the adsorption isotherm by the BJH method). Pore volume determined by nitrogen adsorption at a relative
pressure of 0.98.
Fig. 4 TEM images of the samples. Ts-20(0.5) (a), Ts-20(1.5) (b) and
Ts-20(3.0) (c).
products distribution, the Ts-20(3.0) with the pore size at 7.5 nm
gave a better performance in selectivity for benzaldehyde than
other catalysts. Whereas, the Ts-20(0.5) with the pore size at
2.1 nm show a better selectivity for 1-phenyl-1,2-ethanediol.
This result indicates that different pore size of the catalysts
has an obvious effect on the reaction. Thus, as-prepared cata-
Fig. 6 Catalytic performances on the oxidization of styrene. (a) Effect
of Ti/Si ratio (80 ꢁC, 4 h, H2O2/styrene ¼ 2); (b) effect of pore size of
catalysts (80 ꢁC, 4 h, H2O2/styrene ¼ 2); (c) effect of the H2O2/styrene
lysts with tunable pore size will be advantageous to adjust the
selectivity of the products.
(catalyst: Ts-20(3.0), 80 ꢁC, 4 h); (d) effect of reaction time (catalyst:
Ts-20(3.0), 80 ꢁC, H2O2/styrene ¼ 3).
3.2.3 Effect of H2O2/styrene. The sample Ts-20(3.0) was
chosen to investigate the inuences of H2O2/styrene mole ratio
and the results are shown in Fig. 6c. It is obvious that an
increased oxidant/reactant ratio leads to the facilitation of
styrene conversion. With the H2O2/styrene ratio increasing from
1.5 to 3, the conversion of styrene increase from 63.5% to
86.3%. But simultaneously, the selectivity for 1-phenyl-1,2-
ethanediol decrease obviously from 24.9% to 15.3% and,
benzaldehyde and benzoic acid selectivity rise.
86.3% with prolongation of reaction time from 1 to 4 h. Only
little increment was observed when reaction time was pro-
longed to 6 h. Moreover, the product distribution showed little
changes with reaction time.
3.2.5 Proposed mechanism of oxidation reaction. It is well
accepted that the oxidation of styrene at the side chain can
obtain different products depending on the catalysts and reac-
tion conditions. According to previous reports,41–43 we proposed
that the reaction process may have two major reaction routes
(Scheme 1). On the presence of catalysts, benzaldehyde, 1-
phenyl-1,2-ethanediol and benzoic acid are detected in the
oxidation products. The main product is benzaldehyde, which
is from the direct oxidative cleavage of the styrene side chain
double bond40 (route 1, Scheme 1). Benzaldehyde can also be
from a oxidization of epoxystyrene (route 2–1, Scheme 1), and it
is also readily oxidized to benzoic acid.41 It is interesting that
epoxystyrene is not detected in products compared with
previous reports.2,18 This can be ascribed to the existence of acid
site on our catalysts and the subsequent hydrolysis of epoxy
group.44 Therefore, the product of 1-phenyl-1,2-ethanediol is
derived from the hydrolysis of the epoxystyrene (route 2–2,
Scheme 1). Furthermore, there is a competition between the
3.2.4 Effect of reaction time. Fig. 6d showed the effect of
reaction time on styrene oxidation using Ts-20(3.0). It was
found that styrene conversion increased rapidly from 46.3 to
Fig. 5 NH3-TPD spectra of Ts-20(0.5); Ts-20(1.5); Ts-20(3.0).
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bio-template (nanocellulose) for the rst time. As-prepared
titanosilicates are proved with high surface areas (450–500 m2
gꢀ1) and tunable pore size (2–8 nm). Active framework Ti has
effectively incorporated in the frameworks of silicate. Mean-
while, strong acid sites of the samples have been conrmed by
NH3-TPD. The catalyst tests illustrate that the optimum Si/Ti
atom ratio is 20 and product selectivity can be adjusted
through changing the mesopore size of the catalysts. The recy-
cling tests indicate that the catalysts exhibit low catalytic
deactivation. Hence, the catalysts synthesized with presenting
method will be advantageous to general applications in various
molecular catalysis due to their tunable pore size.
Scheme 1 Proposed reaction mechanism of styrene oxidation.
Acknowledgements
This work was supported by the National Natural Science Foun-
dation of China (No. 21303142), the research fund from the
Xiamen Southern Oceanographic Center (No. 4GZP59HJ29),
Fujian Provincial Department of Ocean and Fisheries (No. 2014-
25), and President Fund of Xiamen University (No. 20720150090).
Fig. 7 Catalyst reusability (Ts-20(3.0); H2O2/styrene ¼ 3; 80 ꢁC; 4 h.)
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