Ultrasound-assisted synthesis of UiO-66-NHSO3H via post-synthetic modification as a heterogeneous Br?nsted acid catalyst

Article abstract of DOI:10.1016/j.poly.2019.03.009

Efficient SO₃H-functionalized metal organic framework, UiO-66-NH-SO₃H, has been successfully prepared through a post-synthetic modification strategy of UiO-66-NH₂ with Chlorosulfonic acid reagent. The UiO-66-NH₂ has been synthesized by an ultrasound-assisted (US) method and compared with the conventional-heating method. The UiO-66-NH-SO₃H was characterized by elemental analysis, SEM, PXRD and FT-IR to serve as an efficient heterogeneous catalyst for the benzimidazole formation and reductive amination reaction. Furthermore, the UiO-66-NH-SO₃H catalyst exhibits good stability, general applicability and excellent recycling performance.

Full text of DOI:10.1016/j.poly.2019.03.009

Accepted Manuscript
Ultrasound-Assisted Synthesis of UiO-66-NHSO H via Post-synthetic Modifi-
3
cation as a Heterogeneous Brønsted acid Catalyst
Mahsa Homaee, Hosein Hamadi, Valiollah Nobakht, Mohamad Javaherian,
Behrang Salahshournia
PII:
S0277-5387(19)30175-5
https://doi.org/10.1016/j.poly.2019.03.009
POLY 13810
DOI:
Reference:
To appear in:
Polyhedron
Received Date:
Revised Date:
Accepted Date:
9 December 2018
19 February 2019
8 March 2019
Please cite this article as: M. Homaee, H. Hamadi, V. Nobakht, M. Javaherian, B. Salahshournia, Ultrasound-
Assisted Synthesis of UiO-66-NHSO H via Post-synthetic Modification as a Heterogeneous Brønsted acid Catalyst,
3
Polyhedron (2019), doi: https://doi.org/10.1016/j.poly.2019.03.009
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Ultrasound-Assisted Synthesis of UiO-66-NHSO H via Post-synthetic Modification as a
3
Heterogeneous Brønsted acid Catalyst
Mahsa Homaee, Hosein Hamadi*, Valiollah Nobakht, Mohamad Javaherian, Behrang
Salahshournia
Department of Chemistry, Faculty of Sciences, Shahid Chamran University of Ahvaz, Ahvaz, Iran.
Fax: +98 613 3331042 E-mail: h.hammadi@scu.ac.ir
Abstract
Efficient SO
prepared through a post-synthetic modification strategy of UiO-66-NH
reagent. The UiO-66-NH has been synthesized by an ultrasound-assisted (US) method and
compared with the conventional-heating method. The UiO-66-NH-SO H was characterized by
elemental analysis, SEM, PXRD and FT-IR to serve as an efficient heterogeneous catalyst for the
3
H-functionalized metal organic framework, UiO-66-NH-SO
3
H, has been successfully
2
with Chlorosulfonic acid
2
3
benzimidazole formation and reductive amination reaction. Furthermore, the UiO-66-NH-SO
3
H
catalyst exhibits good stability, general applicability and excellent recycling performance.
Keywords: UiO-66-NH-SO H, MOF, covalent PSM, Reductive Amination, Heterogeneous catalyst
3
Introduction
The development of new and facile approach for the introduction of Brønsted acidic functionalities
on various insoluble supports (especially porous materials with high surface areas) is a task of great
economic and environmental importance in chemical and pharmaceutical industries [1-4]. At
present, MOFs are attractive candidates as heterogeneous catalysts [5-11]. Because of the
nanometer dimensions of MOFs, these kind of catalysts exhibit a better reaction kinetics as
compared to the conventional supported mesoporous solid heterogeneous catalysts. Additionally,
the porous structure and large surface area make them capable to introduce new catalytically active
species conveniently [12-19].
1

One of the major advantages of MOFs is that the building components can be further modified
following its synthesis by post-synthetic modification (PSM) approach. Howere there are different
types of PSM, but most important form of PSM in MOFs is covalent PSM which defined as
covalently grafting the organic part with the functional species of parent MOFs [20]. Thus far,
various catalytic species, including organometallic, organic catalysts, and biocatalysts were
immobilized on the modified MOFs. Specifically, Brønsted acid MOFs catalysts are highly
desirable as an alternative to traditional homogeneous ones [21].
A number of Brønsted acid MOF catalysts that contain sulfonic acid groups for promoting organic
reactions have been provided by pre-installed sulfonic functional group or PSM [21-32].
On the other hand, there are different synthetic routes for the preparation of MOFs including
solvothermal, electrochemical, layer-by-layer growth, ultrasound assisted, microwave assisted and
mechanochemical methods [33-36]. Among these strategies, unltrasonic preparation of MOFs is a
promising technique which showed shorter reaction time, more energy efficiency and
environmental-friendly properties that make it a low cost scale-up method for the MOFs synthesis
[
37-40].
In this manuscript we report a new Brønsted acid MOF (UiO-66-NH-SO
3
H) obtained via
ultrasound-assisted method (US) and PSM and investigate its catalytic activity under mild
conditions toward benzimidazole formation and reductive amination reactions which is a great and
trustworthy approach for the formation of C–N bonds, in particular for synthesis of primary,
secondary, and tertiary amines [41-49] (Scheme 1 and 2).
Scheme 1. Benzimidazole formation by using UiO-66-NH-SO H
3
Scheme 2. Reductive amination reactions by using UiO-66-NH-SO H
3
2

Results and discussion
In order to compare between two synthetic methods, UiO-66-NH was prepared by combination of
2
Zr(NO
and conventional-heating methods [50]. The as-synthesized UiO-66-NH
Chlorosulfonic acid in chloroform to obtain UiO-66-NH-SO H (Scheme 3). There are many
examples of sulfunation of NH moeities with Chlorosulfunic acid [51-53]. For ensuring of
3
)
4
and 2-amino-1,4-benzenedicarboxylate (NH
2
–H
2
BDC) linker via the ultrasound-assisted
2
then treated with
3
2
conversation and reaction, elemental analysis was performed. Table 1 reveals that the sulfure
element was entirely located in the structure after modification.
Scheme 3. Postsynthetic modification of UiO-66-NH
2
by using ClSO H
3
3

Table 1. Results of elemental analysis of UiO-66-NH
2
and UiO-66-NH-SO
3
H
UiO-66-NH
2
UiO-66-NH-SO H
3
Element
Calculated %
Measured %
Calculated %
Measured %
33.183
1.502
C
H
N
S
33.6735
1.4129
4.9087
0
26.24
1.628
3.295
9.26
26.2954
1.1034
3.8332
8.7751
4.963
0
The crystal structures of the pristine (UiO-66-NH
after PSM were investigated by Powder X-ray diffraction (Figure 1). PXRD pattern of the UiO-66-
NH is in agreement with simulated (Figure 1, red). In addition, PXRD pattern of UiO-66-NH-
SO H (Figure 1, blue) is almost identical to the PXRD pattern of UiO-66-NH [50]. Hence, upon
treatment of chlorosulfonic acid, the framework of UiO-66-NH was remained intact during PSM.
2
) and the modified MOF (UiO-66-NH-SO
3
H)
2
3
2
2
Figure 1. PXRD patterns of simulated (black), UiO-66-NH
2
(red) and UiO-66-NH-SO H (blue)
3
4

The FT-IR spectra of the as-synthesized UiO-66-NH
Figure 2. The FT-IR spectrum of UiO-66-NH (Figure 2, black) was in good agreement to previous
report [50]. The FT-IR spectrum of UiO-66-NH-SO H (Figure 2, red) revealed successful
sulfonation of UiO-66-NH , due to the presence of some new bands correspond to asymmetric and
symmetric stretching of the O=S=O functional group at 1043 cm and S-O stretching vibration at
2
and the UiO-66-NH-SO
3
H are presented in
2
3
2
-1
-1
-1
1
141cm . The band correspond to C-N is appeared at 1290 cm . On the onther hand the stretching
-1
vibration responsible for the S-N bond observed at 645 cm and after the attachment of the sulfunic
acid, the ν -N-H shift to upper frequencies.
Figure 2. FT-IR spectra of UiO-66-NH
2
(black) and UiO-66-NH-SO H (red)
3
Furthermore, the morphology of UiO-66-NH-SO H was characterized by scanning electron
3
microscopy (SEM) (Figure 3). The result shows spherical morphology of the PSM product UiO-66-
5

NH-SO
3
H obtained via ultrasound-assisted method while the conventional-heating method gives
aggregiate flattened structure.
6

Figure 3. The FE-SEM images of UiO-66-NH-SO
3
H a) Ultrasound-assisted b) conventional
by Ultrasound-assisted method
heating synthesis c) the as-synthesized UiO-66-NH
2
Catalytic study
Synthesis of 1,2-Disubstituted Benzimidazole:
The catalytic performance of UiO-66-NH-SO H obtained from ultrasound-assisted and
3
conventional-heating methods were examined in the reaction of benzaldehyde and o-
Phenylenediamine as a model reaction (scheme 4). Optimization of the reaction conditions was
monitored by different conditions such as catalyst amount and solvent at room temprature. The
results are summarized in Table 2. The results point out that the model reaction exhibited the best
performance in the presence of 0.01 g amount of ultrasound-assisted UiO-66-NH-SO
UiO-66-NH-SO H obtained from conventional heating method showed the same catalytic activity
but in longer time (Table 2, entry 6). So the ultra-assisted UiO-66-NH-SO H was selected as the
3
H in ethanol.
3
3
catalyst. The results show that the solvent has significantly impacts on the yield of reaction and also
reactivity of the catalyst. Screening of the different solvent revealed that the excellent appropriate
conditions were obtained when the reaction was executed in CHCl
product 1-benzyl-2-phenyl-1H-benzo[d]imidazole was isolated in quantitative yield (98%) within
0 min (Table 2, entries 2-5).
3
and EtOH as solvent. The
6
7

Table 2. Optimization of conditions for preparation of benzimidazole using UiO-66-NH-
a
SO H
3
-1
Entry Catalyst (gr)
Solvent Time (min) Yields (%) TOF (h )
1
2
3
4
5
6
UiO-66-NH-SO
UiO-66-NH-SO
UiO-66-NH-SO
UiO-66-NH-SO
UiO-66-NH-SO
3
3
3
3
3
H (0.01)
H (0.01)
H (0.02)
H (0.01)
H (0.02)
-
300
60
60
60
50
90
60
97
98
98
98
96
1200
9700
4900
9800
5882
6400
CHCl
CHCl
EtOH
EtOH
3
3
Conventional-heating UiO-66- EtOH
NH-SO H (0.01)
3
7
8
9
1
UiO-66-NH-SO
UiO-66-NH-SO
UiO-66-NH-SO
3
3
3
H (0.01)
H (0.01)
H (0.01)
CH
Hexane 60
3
CN 60
80
50
45
67
75
8000
5000
300
1675
1875
H
2
O
90
0
1
UiO-66-NH
UiO-66-NH
2
(0.01)
(0.01)
CHCl
EtOH
3
240
240
1
2
a
All reactions were carried out in room temperature
However increasing the catalyst amount to 0.02 g, did not affect the rate and yield of the product
Table 2, entries 3 and 5). To investigate the effect of Brønsted acid SO H functional group, under
the same condition UiO-66-NH was also applied in the model reaction. The results reveal low
(
3
2
reactivity at room temperature even after 4 h (Table 2, entries 8 and 9). It can be concluded that the
sulfonic acid moiety in the MOF structure which acquired by post synthetic modification serves as
the Brønsted acid source to promote and proceed the reaction. According to green chemistry the
EtOH was selected as the solvent.
By optimum conditions in hand, in order to determine the scope and versatility of the present
catalytic system, various aromatic aldehydes, bearing electron-withdrawing (Table 3, entries 2-5) as
well as electron-donating groups (Table 3, entries 6–10), were used. Excellent yields were obtained
for both electron-withdrawing and electron-donating groups. The results were compared with the
corresponding reported spectral data.
8

Table 3. Synthesis of 1,2-disubstituted benzimidazoles derivatives
TOF
Mp (˚C)
54, 55]
Time
Yield
(%)
-1
Entry
1
Aldehydes
Products
(h )
(h)
[
1
97
90
90
95
93
97
97
9
700
294-295
2
3
4
5
6
7
3
2
2
2
3
3
3
4
4
4
3
3
000
500
750
650
233
233
301-302
298-299
326
201-202
227-228
276-277
234
8
9
2
90
4500
2
3
90
87
4
2
500
900
281-282
234-236
1
0
9

Reductive Amination
In order to optimize the reaction condition, such as solvent and amount of catalyst, the reaction
between benzaldehyde and aniline at room temperature was selected as model reaction. According
to results summarized in Table 4, the best catalytic activity was acquired with 0.01 g of UiO-66-
NH-SO
3
H in acetonitrile as solvent (Table 4, entries 5 and 8). Under the same conditions the UiO-
gave lower yield in longer time which shows the efficienty of the SO H moity in the UiO-
6-NH-SO H (Table 4, entry 8).
6
6
6-NH
2
3
3
To probe the performance and efficiency of UiO-66-NH-SO H as Brønsted acid catalyst, reductive
3
amination of various aldehydes and amine compounds was executed under optimum condition.
Table 5 provides the results for aldehydes and anilines containing both electron-withdrawing and
electron-donating groups. Concerning the aldehyde groups, with changing in functional groups,
neither the reaction rates nor the yield of products showed significant influence (Table 5, entries 2-
6
).
Table 4. Reductive amination under different conditions a
-
1
Entry Catalyst (g)
Solvent
-
Time (min) Yields (%)
TOF (h )
12000
667
1
2
3
4
5
6
7
8
UiO-66-NH-SO
3
3
3
3
3
3
3
H (0.01)
H (0.01)
H (0.01)
H (0.01)
H (0.01)
30
180
60
5
60
20
70
95
70
50
95
75
UiO-66-NH-SO
UiO-66-NH-SO
UiO-66-NH-SO
UiO-66-NH-SO
UiO-66-NH-SO
UiO-66-NH-SO
H O
2
EtOH
CH CN
CHCl
7000
3
114458
14000
40000
38152
7500
3
30
15
5
H (0.005) CH
3
3
3
CN
CN
CN
H (0.03)
(0.01)
CH
CH
UiO-66-NH
2
60
a
Reaction conditions: 1.0 mmol benzaldehyde, 1.0 mmol aniline and 2 mmol
NaBH at room temperature.
4
10

Conversely, the aromatic amines containing electron-withdrawing groups, gave desired products in
good yield but longer reaction time as result of decreasing the nucleophilic character of amine,
while the aromatic amines containing electron-donating groups require shorter reaction time. For
instance, 4-methoxy aniline reacts in 5 minutes with 97% yield (Table 5, entry 11), whereas, 4-nitro
aniline reacts in longer time (15 min) and lower yield of the product (Table 5, entry 8). Plausible
mechanisms for the synthesis of reductive amination and benzimidazole formation catalyzed by
UiO-66-NHSO
diffusion of precursor and reactant as well, because of enhancing in both the accessibility and
interfacial contact with active sides of the UiO-66-NH-SO H.
3
H are depicted in scheme 4. It is clear that porosity of catalyst facilitates the
3
Scheme 4. Proposed reaction mechanisms of reductive amination and benzimidazole formation
catalyzed by UiO-66-NHSO
3
H
11

Table 5. Reductive aminations of various aldehydes and amines by using NaBH
4
and
a
UiO-66-NH-SO H under the optimized conditions
3
-1
Entry Aldehydes Amines Products
Time (min) Yield (%) TOF (h )
1
5
95
114457
2
3
4
5
6
15
80
32000
30
20
15
15
75
90
90
80
15000
27273
36000
32000
7
10
90
52941
12

8
15
7
90
90
36000
77586
9
1
0
1
7
5
78
97
67241
1
116867
a
Reaction conditions: Aldehyde (1.0 mmol), amine (1.0 mmol), UiO-66-NH-SO
3
H
(
0.01 g), and NaBH (2 mmol) in CH CN (3 mL) at room temperature.
4
3
Recyclability
Once the reaction was over, the catalyst could be recovered by centrifugation, washed with ethanol
and chloroform for removing surplus then the separated catalyst reused at least 5 times in both
reactions. No significant loss of catalytic activity were observed even after five runs (Figures 4).
The PXRD and IR analyses of the used catalyst confirm structural integrity of the catalyst after five
runs (Figures 5 and 6).
13

(a)
(b)
Figure 4. Reusability of the UiO-66-NH-SO
3
H catalyst a) synthesis of 1,2-Disubstituted
Benzimidazole, and b) reductive amination
14

Figure 5. PXRD patterns of fresh (black) and after five times reused UiO-66-NH-SO H (red)
3
th
Figure 6. FT-IR spectra of UiO-66-NH
2
(black), UiO-66-NH-SO
3
H (red) and 5 cycled UiO-66-
NH-SO H (blue)
3
15

Comparison
The activity of UiO-66-NH-SO H for the benzimidazole formation and reductive amination
3
reactions, by considering the yield for the model reaction, has been compared with various
heterogeneous catalysts in Table 6. With precise comparison, we found out that the UiO-66-NH-
SO H has excellent performance in terms of yield and reaction time for both aforementioned
3
reactions.
Table 6. Comparison of various catalysts in Synthesis of 1,2-disubstituted benzimidazoles and
reductive amination reactions
Reaction
Catalyst
Solvent Temp. Time
˚C)
Yield Ref.
(%)
(
Synthesis
benzimidazoles VOSO
of CuO-np/SiO
2
MeOH
EtOH
r.t
r.t
4 h
1 h
93
92
92
88
93
96
[56]
[54]
[57]
[58]
[59]
[59]
[60]
This
work
4
Fe(III)–Schiff base/SBA-15
Nano-ZnO
CoO(II)
H
2
O
Reflux 3 h
Reflux 2 h
r.t
r.t
80
r.t
EtOH
EtOH
EtOH
DMF
EtOH
6 h
4 h
Co(OH)
2
p-TsOH
UiO-66-NH-SO
10 min 85
1 h
3
H
97
Reductive
Amination
CeCl
Silica phosphoic acid
B(OSO H) /SiO
Cellulose sulfonic acid
Ni-ACF@Am-SiO @Fe
UiO-66-NH-SO
3
.7H
2
O
EtOH
THF
r.t
r.t
8 h
93
[61]
15 min 95
10 min 95
45 min 94
20 min 98
5 min 95
[62]
[38]
[63]
[64]
This
work
3
3
2
CH CN r.t
3
EtOH
-
r.t
r.t
2
3
O
4
3
H
CH CN r.t
3
Experimental
Materials and methods
All chemicals were purchased from commercial sources and used without further purification. The

1
infrared spectra (4000-400 cm ) were recorded as KBr discs with a BOMEN MB102 FT-IR
16

spectrometer. Elemental analysis was performed with Elemental Vario EL Cube (Elementar
Analysensysteme GmbH, Germany) CHNS-O analyzer. Powder X-ray diffraction patterns were
recorded on a Philips X’Pert Pro diffractometer (Cu Kα radiation, λ= 1.54184 Å) in the 2θ range
5
−50°. The simulated powder XRD pattern based on single crystal data was prepared using
Mercury software. FE-SEM images were also recorded using TE-SCAN scanning electron
microscope operating at an acceleration voltage 20 kV.
Synthetic procedures
Conventional-HeatingPreparation of UiO-66-NH
Briefly, acetic acid (11.4 mL, 3.4 mmol) was added to a solution of Zr(NO
DMF (150 mL) and stirred at 55 C. Then a solution of 2-aminoterephthalic acid (1.2 g, 6.8 mmol)
in 50 mL DMF and 0.5 mL water were added to the solution and the final mixture sonicated at
C. The mixture was kept in an oil bath at 120 C for 24 h. After cooling the mixture to room
temperature the precipitate was isolated by centrifugation. The product was washed with DMF
2×10 mL) and EtOH (3×10 mL) and dried under reduced pressure (80 C, 3h).
2
3
4
) (1.6 g, 6.8 mmol) in
̊
6
0
̊
̊
(
̊
Ultrasound-Assisted Synthesis of UiO-66-NH
Briefly, acetic acid (11.4 mL, 3.4 mmol) was added to a solution of Zr(NO
DMF (150 mL) and stirred at 55 C. Then a solution of 2-aminoterephthalic acid (1.2 g, 6.8 mmol)
in 50 mL DMF and 0.5 mL water were added to the solution and the final mixture was sonicated at
C for 60 minutes. After cooling the mixture to room temperature the precipitate was isolated by
centrifugation. The product was washed with DMF (2×10 mL) and EtOH (3×10 mL) and dried
under reduced pressure (80 C, 3h).
2
3
4
) (1.6 g, 6.8 mmol) in
̊
60 ̊
̊
17

Synthesis of UiO-66-NH-SO H
3
The as-synthesized UiO-66-NH
2
(1.77 g, 1.0 mmol) was thoroughly suspended in CHCl (30 ml),
3
and under gradually stirring the Chlorosulfonic acid (0.234 g, 2.0 mmol) was added and remained
for 12 h at 25 °C. By the end of period, the supernatant was centrifuged and the obtained crystals
was washed with CHCl
SO H catalyst.
3
and dried under reduced pressure at 40 °C to obtain activated UiO-66-NH-
3
General Procedure for the Synthesis of 1,2-Disubstituted Benzimidazoleby using UiO-66-NH-
SO
Activated UiO-66-NH-SO
3
H
3
H (0.01g) was added to a solution of aldehyde (1 mmol) and o-
Phenylenediamine (1.2 mmol) in EtOH (3 mL). The reaction mixture was stirred at room
temperature and progress of the reaction was monitored by TLC. After completion of the reaction,
the suspension was centrifuged for separation of the catalyst. Then the the solvent was evaporated
and the product was extracted with CHCl (3×10 mL), dried over anhydrous sodium sulfate and
3
concentrated under vacuum to give desired product.
General Procedure for the Reductive Amination
NaBH
NH-SO
Progress of the reaction was monitored by TLC. After completion, the catalyst was easily separated
by centrifugation. Then, crude product was washed with H O (2×10 mL) and dried over anhydrous
4
(2 mmol) was added to a mixture of aldehyde (1.0 mmol), amine (1.0 mmol) and UiO-66-
3
H (0.01 g) in CH CN (3 mL) and the reaction mixture was stirred at room temperature.
3
2
sodium sulfate. After removal of the solvent, the pure product was obtained and more purified by
recrystallization.
Conclusion
In summary, we synthesized the UiO-66-NH-SO H through Urtrasound-assisted method following
3
by covalent post synthetic modification approach. After characterization of the catalyst, its activity
was investigated toward the benzimidazole formation and reductive amination reaction at room
18

temperature. The obtained products with high yields and short reaction time in each reaction,
strongly confirmed that the catalyst could serve as an efficient Brønsted acid heterogeneous
catalyst. Also the catalyst could be reused at least five cycles without losing its catalytic activity.
Acknowledgements
The authors thank Shahid Chamran University of Ahvaz for financial support (Grant No.
3
1400.02.3.95).
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21

Graphical Abstract
22

Highlights
-
-
-
The nanoscale UiO-66-NH has been synthesized by an ultrasound-assisted (US)
method and compared with the conventional-heating method.
2
UiO-66-NH-SO H as Brønsted acid heterogeneous catalyst through Post-
3
synthetic modification of UiO-66
UiO-66-NH-SO H as an excellent Brønsted acid heterogeneous catalyst for
3
benzimidazole formation and reductive amination reaction at room temperature.
23