Design and synthesis of micro-meso-macroporous polymers with versatile active sites and excellent activities in the production of biofuels and fine chemicals

Article abstract of DOI:10.1039/c6gc02237e

Micro-meso-macroporous polymers (MOPs) grafted with versatile functional groups, such as sulfonate, amine, triazole, pyridine, strong acidic ionic liquids and triphenylphosphine, were synthesized by in situ cross-linking of different functional molecules with 1,4-bis(chloromethyl)benzene in the presence of Lewis acid catalysts without using additional templates. The resultant hyper-cross-linked nanoporous polymers show unique characteristics such as large BET surface areas (up to 1523 m² g^-1), abundant micro-meso-macropores (4.5-131 nm), and tunable and versatile active sites (acid, base and palladium). These functional polymers exhibit excellent activities and good reusability in biomass conversions, cross-coupling reactions and condensation. The catalytic activities are much better than those of various conventional catalysts such as H₃PW₁₂O₄₀, SBA-15-SO₃H, Amberlyst 15, and mesoporous H-ZSM-5 Pd/C and even as comparable as those of homogeneous H₂SO₄ and HCl in the depolymerization of crystalline cellulose into fine chemicals and towards transesterification to biodiesel. This work highlights a low cost route to the synthesis of solid catalysts based on functional nanoporous polymers for catalyzing the production of clean biofuels and fine chemicals.

Full text of DOI:10.1039/c6gc02237e

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ARTICLE
Design and synthesis of micro-meso-macroporous polymers with
versatile active sites and excellent activities in production of
biofuels and fine chemicals
Received 00th January 20xx,
Accepted 00th January 20xx
a,b
a
a
a
d
b,c
Fujian Liu*, Chen Liu , Weiping Kong , Chenze Qi , Anmin Zheng* and Sheng Dai*
DOI: 10.1039/x0xx00000x
www.rsc.org/
Micro-meso-macroporous polymers (MOPs) grafted with versatile functional groups such as sulfonate, amine, triazole,
pyridine, strong acidic ionic liquids and triphenylphosphine, were synthesized from in-situ cross linking of different
functional molecules with 1,4-bis(chloromethyl)benzene in the presence of Lewis acids catalysts without using additional
templates. The resultant hyper-cross-linked nanoporous polymers show unique characteristics such as large BET surface
2
areas (up to 1523m /g), abundant micro-meso-macropores (4.5-131nm), and tunable and versatile active sites (acid, base
and palladium). These functional polymers exhibit excellent activities and good reusability in biomass conversions, cross-
coupling reactions and condensation. The catalytic activities are much better than those of various conventional catalysts
such as H
3
PW12O
40, SBA-15-SO
3
H, Amberlyst 15, mesoporous H-ZSM-5 Pd/C and even as comparable as those of
homogeneous H
2
4
SO and HCl in depolymerization of crystalline cellulose into fine chemicals and towards
transesterification to biodiesel. This work highlights a low cost route to the synthesis of solid catalysts based on functional
nanoporous polymers for catalyzing the production of clean biofuels and fine chemicals.
1
-11,13
blocks without using additional templates.
The resultant
Introduction
microporous polymers were mainly used for gas adsorption and
1
-11,13,25
storage or for small-molecule catalysis.
However, the solo
Porous organic polymers (POPs) act as a class of state-of-the-art
materials that have attracted extensive attentions because of their
wide applications in the areas of adsorption, water treatment, gas
microporous structures in these materials severely limit their
responses to bulky molecules, which usually are present in
biological systems, pharmaceutical processes, and heterogeneous
1
-13
storage and separation, and heterogeneous catalysis. In general,
nanopores in POPs can be generated via the introduction of
porogens during the curing processes. Various porogens can be
26
catalysis. In addition, relatively high synthetic cost also limits the
synthesis of these microporous polymers on a large scale.
POPs materials with combined micro-mesopores exhibit unique
characteristics such as large BET surface areas and pore volumes,
enhanced accessibility of catalytically active sites, much decreased
used, such as SiO
2
spherical hard templates or surfactant soft
1
4-19
templates.
They result in the formation of controllable, ordered
nanopores in polymers such as phenol-formaldehyde resin,
exhibiting excellent properties in adsorption, separation and
8
,9
diffusion limitation for various guest molecules, which strongly
enhance their abilities of resistance to carbon deposition and
responses to bulky molecules in the area of heterogeneous
1
7-21
heterogeneous catalysis.
However, the use of these nanoporous
polymers in industry is limited because of the difficulty of removing
8,9,17-23
6,22- catalysis.
1
Notably, catalytic processes (especially biomass
the templates and the complexity of the synthetic procedures.
2
4
conversions) are very important tools for the synthesis of various
useful chemicals and biofuels in industry. Recently, Xiao and
coworkers have successfully synthesized a series of nanoporous
polymer-based solid catalysts with adjustable nanopore sizes (3–
An alternative way of synthesizing porous organic polymers, such
as crystalline covalent-organic frameworks (COFs), porous polymer
networks (PPNs), porous aromatic frameworks (PAFs), polymer of
intrinsic microporosity (PIMs) and conjugated microporous
polymers was achieved by co-condensing small-molecule building
5
0nm), controllable surface wettability and active sites. They
showed excellent activities and good reusability for catalyzing
conversion of low cost biomass into clean biofuels and fine
a.
8,9
College of Chemistry and Chemical Engineering, Shaoxing University, Shaoxing,
3
chemicals.
These functional porous organic polymers were
12000 (China). E-mail: fjliu@usx.edu.cn.
Department of Chemistry, University of Tennessee, Knoxville TN 37996 (USA).
Chemical Sciences Division, Oak Ridge National Laboratory, Oak Ridge TN 37831
synthesized via copolymerization of divinylbenzene with functional
monomers under high-temperature solvothermal conditions in the
b.
c.
8
,9,22
(
USA). E-mail: dais@ornl.gov
absence of any templates.
However, the energy consumption of
d.
National Center for Magnetic Resonance in Wuhan, State Key Laboratory of
Magnetic Resonance and Atomic and Molecular Physics, Wuhan Institute of
Physics and Mathematics, Wuhan 430071 (China). Email: zhenganm@wipm.ac.cn
high-temperature hydrothermal or solvothermal technologies, and
safety concerns associated with them, limit their use in the
preparation of functional porous organic polymers with enhanced
Electronic Supplementary Information (ESI) available: [details of any
supplementary information available should be included here]. See
DOI: 10.1039/x0xx00000x
2
7
nanopore sizes in industry.
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Up to now, it remains a challenge to find a template free Notably, the volume ratios of micro/meso/macropores were
approach to synthesize porous polymer based solid catalysts distributed in the range of 1/2.7~5.7/0.2~2.7 (Table 1). These
with combined micro-meso-macropores, tunable and versatile results suggest functional MOP materials with large BET surface
1
,28
functional groups under rather mild conditions.
Herein, we
report a generalized, template-free route to the synthesis of
multiple groups functionalized, catalytically active micro-meso-
macroporous polymers (MOPs) with abundant nanopores and
tunable active sites. This route was achieved by the direct
alkylation of various functional molecules with 1,4-
bis(chloromethyl)benzene catalyzed by Lewis acids such as
1
400
a
b
c
d
e
f
1200
1
1000
4 4
SnCl and TiCl under normal pressure and low temperatures.
8
00
To the best of our knowledge, there is still few reports on
targeted design and synthesis of micro-meso-macroporous
polymers with versatile and tunable active sites. The resultant
hyper-cross-linked porous polymers showed abundant micro-
meso-macropores, very large BET surface areas, excellent
thermal stabilities, and good wettability for various organic
substrates. It is noteworthy that various functional
molecules—such as resorcinol, triazole, amine, pyridine,
ethylbenzene, sulfonate, imidazole, and triphenylphosphine—
were directly cross-linked to produce correspondingly active
0
.1
600
400
a
b
c
d
e
f
2
00
0.01
0
.0
0.2
0.4
0.6
0.8
1.0
10
100
Relative pressure (p/p0)
Pore diameter (nm)
nanoporous polymers. These nanoporous polymers could be Fig. 1. N
2
adsorption-desorption isotherms and pore size distribution of (a) MOP-
used as highly efficient supports for grafting with different P(Ph)
3
, (b) MOP-aniline, (c) MOP-phloroglucinol, (d) MOP-ethylbenzene, (e) MOP-
active sites such as sulfonic acid, strong acid ionic liquid, bases, pyridine, and (f) MOP-triazole.
or palladium. The resultant nanoporous polymers could be
used as highly efficient and reusable solid catalysts in
areas and abundant micro-meso-macropores were successfully
condensation, cross coupling reactions and biomass
conversions, such as reactions toward transesterification to
biodiesel, depolymerization of crystalline cellulose into fine
chemicals. This work develops a facile, cost-effective approach
to the synthesis of micro-meso-macroporous polymeric solid
catalysts with abundant nanopores, tunable and versatile
active sites, and excellent catalytic activities for catalyzing
conversion of low cost biomass into renewable biofuels and
useful chemicals, which are the hot topics in the area of green
and sustainable chemistry.
prepared in this work. The nanoporous structures, amount of
Table 1. The textural parameters and active sites contents of various samples.
f
Samples
Contents of
active sites
S
BET
V
t
Volume
p
D (nm)
2
3
e
(m /g)
(cm /g)
ratios
d
d
(mmol/g)
b
MOP-[C
4
mim]Cl
0.14
1523
1265
1238
1189
987
2.86
1.94
1.96
1.77
1.62
1.08
1.60
1.27
0.78
1/3.9/2.3
1/4.5/0.9
1/4.3/1.1
1/5.7/0.6
1/4.1/1.5
1/3.9/0.3
1/2.7/2.7
1/4.3/0.2
1/3.8/0.8
31.6&131
24.3
b
MOP-triazole
0.18
b
MOP-imidazole
0.26
16.7
MOP-P(Ph)
3
-
22.9
c
MOP-P(Ph) -Pd
3
1.08
21.8
Results and discussion
MOP-ethylbenzene
-
-
956
9.6
a
MOP-benzene
926
67.5&116.8
26.2
Fig. 1 and Fig. S1 show N
2
isotherms and pore size distributions
, MOP-
b
MOP-pyridine
2.20
868
of various groups of functionalized MOPs: MOP-P(Ph)
3
b
MOP-ethylbenzene-
1.52
580
7.5
aniline, MOP-phloroglucinol, MOP-ethylbenzene, MOP-pyridine,
MOP-triazole, and MOP-benzene. MOP-benzene exhibits a type-IV
isotherm with a steep increase in adsorption at relative pressures
ranging from 0.85 to 0.975, which results in hierarchical nanopore
sizes centered at around 67.5 and 116.8nm. These values indicate
the formation of abundant macropores in the sample (Fig. S1 and
Table 1). On the other hand, various functional groups
functionalized MOPs exhibit typical type-IV isotherms with steep
3
SO H
b
MOP-benzenesulfonic
acid
1.21
472
317
217
0.81
0.31
0.31
1/3.3/0.9
1/4.0/0.8
1/3.5/0.8
28.3
4.5
b
MOP-phloroglucinol-
1.95
SO H
3
b
MOP-aniline
2.35
22.9
a
b
Synthesized from self cross linking of 1,4-bis(chloromethyl)benzene. Nitrogen
c
and sulfur contents were measured by elemental analysis. Pd contents was
increases at a relative pressure of 0.4<P/P
0
<0.975, which results in
d
measured by ICP. Single point total pore volumes were calculated at the
nanopore sizes ranging from 4.5 to 31.6 nm (Fig. 1), indicating
e
8,9
relative pressure of 0.99. Volume ratios of micro/meso/macropores.
formation of abundant mesopores in these samples.
Correspondingly, the BET surface areas and pore volumes of these
Micropore: 0–2 nm, mesopore: 2–50 nm, macropore: 50–300 nm; Micropore
volume was calculated by t-plot method, mesopore and macropore volume
2
3
samples ranged from 217 to 1523m /g and 0.31 to 2.86cm /g (Table
), respectively. Besides mesopores, certain amounts of micropores
and macropores could also be observed in these samples (Fig.1).
f
were calculated by BJH model; Pore size distribution estimated from BJH
1
model.
2
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micropores, mesopores and macropores may be adjusted through micro-meso-macropores in MOPs such as MOP-ethylbenzene-SO
changing the synthetic solvents, functional molecules and their MOP-pyridine, MOP-P(Ph) -Pd, MOP-triazole, MOP-aniline, and
Meanwhile, the MOP-benzene (Fig. S4). On the other hand, X-ray photoelectron
concentrations of functional groups in MOP materials ranged from spectroscopy (XPS) results further confirm that various active sites
.14 to ~2.35mmol/g (Table 1), further confirming that functional such as sulfonic acid, amine, and Pd have been successfully
molecules with different contents were successfully grafted onto introduced into MOPs materials. For instance, MOP-ethylbenzene-
the network of MOPs. The resulting MOP materials were used as SO H showed the signals of C1s, S2p, and O1s, MOP-aniline showed
3
H,
3
8
,9,22
ratio to cross linker during synthetic processes.
0
3
effective supports for palladium, sulfonic groups, and acidic ionic the signals of C1s and N1s, and MOP-P(Ph)
liquids, which still showed large BET surface areas and abundant of C1s, P2p and Pd3d (Fig. S5).
3
-Pd showed the signals
1
3
nanopores (Table1). Notably, it is possible that the loading of SO
groups and palladium active sites might block the nanopores and spectra of MOP-P(Ph)
increase weight of the samples, which would partially reduce the which were measured to reveal the cross-linked structures of the
surface areas and pore volumes of the samples (Table 1). samples. Notably, the band at around 18ppm was assigned to the
Fig. 2a shows scanning electron microscope (SEM) image of methyl end group in the cross-linker 1,4-bis(chloromethyl)benzene,
MOP-ethylbenzene-SO H, exhibiting rough surface characteristics and the bands at around 37, 42, and 45ppm were assigned to the
with abundant porosities and cavities, which were distributed on methylene linker in the 1,4-bis(chloromethyl)benzene found in
the mesoporous and macroporous scales, in agreement with N these samples, which were confined in different chemical
3
H
Fig. 3 shows C CP/MAS nuclear magnetic resonance (NMR)
3
, MOP-phloroglucinol, and MOP-pyridine,
3
2
adsorption-desorption isotherms results; similar abundant environments. The band at 129 and 137ppm was assigned to
porosities were also found in other MOPs samples (Fig. S2). aromatic carbon in cross-linked 1,4-bis(chloromethyl)benzene
1
8,28
Scanning transmission electron microscope (STEM) images further building blocks.
confirm that rough surfaces and abundant meso-macropores in
3
For the MOP-P(Ph) sample, the bands at 129
MOP-ethylbenzene-SO
3
H, and carbon, sulfur active sites were
homogeneously dispersed in the sample. Meanwhile, MOP-P(Ph)
3
-
Pd also showed abundant nanopores, and C, P, and Pd with
homogeneously dispersed in the sample. Similar results were found
c
b
a
3
in MOP-triazole and MOP-P(Ph) (Fig. S3), which confirms that
various functional groups were successfully introduced into MOP-
type materials. Moreover, TEM images further confirmed abundant
a
b
1
3
Fig. 3. C solid state nuclear magnetic resonance (NMR) spectra of (a) MOP-
P(Ph) , (b) MOP-phloroglucinol, and (c) MOP-pyridine. Asterisks denote spinning
3
sidebands.
and 137 ppm were assigned to aromatic carbon and unsubstituted
aromatic carbon in both cross-linked 1,4-bis(chloromethyl)benzene
1
8,29
31
c
Carbon 91.2%
d
Sulfur 5.6%
e
and the P(Ph)
state NMR spectrum indicated the signal of the P(Ph)
an oxidation state (Fig. S6). For MOP-phloroglucinol, the band at
10 ppm was assigned to substituted aromatic carbon in
building blocks.
On the other hand, a P solid
3
3
group with
1
phloroglucinol; and the band at around 155 ppm was assigned to
carbon atoms connected with the hydroxyl group in phloroglucinol.
Similar results were also observed for MOP-pyridine, except for the
characteristic peaks of the 1,4-bis(chloromethyl)benzene cross-
linker. The band at 146 ppm was assigned to carbon atoms
connected with nitrogen in the pyridine ring, and the band at 165
ppm was assigned to substituted carbon by the 1,4-
bis(chloromethyl)benzene cross-linker in the pyridine ring. As with
f
Carbon 90.3%
g
Phosphorus 3.4%
h
Palladium 1.6%
3
MOP-P(Ph) and MOP-phloroglucinol, the new band at around 61
ppm was assigned to the methylene linker directly connected with
3
H. nitrogen atoms in the pyridine ring. The combination of elemental
Fig. 2. (a) Scanning electron microscope (SEM) image of MOP-ethylbenzene-SO
(
b) Scanning transmission electron microscope (STEM) image, (c and d) element analysis, XPS spectra, energy-dispersive x-ray spectroscopy, and
maps and contents of MOP-ethylbenzene-SO
3
H. (e-h) STEM image, element maps solid state NMR results enables us to conclude that various
and contents of MOP-P(Ph)
3
-Pd. The scale bars of (a) is 200 nm, and (b-h) are 1 functional groups were successfully grafted onto MOP networks via
alkylation induced hyper-cross-linking of various functional
µm.
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a
Table 2 Catalytic data in transesterification of sunflower oil with methanol over various acid catalysts
Catalysts
Yields of methyl esters (%)
Methyl
Methyl
Methyl
Methyl
Methyl
Methyl 11-
Methyldocos Methyltetra
palmitate
stearate
oleate (C18:2
)
linoleate
arachidate
eicosenoate
anoate
cosanoate
(C
16:0
)
(C18:1
)
(C18:3
)
(C20:0
)
(C20:1
)
(C22:0
)
(C24:0)
MOP-aniline-[C
MOP-phloroglucinol-SO
MOP-ethylbenzene-SO
4
][SO
3
CF
3
]
92.8
87.4
85.4
94.2
82.8
76.8
95.6
80.5
79.3
96.3
89.1
78.7
80.6
89.2
86.4
83.4
90.4
85.3
78.9
91.8
81.9
79.7
3
H
82.3
83.6
3
H
b
MOP-ethylbenzene-SO
3
H
84.5
84.2
83.7
84.3
60.2
57.9
50.7
76.3
76.5
76.1
75.4
65.4
57.3
48.2
78.6
77.4
77.1
77.6
59.1
54.8
42.6
82.7
81.4
79.1
79.2
62.3
53.3
46.5
79.2
78.8
78.3
78.9
55.4
43.5
28.3
82.5
81.2
81.7
80.1
62.3
38.9
29.8
79.2
77.8
78.3
77.1
68.9
43.2
36.5
79.1
78.4
77.8
76.8
54.8
40.7
14.2
c
MOP-ethylbenzene-SO
3
H
d
MOP-ethylbenzene-SO
3
H
e
MOP-ethylbenzene-SO
3
H
3 40
H PW12O
SBA-15-SO
3
H
Amberlyst 15
a
1
mL sunflower oil; 2.5 mL methanol; 0.1 g catalyst; reaction temperature 80°C; reaction time 16 h. The catalytic activity of the catalysts was characterized
quantitatively by the conversion of fatty acid methyl esters (FAME, Y %) which was calculated as follows: Yield=(M /M )×100 %, where M and M are the number
is the number of moles of FAME catalyzed by 0.1 g of H SO in 24 h, performed at
D
T
D
T
of moles of each FAME produced and expected, respectively. In this section, M
T
2
4
b
c
d
e
8
0°C with the same content of feedstock as that of MOP solid acids. The 2nd, 3rd, 4th and 5th recycles in transesterification of sunflower oil with methanol.
3 3 3
molecules with 1,4-bis(chloromethyl)benzene. MOPs exhibit ethylbenzene-SO H, (c) H PW12O40, (d) SBA-15-SO H, (e) Amberlyst 15, and (f)
superior thermal stabilities, and the decomposition temperatures of mesoporous H-ZSM-5.
both functional groups and networks in MOPs were higher than 300
and 500°C respectively (Fig. S7).
Fig. 4 shows the transesterification of tripalmitin with methanol of C16:0 catalyzed by MOP solid acids increased to 92.6 and 86.7%,
to produce biodiesel over various catalysts. MOP-based solid acids whereas heteropolyacid, SBA-15-SO H, Amberlyst 15, and
3
exhibited much improved catalytic activities in comparison with mesoporous H-ZSM-5 still gave relatively low yields of biodiesel at
H PW O , SBA-15-SO H, Amberlyst 15, and mesoporous H-ZSM-5. 68.6, 48.4, 40.1, and 10.9%, respectively.
3
12 40
3
The yields of biodiesel (C16:0) catalyzed by MOP-aniline-[C ][SO CF ]
Besides purified oil, MOP-based solid acids were also very active
4
3
3
and MOP-ethylbenzene-SO H were 67.9 and 63.2% after 8h of for catalyzing the conversion of sunflower oil into biodiesel; the
3
incubation, much better than the yields of heteropolyacid (47.8%), main biodiesel products were methyl palmitate (C16:0), methyl
SBA-15-SO H (37.6%), Amberlyst 15 (29.7%) and mesoporous H- stearate (C18:1), methyl oleate (C18:2), methyl linoleate (C18:3),
3
methyl arachidate (C20:0), 11-eicosenoic methyl (C20:1),
a
b
90
80
70
60
50
40
30
20
10
0
methyldocosanoate (C22:0), and methyltetracosanoate (C24:0).
Notably, the yields of biodiesel [C16:0 (85.4~92.8%), C18:1
(
(
(
76.8~94.2%), C18:2 (79.3~95.6%), C18:3 (82.3~96.3%), C20:0
78.7~89.1%), C20:1 (83.4~89.2%), C22:0 (78.9~90.4%) and C24:0
c
79.7~91.8%)] catalyzed by MOP-phloroglucinol-SO H, MOP-
3
d
e
ethylbenzene-SO H, and MOP-aniline-[C ][SO CF ] were much
3
4
3
3
higher than the yields of H PW O , Amberlyst-15, and SBA-15-
3
12 40
SO H (as presented in Table 2). Compared with sulfonic group
3
grafted MOPs, the enhanced activity of MOP-aniline-[C ][SO CF ]
4
3
3
should be attributed to its unique strong ionic liquid active site,
f
9,22
which was very active for catalyzing biomass conversions.
In
addition, MOPs solid acids showed very good recyclability, and no
obvious decrease was seen in biodiesel yields catalyzed by MOP-
0
2
4
6
8
10
12
14
16
Reaction time (h)
ethylbenzene-SO H recycled for five times (Table 2). The excellent
3
ZSM-5 (7.8%). Further prolong the reaction time to 14 h, the yields
catalytic activities and good reusability found in MOP-based solid
acids can be attributed to their large BET surface areas, abundant
Fig. 4. Dependences of catalytic activities on time in transesterification of nanopores, good stabilities, strong and tunable acid sites. Abundant
tripalmitin with methanol catalyzed by (a) MOP-aniline-[C
4
3
][SO CF
3
], (b) MOP- nanopores could strongly enhance the mass transfer during various
4
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be a green, low-cost way of transforming biomass into important
intermediates and useful chemicals. Notably, the catalytic activities
Table 3 Yields of sugars and dehydration products in the depolymerization
a
of Avicel catalyzed by various solid acids .
3 4 3 3
of MOP-ethylbenzene-SO H and MOP-aniline-[C ][SO CF ] were
c
Samples
Glucose
Cellobiose
HMF yield TRS (%)
much better than those of Amberlyst 15 and even homogeneous
HCl catalysts (Table 3). For example, the total reduced sugar (TRS)
b
b
b
yield (%)
15.2
yield (%)
(%)
Amberlyst 15
16.8
26.3
27.1
2.9
9.8
8.9
39.7
85.6
83.7
3 4 3 3
values of MOP-ethylbenzene-SO H and MOP-aniline-[C ][SO CF ]
d
HCl
40.7
were 83.7 and 90.4%, and the TRS value of HCl was 85.6%. On the
other hand, the TRS value of Amberlyst 15 was as low as 39.7%. The
main products were glucose, fructose, and HMF; and the yields of
those products catalyzed by MOP solid acids were higher than
yields catalyzed by HCl and much higher than those catalyzed by
Amberlyst 15 (Table 3).
MOP-ethylbenzene-
38.8
SO
MOP-aniline-
][SO CF
3
H
42.6
32.9
10.3
90.4
[C
4
3
3
]
a
0
.1g of Avicel, 1.5g of [C
4
mim]Cl ionic liquid, and 0.5mL of DMSO mixed
MOPs could also be used as efficient support for loading with
palladium, which are still used as highly efficient and reusable
catalysts in cross-coupling reactions (Table 4). Cross coupling
reactions such as Suzuki and Heck reactions could be acted as an
effective tool for the synthesis of useful chemicals in the areas of
pharmaceutical process and organic synthesis. Notably, MOP-
b
solvents, 20mg of catalyst; the reaction was performed at 100°C for 5h.
c
d
Measured by HPLC method. Measured by DNS method. The same number
of acidic sites as in MOP-ethylbenzene-SO H.
3
catalytic reactions, strong and tunable acid sites could effectively
activate reactants. The above characteristics result in the synergistic
effect, which leads to the higher catalytic performances of the
MOP-based catalysts.
P(Ph)
was employed as substrate, the yields of products was nearly 100%
within 1h, even after being recycled for 5 times, MOP-P(Ph) -Pd still
exhibited excellent activity, giving the products yield at 99.2%.
Similar high activity in MOP-P(Ph) -Pd could also be found in Heck
3
-Pd was very active in these reactions. When iodobenzene
3
We further investigated the catalytic performances of MOP-
based solid acids in the depolymerization of crystalline cellulose
into sugars and hydroxymethylfurfural (HMF), which is thought to
3
reaction, in the reactions of iodobenzene with styrene and n-butyl
acrylate, the yields of products were up to 99.8 and 98.7%,
3
respectively. Except for iodobenzene, MOP-P(Ph) -Pd was also very
3
Table 4 Catalytic data of MOP-P(Ph) -Pd solid catalyst in Heck and Suzuki cross-
active for catalyzing cross coupling of bromobenzene, after 5h
reaction, the yields of products in Heck and Suzuki coupling
reactions were 96.5 and 98.3%, respectively. Further expand the
coupling reactions with different substrates.
O
O
4 9
n-C H
R
R
X
X
+
MOP-P(Ph)
3
-Pd
O
n-C
4
H
9
3
substrate to chlorobenzene, MOP-P(Ph) -Pd still gives relative high
O
R
R
product yield as high as 68.5%.
MOP-P(Ph)
3
-Pd
Furthermore, MOPs could also be grafted with basic sites such
as amine and pyridine, which still can be used as highly efficient and
reusable nanoporous solid bases in Knoevenagel condensation. The
activities of MOP solid base were much better than that of basic
resin of Amberlite 400 (As presented in Table 5). For instance, in the
reaction of benzaldehyde with malononitrile, the yield of the
+
HO
MOP-P(Ph) -Pd
3
R
X
+
B
R
HO
Samples
Substrate 1
Substrate 2
Yields (%)
99.8
O
Me
I
n-C4H9
O
MOP-P(Ph)
MOP-P(Ph)
MOP-P(Ph)
MOP-P(Ph)
MOP-P(Ph)
3
3
3
3
3
-Pd
-Pd
-Pd
-Pd
-Pd
Table 5 The catalytic activities in Knoevenagel condensation over various
O
I
OMe
4
n-C H
9
99.5
samples.
O
Me
I
I
98.7
Catalysts
MOP-Pyridine
MOP-Aniline
Substrates
Products
Yields (%)
>99.5
>99.5
98.5
OMe
99.2
NC
O
CN
HO
Me
Me
I
I
B
~100
99.2
HO
HO
NC
O
a
CN
MOP-P(Ph)
3
-Pd
B
B
HO
HO
O
CN
CN
b
Palladium acetate
MOP-aniline-Pd
Me
Me
I
99.6
HO
MOP-Pyridine
MOP-Aniline
OH
O
OH
O
Br
CN
CN
4
n-C H
9
96.5
O
HO
OH
NC
97.8
OH
O
Br
Cl
Cl
B
MOP-P(Ph)
MOP-P(Ph)
3
3
-Pd
-Pd
Me
Me
Me
98.3
HO
HO
CN
CN
Amberlite 400-OH
64.6
B
B
68.5
HO
HO
NC
O
b
a
Palladium acetate
29.3
MOP-Aniline
99.1
HO
a
b
a
th
The sample has been recycled for five times. The same number of active site
The
5
recycles in Knoevenagel condensation of benzaldehyde with
as that of MOP-P(Ph) -Pd.
3
malononitrile.
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product catalyzed by MOP-Pyridine and MOP-Aniline were higher methanol, sunflower oil, dodecane were obtained from
than 99.5% for 1h reaction, while Amberlite-400 gave very low yield Sinopharm Chemical Reagents Co. Ltd.
at 64.6%. In addition, even after being recycled for 5 times, MOP-
aniline still gave the product yield as high as 99.1%, indicating its Synthesis of samples
very good reusability. Similar results could also be observed in other
substrate such as salicylaldehyde (Table 5). The excellent catalytic
MOPs were synthesized by the alkylation cross-linking of
functional molecules with 1,4-
activities found in MOPs solid catalysts are attributable to their different
large BET surface areas, abundant micro-meso-macropores, bis(chloromethyl)benzene. In a typical run for the synthesis of
controllable surface wettability, tunable and homogeneous triphenylphosphine functionalized nanoporous polymers, 1.0g
dispersion of active centers, which strongly enhance accessibility of of 1,4-bis(chloromethyl)benzene was dispersed into 15 mL of
active sites to various substrates. This work develops an efficient 1,2-dichloroethane solvent, followed by the addition of 3 mL of
4 4
and generalized approach to targeted synthesis of multifunctional SnCl or TiCl at 0°C under vigorous stirring. Then, 0.8 g of
porous polymers based solid catalysts that offer great opportunity triphenylphosphine was added into the mixture, and alkylation
for wide application of MOPs to catalyze the production of biofuels was performed at 65–75°C for 24h under an insert gas. The
and fine chemicals with different molecule sizes.
resulting hyper-cross-linked sample was washed with a hot
ethanol–HCl mixed solution several times to remove the Lewis
acid catalysts and then dried under vacuum at 60°C for 24h.
Conclusions
The final samples were denoted as MOP-P(Ph)
functional groups can be introduced into MOPs via a similar
procedure. After good dispersion of 1,4-
bis(chloromethyl)benzene and SnCl into a 1,2-dichloroethane
3
. Other
In summary, this work develops a facile, generalized approach
to the targeted synthesis of the micro-meso-macroporous
polymers functionalized with various functional groups, which
was achieved via one-step alkylation of functional small
molecules with 1,4-bis(chloromethyl)benzene without using
organic templates. MOPs have large BET surface areas,
abundant micro-meso-macropores, tunable and versatile
active sites. The above characteristics result in their excellent
activities and reusabilities for catalyzing conversion of low cost
biomass into green and renewable biofuels and fine chemicals,
which are very important for their wide applications in the
areas of green and sustainable chemistry.
4
solvent, a certain content of functional small molecules—such
as phloroglucinol, triazole, aniline, pyridine, ethylbenzene, p-
4
styrene sulfonate, imidazole, and [C mim]Cl—were added into
the mixture; and alkylation-induced cross-linking was
accomplished by heating the mixture at 65–75°C for 24h. Self
cross-linking of 1,4-bis(chloromethyl)benzene can also be
accomplished using similar procedures without adding other
functional molecules, which results in MOPs with pure
benzene
networks.
Typically,
1.8g
of
1,4-
bis(chloromethyl)benzene was dispersed into 15mL of 1,2-
dichloroethane solvent, followed by the addition of 3mL of
Acknowledgements
4 4
SnCl or TiCl as the catalyst at 0°C under vigorous stirring.
Then self-alkylation of 1,4-bis(chloromethyl)benzene was
performed at 65–75°C for 24h. The resulting hierarchical
nanoporous polymer was obtained by washing with an
abundant amount of a hot ethanol–HCl mixed solution several
times, and drying under vacuum at 60°C for 24h. The sample
was designated as MOP-benzene.
FL and AZ was supported by the National Natural Science
Foundation of China (21573150, 21203122, 21522310,
21473244), and the Natural Science Foundation of Zhejiang
Province (LY15B030002). SD was supported by the Division of
Chemical Sciences, Geosciences and Biosciences, Office of
Basic Energy Sciences, U.S. Department of Energy.
Palladium-loaded MOPs were synthesized by stirring
nanoporous polymers into a solution containing methanol and
weight-quantitative palladium acetate, based on the unique
interactions between palladium species and functional groups
Experimental
Chemical and reagents
in MOPs. As a typical run for synthesis of MOP-P(Ph)
of MOP-P(Ph) was added into a solution containing 40mL of
methanol and 0.01g of palladium acetate. After the mixture
was stirred for 12h under refluxing (65°C), MOP-P(Ph) -Pd was
3
-Pd, 1.0g
3
All reagents were of analytical grade and used as
purchased without further purification. Microcrystalline
3
cellulose (Avicel), 1-n-butyl-3-methylimidazolium ([C
phloroglucinol, triazole, aniline, pyridine,
4
mim]Cl),
1,4-
obtained via vacuum distillation at 45°C to remove the solvent,
washing with a large amount of dimethyl ether, and drying at
bis(chloromethyl)benzene, ethylbenzene, p-styrene sulfonate,
imidazole, triphenylphosphine, palladium acetate, and
tripalmitin were purchased from Sigma-Aldrich Co.
6
0°C for 12h. In addition, other nitrogen-doped MOPs, such as
MOP-pyridine and MOP-imidazole, were used as effective
supports for loading with palladium species. In comparison,
palladium-loaded ordered mesoporous silica (SBA-15-Pd) and
activated carbon (activated carbon-Pd) were synthesized by
4 4
Dichloroethane, SnCl , TiCl , ethanol, THF, iodobenzene, n-
butyl acrylate, salicylaldehyde, benzaldehyde, malononitrile,
styrene, dichloromethane, N,N-Dimethylformamide (DMF),
similar procedures to that used for MOP-P(Ph)
Sulfonic groups functionalized MOP could be synthesized
from sulfonation of MOP supports with HSO Cl in presence of
3
-Pd.
3 2 4
1,3-propanesultone, HCl, HSO Cl, H SO , DMSO, ethanol,
3
6
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ARTICLE
dichloromethane solvent at 0°C; Typically, 1.0g of MOP Auriga Crossbeam field emission scanning electron microscope
1
mixture contains 40mL at an acceleration voltage of 5kV. The C solid state NMR
3
samples was added into
dichloromethane and 8mL HSO
a
3
Cl, after stirring of the mixture experiments were carried out on a Varian Infinityplus-300
at 0°C for 24h, the reaction mixture was dispersed into 300mL spectrometer at resonance frequencies of 299.78 and
1
13
of water. Finally, the product was obtained from filtering, 75.38MHz for H and C, respectively. The experiments were
washing with a large amount of water until neutral, stirring in recorded using a 4mm double-resonance MAS probe at a
1
3
dioxane, and drying at 80°C. MOP-benzene, MOP- spinning rate of 10 kHz. Pulse width (π/2) for C was
phloroglucinol and MOP-ethylbenzene could be used as measured to be 4.1 μs. A contact time of 4 ms and a recycle
1
delay of 3s were used for the H- C CP/MAS measurement.
13
suitable supports for grafting with sulfonic group.
1
3
Sulfonic group functionalized MOP can also be synthesized The chemical shift of C was externally referenced to
from cross linking of sodium benzenesulfonate by using 1,4- hexamethylbenzene.
bis(chloromethyl)benzene. Typically, certain contents of 1,4-
4
bis(chloromethyl)benzene and SnCl were dissolved into 1,2- Catalytic reactions
dichloroethane solvent, then sodium benzenesulfonate
functional molecules were added into the mixture, the Suzuki reaction
alkylation cross linking was performed at 65-75°C for 24h
0.25mmol of 4-iodotoluene, 0.375mmol of aryl boronic
under vigorous stirring. The resultant solid product could be acids, and 0.5mmol of K
2
CO
3
were mixed into a flask, followed
-Pd (10mg, 1.0wt% of
solution for several times, and dried under vacuum condition palladium acetate) catalyst, subsequently, 3.0mL of EtOH and
at 60°C for 24h to gave sulfonic group functionalized 1.0mL of H O was also introduced as the solvents. The reaction
obtained from washing with abundant hot ethanol-HCl mixed by addition of 10mg of MOP-P(Ph)
3
2
nanoporous polymers. To adjust concentrations of sulfonic mixture was heated at 80°C for 30min under refluxing
groups, different contents of sodium benzenesulfonate was condition. When 4-bromotoluene was employed as substrate,
added in the initially synthetic process.
Strong acid ionic liquid groups can also be grafted onto the acids, and 0.5mmol of K
networks of MOPs. Typically, 1.0g of MOP-aniline or MOP- by addition of 10 mg of MOP-P(Ph)
pyridine were added into a mixture contains 0.3g of 1,4- palladium acetate) catalyst, subsequently, 3.0 mL of DMF and
butanesultone and 25mL of toluene, then the reaction 1.0mL of H O was also introduced as the solvents. The reaction
temperature was increased up to 100°C and kept at 100°C mixture was performed at 120°C for 5h. When 4-chlorotoluene
for 12h. After cooling to room temperature, 2.5mL of HSO CF was employed as substrate, 0.25mmol of 4-chlorotoluene,
was introduced, after stirring of the mixture for 24h at room 0.375mmol of aryl boronic acids, and 0.5mmol of K CO were
temperature. The sample could be collected from filteration, mixed into a flask, followed by addition of 10 mg of MOP-
washing with abundant CH Cl -ethanol mixed solvents for P(Ph) -Pd (10mg, 1.0wt% of palladium acetate) catalyst,
removing of residual HSO CF , and drying at 80°C under subsequently, 4.0mL of DMF was also introduced as the
vacuum condition. MOP-aniline-[C
][SO CF ] were obtained (Where C
butanesultone and SO CF
of HSO CF ). The above acidification methods result in the yields of various products were analyzed by gas
0.25mmol of 4-bromotoluene, 0.375mmol of aryl boronic
CO were mixed into a flask, followed
-Pd (10mg, 1.0wt% of
2
3
3
2
3
3
2
3
2
2
3
3
3
4
][SO
3
CF
3
] or MOP-pyridine- solvents. The reaction mixture was performed at 120°C for 7h.
stands for 1,4- In these reactions, 1mmol of dodecane as internal standard
[C
4
3
3
4
3
3
stands for the anion exchanged acid was also introduced into the reaction mixture, and the GC
3
3
9
,22,23
samples functionalized with typical Bronsted acid sites.
chromatography of Agilent 7890.
Characterizations
Heck reaction
Nitrogen isotherms of the samples at -196°C were
3
1mmol of aromatic halide, 2mmol of alkenes, MOP-P(Ph) -
measured using a Micromeritics ASAP 2020 M system. The Pd catalyst (2µmol Pd) and 3mmol of potassium acetate was
samples were outgassed for 6h at 200°C before dispersed into 3mL of DMSO solvent into a three-necked flask
measurements, the pore-size distribution of nanopores in the equipped with a condenser and a magnetic stirrer. Then, the
sample was calculated by using the Barrett−Joyner−Halenda reaction mixture was heated up to 110°C and lasted for 5h,
(BJH) model. Thermogravimetric analyses (TG) were after cooling to room temperature, the reaction mixture was
performed on a Perkin-Elmer TGA7 in flowing air with a diluted with acetone, filtered and analyzed by gas
heating rate of 20°C/min. The acid exchange capacities of the chromatography of Agilent 7890 to give the GC yields of
catalysts were determined by acid−base ꢀtraꢀon with various products. In this reaction, 1mmol of dodecane as
standard NaOH solution. XPS spectra were performed on a internal standard was also introduced into the reaction
Thermo ESCALAB 250 with Al Kα radiation, and binding mixture.
energies were calibrated using the C1s peak at 284.9eV. CHNS
elemental analysis was performed on a Perkin-Elmer series II Knoevenagel condensation
CHNS analyzer 2400. TEM images were performed on a FEI
Tecnai G2 F20 s-twin D573 transmission electron microscope
Knoevenagel condensation of aldehydes with malononitrile
working at 200kV. SEM results were performed on n a Zeiss was performed at 80°C catalyzed by MOP-Aniline and MOP-
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4
Pyridine solid bases. Typically, 2mmol of aldehydes [C mim]Cl ionic liquid and 0.5mL of DMSO, which was basically
(
benzaldehyde, salicylaldehyde), 0.02g of catalyst and 2mmol dissolved after vigorous stirring at 100°C for 3-5h, then 20mg
of malononitrile were mixed well into 5mL of ethanol solvent, of MOP-ethylbenzene-SO H solid acid was added. After that,
then the reaction temperature was rapidly increased up to 600μL of water acted as reactant was slowly introduced into
0°C, the reaction was lasted for 1h. The products were the reaction mixture. At different time intervals, the reaction
3
8
analyzed by using gas chromatography systems (Agilent 7890) mixture was withdrawn, weighed, quenched immediately with
with a flame ionization detector (FID). The yields of products cold water, and centrifuged at 14,800rpm for 5min to separate
were calculated through the internal standard (dodecane) unreacted cellulose. For comparison, Amberlyst 15 and HCl
method. In addition, the catalysts could be regenerated from were also used as catalysts for catalyzing depolymerization of
centrifugation, washing with abundant ethanol and drying at Avicel, which were performed with similar procedures as that
3
60°C. The regenerated catalyst was used directly for the next of MOP-ethylbenzene-SO H. Notably, the isolated crystalline
run.
cellulose was thoroughly washed with water, and recovered
through centrifugation. The amount of isolated cellulose could
be determined by weighing.
Transesterifications
Transesterification of tripalmitin with methanol was Total Reducing Sugar (TRS)
performed as follows: 0.84g (1.04mmol) of tripalmitin was
added into a three-necked round flask equipped with a
condenser and magnetic stirrer, then the reacted technology to evaluate depolymerization degree of crystalline
temperature was rapidly increased to 65°C. After tripalmitin cellulose, which was tested via DNS method
In this work, TRS method was thought to be a reliable
a
30-32
. Typically, a
melting, 2.47mL (61mmol) of methanol and 0.1g of catalyst mixture contains 0.5mL of 3,5-dinitrosalicylicacid (DNS)
was quickly added under vigorous stirring, the reaction was reagent and 0.5mL of isolated reaction mixture was heated for
lasted for 14h at 65°C. The molar ratio of tripalmitin/methanol 5min at 100°C. Then, the mixture was diluted by using 4mL of
was 1/58.7 and the mass ratio of catalyst/tripalmitin was deionized water. The color changes of the mixture were
0
.119. The product was methyl palmitate with selectivity near measured in a NanoDrop 2000 UV-spectrophotometer at the
00%. For products analysis, 0.5mL of the reaction mixture wave length of 540nm. The concentrations of the total
1
was firstly dispersed into 5mL of acetone, filtered and analyzed reducing sugars was calculated based on a standard curves.
by gas chromatography of Agilent 7890. The column was HP- In this reaction, the concentrations of the products such as
INNOWax capillary column (30m); the initial temperature was glucose, cellobiose and HMF were measured by the Shimadzu
00°C with the ramping rate of 20°C/min, and final LC-20A HPLC system based on standard curve method, which
temperature was 280°C; the temperature of FID detector was was equipped with a SCR-101N column using extra-pure water
00°C and dodecane was used as internal standard. as mobile phase with a flow rate of 0.5mL/min. The column’s
Transesterification of sunflower oil with methanol was temperature was set to 50°C. In the meantime, a refraction
1
3
performed as follows: 1.0g of sunflower oil (1.16mmol) was index was used for detection of sugars in the water. The UV
added into a three-necked round flask equipped with a detector with wavelength number at 254nm was used for
condenser and a magnetic stirrer, and the temperature was detection of 5-hydroxymethylfurfural (HMF) based on
increased to 65°C. Then, 3.5mL of methanol (86.3mmol) and standard curve method, which was equipped with a CAPCELL
0.1g of catalyst were quickly added under vigorous stirring, the PAK
C18
column
using
methanol
and
water
reaction was lasted for 18h. The molar ratio of sunflower (methanol/water=80:20) as mobile phase, at a flow rate of
oil/methanol was 1/72.1 and the mass ratio of 0.7mL/min and the column’s temperature was set at 50°C.
catalyst/sunflower oil was 0.1. The main products were methyl
palmitate (C16:0), methyl stearate (C18:1), methyl oleate
Notes and references
(C18:2), methyl linoleate (C18:3), methyl arachidate (C20:0),
1
1-eicosenoic methyl (C20:1), methyldocosanoate (C22:0) and
1
2
3
4
5
6
7
8
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Green Chemistry
Page 10 of 10
View Article Online
DOI: 10.1039/C6GC02237E
HOH
H O
HH O
HOH
HO O
H O
OH
HO
H
O
O H
H
H
H
OH
H
OH
OH
OH
H
OH
OH
OH
H
n
X
NH
2
HO
3
S
P
Hyper-cross-linked
Template-free
+
Micro-meso-macroporous
polymers derived solid
catalysts
N
H
N
NH
N
X
N
3
SO H
3 3
SO CF
X=Cl, Br
R=Various functional molecules
OH
H
O
OH
HO
OH
HO
O
H
OH
H
OH
H
O
O
Micro-meso-macroporous polymeric solid catalysts with versatile active sites were synthesized
from hyper-cross-linking of various functional molecules, which exhibit excellent catalytic
activities for biofuels production and fine chemicals synthesis.