Arenesulfonic acid functionalized ordered mesoporous silica as solid acid catalyst for solvent free dehydration of sorbitol to isosorbide

Article abstract of DOI:10.1016/j.catcom.2015.06.017

Abstract Organosulfonic acid functionalized ordered mesoporous silicas with different moieties have been synthesized and used as solid acid catalysts for solvent free dehydration of sorbitol to isosorbide. In screening experiments with distinct solid acids, the arenesulfonic acid functionalized SBA-15 (Ar/SBA-15) showed higher catalyst performance as compared to propyl and fluorosulfonic acid sites. Under optimum reaction condition, Ar/SBA-15 afforded 100% sorbitol conversion with 71% isosorbide selectivity in 2 h at moderate temperature of 170°C. The high activity of catalyst ascribed to its ordered mesoporous structure and ease to access Br?nsted acid sites with high acid strength.

Full text of DOI:10.1016/j.catcom.2015.06.017

Arenesulfonic acid functionalized ordered mesoporous silica as solid acid
catalyst for solvent free dehydration of sorbitol to isosorbide
Aasif A. Dabbawala, Jung J. Park, Anil H. Valekar, Dinesh K. Mishra,
Jin-Soo Hwang
PII:
DOI:
Reference:
S1566-7367(15)30004-2
doi: 10.1016/j.catcom.2015.06.017
CATCOM 4367
To appear in:
Catalysis Communications
Received date:
Revised date:
Accepted date:
2 April 2015
17 May 2015
22 June 2015
Please cite this article as: Aasif A. Dabbawala, Jung J. Park, Anil H. Valekar, Dinesh
K. Mishra, Jin-Soo Hwang, Arenesulfonic acid functionalized ordered mesoporous silica
as solid acid catalyst for solvent free dehydration of sorbitol to isosorbide, Catalysis
Communications (2015), doi: 10.1016/j.catcom.2015.06.017
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ACCEPTED MANUSCRIPT
Arenesulfonic acid functionalized ordered mesoporous silica as solid acid catalyst for
solvent free dehydration of sorbitol to isosorbide
Aasif A. Dabbawala a, Jung J. Park a, Anil H. Valekar a, Dinesh K. Mishra a, Jin-Soo Hwanga *
a Bio-refinery Research Center, Korea Research Institute of Chemical Technology (KRICT),
Yuseong, Daejeon 305-600, Republic of Korea
* Corresponding Author: Tel.: +82-42-860-7382; fax: +82-42-860-7676
E-mail address: jshwang@krict.re.kr (J.-S. Hwang)
Abstract
Organosulfonic acid functionalized ordered mesoporous silicas with different moieties have
been synthesized and used as solid acid catalysts for solvent free dehydration of sorbitol to
isosorbide. In screening experiments with distinct solid acids, the arenesulfonic acid
functionalized SBA-15 (Ar/SBA-15) showed higher catalyst performance as compared to
propyl and fluorosulfonic acid sites. Under optimum reaction condition, Ar/SBA-15 afforded
100% sorbitol conversion with 71% isosorbide selectivity in 2 h at moderate temperature of
170 °C. The high activity of catalyst ascribed to its ordered mesoporous structure and ease to
access Brönsted acid sites with high acid strength.
Keywords: Dehydration; Sorbitol; Selectivity; Isosorbide; Mesoporous organosilica
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1. Introduction
The catalytic conversion of cellulosic biomass or biomass-derived carbohydrates to value
added chemicals have received considerable interest in the recent years due to the depletion
of fossil fuel and environment concern [17]. The sorbitol (a sugar alcohol) can be obtained
from cellulose via glucose hydrogenation and is considered as an important platform
molecule to synthesized number of chemicals [6,7]. By acid catalyzed dehydration, sorbitol is
converted into anhydro-sugar alcohols such as sorbitan and isosorbide (scheme 1). Both
anhydro-sugar alcohols can be extensively useful to synthesize a variety of intermediates
applicable in the preparation of surfactants, pharmaceuticals, cosmetics and synthetic
polymer industries [811].
OH
HO
OH
H
OH OH
O
OH
OH
O
HO
-H2O
-H2O
OH
1,4-Sorbitan
O
OH OH
Sorbitol
H
HO
Isosorbide
Scheme 1 Cyclodehydration of sorbitol to isosorbide
The dehydration of sorbitol to isosorbide (IS) was studied first using homogeneous
mineral acids especially in the presence of sulfuric acid [9]. It is known that mineral acid
based process has many disadvantages, such as risk in handling of acid, corrosion of
equipments and required tedious product purification. Consequently, the research in the field
of sorbitol cyclodehydration has been focused to develop solid acid catalyst and process
alternate to mineral acids [1017]. The various solid acid heterogeneous catalysts, such as
Metal (IV) phosphates (65% IS selectivity, 300 °C) [12], phosphoric acid modified Ta2O5 (48%
IS selectivity, 225 °C) [13], supported heteropolyacid (65% IS selectivity, 250 °C) [14],
sulfated CuO (67% IS selectivity, 200 °C) [15] and sulfated ZrO2 (61% IS selectivity, 210 °C)
[16] have been employed for the dehydration of sorbitol to isosorbide. All the studied solid
acid catalysts have their own advantages compared to homogeneous mineral acids. However,
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the most of studied solid acid catalysts require comparatively high reaction temperature
(200−300 °C) for significant production of isosorbide. Therefore, the development of
efficient solid acid catalyst that catalyzed this reaction at moderate temperature and produced
high isosorbide selectivity is highly desirable.
The functionalized ordered mesoporous silicas (OMS) possess superior physicochemical
properties and their applications in the field of catalysis and adsorptions have greatly been
explored [18]. The use of sulfonic acid modified OMS as catalyst has been increased for the
conversion of biomass-derived carbohydrates due their ordered porous structure and number
of accessible Brönsted acid sites [19,20]. However, the proper studies on cyclodehydration of
sorbitol to isosorbide using functionalized mesoporous materials are limited [21]. Herein, we
synthesized sulfonic acid functionalized OMS having different organic moieties and
evaluated their catalyst performance in solvent free cyclodehydration of sorbitol to isosorbide.
The experiment results of catalysts are discussed based on their organic functionalities and
anhydro-alcohols selectivity. Moreover, the effects of reaction temperature, catalyst amount
and reaction time on sorbitol conversion and isosorbide selectivity were studied and the
catalyst was also reused.
2. Experimental
2.1. General remarks
SBA-15 was prepared according to reported synthesis procedure [22]. The
propylsulfonic acid functionalized SBA-15 (Pr/SBA-15) and arenesulfonic acid
functionalized SBA-15 (Ar/SBA-15) were synthesized in two steps according to reported
method by changing precursors 3-mercaptopropyltrimethoxysilane (MPTMS) and 2-(4-
chlorosulfonylphenyl)ethyltrimethoxysilane (CSPTMS) respectively (Scheme 2) [20]. For
comparison, Pr/SiO2 was synthesized from amorphous silica (SiO2) and MPTMS precursor.
Sulfated zirconia (SZ) was prepared according to previously reported procedure [15]. The
fluorosulfonic acid functionalized acidic resins such as NR-50 (DuPontTM) and Nafion®
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SAC-13 (NF-SAC, fluorosulfonic acid Nafion® polymer on amorphous silica, 10–20 wt%)
were procured from Sigma–Aldrich. The total acid sites in catalyst samples were determined
by Acid-base back titration using molar solutions of NaOH and HCl with phenolphthalein as
indicator [23]. In a typical experiment, 0.050 g of catalyst was added to a 0.01 M NaOH
aqueous solution (20 mL). The mixture was stirred for 60 min at room temperature. After
separating catalyst by centrifuge, the supernatant solution was titrated by a 0.01 M HCl
solution using phenolphthalein as an indicator. The solvent free dehydration of sorbitol was
performed in simple reactor setup under reduce pressure and the composition of products was
analyzed using HPLC [24]. For catalyst reuse and regeneration, the water/ethanol was added
to the reaction mixture to dissolve product and then filtered to separate solid catalyst from the
product. The recovered catalyst was thoroughly washed with water and THF. The catalyst
was then dried and finally calcined at 300 °C for 2 h to get regenerated catalyst.
Scheme 2 Synthesis of Ar/SBA-15 and Pr/SBA-15
3. Results and Discussion
3.1. Characterization of the catalysts
The synthesized Pr and Ar/SBA-15 (SAS catalysts) were characterized by various
physicochemical analyses. The BET-surface area, pore size, pore volume and S content of the
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SAS samples are listed in Table 1. As compared to pristine SBA-15, the SAS catalysts
showed lower BET surface area, pore volume and pore diameter. The changes in above
parameters can be considered due to the functionalization and such parameters were
decreased depending on size of organic moieties. SAS catalysts showed type IV N2
adsorption-desorption isotherm similar to SBA-15 characteristic of ordered mesoporous solid
with average pore size 4 nm (Fig. S1). TEM and SEM images of SAS catalysts (Fig. 1)
showed long channels and morphological view of catalysts with hexagonal pore structure
whereas SEM-EDX spectrum confirms the presence of Si, O, C and S in both catalysts. This
suggests the incorporation of sulfonic acid organic moieties on SBA-15 surface and the
functionaliation did not alter the morphology and structure of SBA-15.
Table 1 Physicochemical properties of SBA-15 and SAS catalysts
a
b
c
SABET
PDavg
(nm)
PVtotal
S content d
(%)
Acidity
(mmol/g)
Catalyst
(m2/g)
(cm3/g)
SBA-15
Pr/SBA-15
Ar/SBA-15
692.52
6.19
4.88
4.80
0.89
-
0.1
353.84
0.43
1.81
3.56
0.81
1.15
291.78
0.36
a
b
c
d
Surface area (BET), Average pore diameter, Total pore volume, Sulfur content
(determined by elemental analysis)
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Fig. 1 TEM, HRTEM, SEM images and TEM-EDX spectrum of Pr/SBA-15 (P series) and
Ar/SBA-15 (A series).
Powder XRD patterns of SBA-15 (Fig. 2a) showed characteristic diffraction peaks
below at 2° corresponding to the (1 0 0), (1 1 0) and (2 0 0) planes which agree with its
uniform hexagonal structures [20]. These diffraction peaks for SAS catalysts do not alter
significantly but intensities of peaks decrease marginally confirming that the structure SBA-
15 of do not collapse during surface modification. The FTIR spectra of pyridine adsorbed
Ar/SBA-15 catalyst showed the absorption bands at 1636, 1543 and 1489 cm-1 attribute to the
interaction of pyridine with Brönsted acid sites which led to the formation of pyridinium ion.
Another broad band at 1440 cm-1 was attribute to the Lewis acid site and was originated due
to the electron inductive effect of the S=O double bond [25]. The characteristic bands for acid
sites were observed even at 300 ºC indicating the presence of relatively strong acid sites in
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catalyst (Fig. 2c). The acid strengths of catalysts were determined by NH3-TPD (Fig. S2).
The acid strength of catalyst having SO3H sites is depend on its molecular environment and
-SO3H attached to an aromatic ring shows comparative high acid strength than alkyl moiety
[20]. The total acid amount of catalysts were measured by acid-base titration and presented in
Table 1. From the TGA profile, it can be concluded that the SAS catalysts are stable up to
300 °C (Fig. 2b).
SBA-15
Pr/SBA-15
Ar/SBA-15
(a)
1
2
3
4
5
2 theta (deg)
(b)
100
95
90
85
80
75
70
SBA-15
Pr/SBA-15
Ar/SBA-15
100
200
300
400
500
600
700
800
Temperature (C)
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2.5
2.0
1.5
1.0
0.5
0.0
(c)
300 C
200 C
100 C
50 C
RT
1700
1650
1600
1550
1500
1450
1400
Wavenumer (cm-1)
Fig. 2 XRD patterns (a) and TGA profile (b) for SBA-15 and SAS catalysts, (c) FTIR spectra
of Ar/SBA-15 catalyst after pyridine adsorption at RT to 300 °C.
3.2. Catalytic dehydration of sorbitol
The catalyst performances of SAS catalysts were evaluated in dehydration of sorbitol
under solvent free condition. To understand the role and effect of different functional groups,
the commercially available acidic resins (NR-50 and Nafion® SAC-13) and sulfated ZrO2
were also tested for comparison purpose. The sorbitol dehydration was performed using
distinct solid acids by keeping similar acid value as studied catalysts have different acid
amount (Table S1). The major dehydrated products indentified were 1,4−sorbitan and
isosorbide along with small amount of 1,5−sorbitan. Non-indentified soluble or insoluble
colored polymeric compounds are termed here as ‘others’. From the results (Fig. 3), it can be
seen that SZ showed only 52% sorbitol conversion with very low isosorbide selectivity (5%)
in 30 min. In the case of fluorosulfonic acid functionalized resins, NF-SAC exhibited
comparative higher catalyst performance than NR-50. NF-SAC yielded sorbitol conversion
up to 75% with 16% isosorbide selectivity. However, the formations of side products were
high in the case of such acidic resins. Form the results of –SO3H functionalized catalysts, it
can be seen that the formation of side products were low compared to fluorosulfonic acid
based catalysts.
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% (others)
% (Sorbitan)
% (Isosorbide)
100
80
60
40
20
0
100
80
60
40
20
0
0
5
C
A
A
B
0
C
A
A
B
SZ
5
-
A
O2
i
S
B
-
SZ
A
O2
i
B
S
-
S
/
S
/
r
R
N
S
-
S
/
S
/
r
R
S
/
r
/
r
P
r
r
F
N
N
F
P
A
P
A
P
N
Fig. 3 Catalytic performance of distinct solid acid catalysts in dehydration of sorbitol;
Sorbitol = 32.9 mmol, catalyst (acid amount) = 0.17 mmol, temp. = 180 °C, reaction time =
30 min.
Interestingly, the high sorbitol conversions with considerable isosorbide formation were
attained with SAS catalysts. It is also observed that the sorbitol conversion and isosorbide
yield were found to depend on functionalized organic moiety. Pr/SBA-15 produced 18%
isosorbide yield with 90% of sorbitol conversion. In comparison to Pr/SBA-15, Ar/SBA-15
showed higher catalyst performance. Notably, the complete conversion of sorbitol with 31%
isosorbide yield was achieved only in 30 min (Fig. 3). The sorbitol dehydration is influence
by catalyst acid strength and nature of acid sites. The catalysts with Brönsted acid sites are
more efficient for the production of isosorbide [24]. Ar/SBA-15 contains Brönsted acid site
with high acid strength than Pr/SBA-15 (Fig. S2). The substrate molecules can easily
approach to acid sites without diffusion limitation due to the ordered mesoporous structure. In
turn, the remarkable catalyst activity can be realized with Ar/SBA-15. On the other hand, the
fluorosulfonic acid functionalized resins catalyst (NR-50 and NF-SAC) showed lower
catalyst performance and produced high amount of side products even though they have
macroporous structure. The low catalytic activity of such catalysts may be ascribed to their
low surface area and very hygroscopic nature which limits the accessibility of acid sites [26].
In addition, the fluorosulfonic acid site has higher acid strength than arene or propylsulfonic
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acid due the presence of highly electronegative fluorine atoms. The higher acid strength of
such catalysts may also be another reason for their low selectivity. In our previous study
using distinct homogeneous acid catalysts, we observed that the triflic acid having higher acid
strength produced higher amount of side products than p-toluene sulfonic acid and methane
sulfonic acid catalysts [24]. The above achieved results with distinct catalysts having
different organoacid sites clearly point out important of type of functional acidic group and
influence of ordered mesoporous structure in improvement of catalyst performance. In order
to achieve maximum selectivity of isosorbide using Ar/SBA-15 catalyst, the effect of
temperature, catalyst amount and reaction time were studied.
The effect of reaction temperature on sorbitol dehydration was studied at different
reaction temperatures (160 to 190 °C) for 1 h reaction time using Ar/SBA-15 (Fig. 4). The
selectivity of anhydro-alcohols was considerably influence by variation in temperature while
the complete sorbitol conversion was achieved in all cases. Initially at low temperature, the
sorbitan selectivity was high. With an increase of temperature, the isosorbide selectivity was
increased via sorbitan intermediate. Due to the sequential reaction, the quantitative formation
of isosorbide was observed after the complete sorbitol conversion. However, the formations
of side products were also increased with an increase of reaction temperature (Fig. 4).
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% Conv. (Sorbitol)
% Selc. (Sorbitan)
% Selc. (Isosorbide)
% Selc. (Others)
100
90
80
70
60
50
40
30
20
10
0
160
170
180
190
Temp. (C)
Effect of temperature on Ar/SBA-15 catalyzed sorbitol dehydration; sorbitol = 32.9
Fig. 4
mmol, catalyst (acid amount) = 0.17 mmol, reaction time = 60 min.
o
The effect of catalyst acid amount was investigated at 170 C by varying catalyst
amount and reaction time (Fig. 5). With an increase of acid amount, the complete sorbitol
conversion was attained relatively in shorter reaction time. The isosorbide yield increased
significantly from 24 to 50 % in 1 h with an increase of acid amount (up to 0.29 mmol) due to
higher availability of numbers of bronsted acid sites. By extending the reaction time, the
maximum 71% isosorbide yield was achieved in 2 h. The further increase in reaction time
and catalyst acid amount has no significant influence on yield. At acid amount of 0.29 mmol,
100% sorbitol conversion and best isosorbide selectivity (71%) was achieved in 20 min and 2
o
h respectively at 170 C. It is worth to note that Ar/SBA-15 used first time for sorbitol
dehydration and exhibited high isosorbide yield (71%) at moderate temperature compared to
reported phosphated, sulfated metal oxide and heteropoly acid supported catalysts (Table S2)
[12−16]. This result indicates the effectiveness of Ar/SBA-15 in dehydration of sorbitol to
isosorbide.
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80
(b)
(a)
0.13 mmol
0.17 mmol
0.23 mmol
0.29 mmol
100
80
60
40
20
0
70
60
50
0.13 mmol
40
0.17 mmol
0.23 mmol
0.29 mmol
30
20
10
0
0
20
40
60
80
100
120
0
10
20
30
40
50
60
Time (min)
Time (min)
Effect of acid amount on sorbitol conversion (a) and isosorbide yield (b) in Ar/SBA-15
Fig. 5
catalyzed dehydration of sorbitol; sorbitol = 32.9 mmol, temp. = 170 °C.
The catalyst re-use experiments using Ar/SBA-15 have also been carried out for several runs
at 170 °C for 30 min with 0.2 g of catalyst (Fig. S3). Sorbitol conversion was found almost
similar up to fourth run with regenerated catalyst. The decrease in isosorbide selectivity at
each run may be due to the deposition of organic impurities and thereby generation of char on
catalyst surface during regeneration treatment (Fig. S4 and S5) as ICP analysis of the product
solution indicated no leaching of sulfur and the morphology of used catalyst retained almost
similar (Fig. S6). By regenerating catalyst, it can be reused up to three times without
significant loss in conversion and selectivity.
4. Conclusions
Dehydration of sorbitol to isosorbide has been investigated under solvent free condition using
sulfonic acid functionalized organosilicas. The results demonstrated that the isosorbide
production influence by type of organo-acid site and ordered porous structure of catalyst.
Arenesulfonic acid functionalized SBA-15 (Ar/SBA-15) was found to be efficient for the
dehydration of sorbitol to isosorbide. In comparison to propyl/fluorosulfonic acid site and
phosphated/sulfated metal oxide catalysts, Ar/SBA-15 catalyzed the dehydration of sorbitol at
comparatively lower reaction temperature and produced high isosorbide yield (71%) at
170 °C.
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Acknowledgement
This work was supported by the Institutional Research Program of KRICT (SI-1501) and by a
grant (B551179-10-03-00) funded by the Korea Research Council Industrial Science and
Technology, Republic of Korea.
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Arenesulfonic acid functionalized ordered mesoporous silica as solid acid catalyst for
solvent free dehydration of sorbitol to isosorbide
Aasif A. Dabbawala a, Jung J. Park a, Anil H. Valekar a, Dinesh K. Mishra a, Jin-Soo Hwanga *
a Bio-refinery Research Center, Korea Research Institute of Chemical Technology (KRICT),
Yuseong, Daejeon 305-600, Republic of Korea
* Corresponding Author: Tel.: +82-42-860-7382; fax: +82-42-860-7676
E-mail address: jshwang@krict.re.kr (J.-S. Hwang)
Graphical Abstract
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Research highlights

Solvent free dehydration of sorbitol investigated using –SO3H functionalized SBA-
15



Isosorbide formation influenced by type of organoacid site and porous structure
Arene –SO3H modified SBA-15 (Ar/SBA-15) showed higher catalyst performance
Ar/SBA-15 exhibited high isosorbide selectivity (71%) at moderate temperature
16