Mesoporous imine-based organic polymer: catalyst-free synthesis in water and application in CO2 conversion

Article abstract of DOI:10.1039/c8cc03346c

A mesoporous imine-functionalized organic polymer (Imine-POP) was prepared based on the reaction of an aryl ammonium salt with an aromatic aldehyde in water without any catalyst and template. The Pd coordinated Imine-POP exhibited high catalytic activity for the N-formylation of amines with CO₂/H₂ at 100 °C, affording a series of formamides in high yields.

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Mesoporous Imine-Based Organic Polymer: Catalyst-
Free Synthesis in Water and Application in CO2
Conversion
pCite this: DOI: 10.1039/x0xx00000x
a, b
a
a, b
a, b
a
Xiaoxiao Yu,‡ Zhenzhen Yang,‡ Shien Guo Zhenghui Liu, Hongye Zhang, Bo
a
a
a, b
Received 00th January 2012,
Accepted 00th January 2012
Yu, Yanfei Zhao, and Zhimin Liu*
DOI: 10.1039/x0xx00000x
www.rsc.org/
Mesoporous imine-functionalized organic polymer (Imine-
In recent years, porous organic polymers (POPs) have emerged
POP) was prepared based on the reaction of aryl ammonium as promising materials because they can be designed with specific
salt with aromatic aldehyde in water without any catalyst and functionalities, and thus have wide applications in many areas due to
template. Pd coordinated Imine-POP exhibited high catalytic their advantages such as permanent porosity, high surface area, good
o
activity for N-formylation of amines with CO /H at 100 C, stability, good ability to complex with metal species, and so on. In
2
2
1
2
-philic functionalities (e.g. fluoro, nitrogen-
affording a series of formamides in high yields.
particular, POPs with CO
2
1
containing groups ) have been prepared via different strategies,
3
1
4
As a renewable and environment-friendly C1 building block, carbon
dioxide (CO )-involved synthesis of chemicals has attracted much
which show good performances in CO
2
adsorption and conversion.
2
As heterogeneous catalysts, mesoporous structures in POPs are
1
5
attention because it can reduce the predominant dependence on
1
petrochemical feedstocks for chemical supply chain. Formamides are
highly desirable because they are favourable to mass transfer. To
date, different approaches have been developed for the synthesis of
mesoporous POPs, and in most cases metal catalysts, templates and
a class of chemicals with widespread applications in industry, which
can be used as solvents (e.g. N, N-dimethylformamide (DMF)) and raw
2
materials for organic synthesis. Although preparation of DMF from
1
4b-14d, 16
organic solvents are required.
For example, Dai’s group
prepared mesoporous phenolic polymers and ionic organic networks
1
using F127 as a soft template and SiO as a hard template. Xiao et
2
7
18
CO , H
3
970, the N-formylation of other bulky amines using CO
2
2
and dimethylamine has attracted long-term interest since
/H has only
1
2
2
al. reported a solvent-mediated approach for the synthesis of
mesoporous phosphine-functionalized POPs based on divinylbenzene
1
polymerization. Our group presented preparation of mesoporous
4
5
6
been realized over Ru, Co, Cu complexes and several
heterogeneous catalysts in recent years. In contrast, heterogeneous
catalysts are more desirable for industrial applications owing to the
convenience of recovery and recycling. The reported heterogeneous
9
Tröger’s base-functionalized polymers using an ionic liquid/H
2
system. The synthesis of POPs in water is seldom reported due to
2
O
0
2
1
2 2
catalytic systems for N-formylation of amines with CO /H mainly
the limited solubility of monomers in water. In contrast, preparation
of mesoporous POPs without template in aqueous media can avoid
utilization of toxic organic solvents, removal of template, as well as
tedious operation and posttreatment, which may provide green route
for the preparation of POPs.
7
8
9
10
2 3 2
include Pd/Al O , Au/TiO , Pd−Au/carbon nanotubes, Pd/C and
1
1
Ru/POP, which generally made the formylation of amines proceed
o
at temperatures >100 C. Hence, development of heterogeneous
2 2
materials for efficient N-formylation of amines with CO /H under
mild conditions are of importance for their practical applications.
Herein, we present a novel approach to prepare imine-based POP
(
Imine-POP) with mesoporous structure based on the reaction of aryl
ammonium salt with aromatic aldehyde in water without any catalyst
2
a
Beijing National Laboratory for Molecular Sciences, Key Laboratory of
Colloid, Interface and Thermodynamics, CAS Research/Education Center
for Excellence in Molecular Sciences, Institute of Chemistry, Chinese
Academy of Sciences, Beijing 100190, China. E-mail: liuzm@iccas.ac.cn
University of Chinese Academy of Sciences, Beijing 100049, China.
These authors contributed equally to this work.
-1
g
or template. The resulting p0lymer had surface area of 194 m
dominated from the mesopores (2-30 nm). The presence of imine
groups made the polymer be able to chelate with Pd species, and the
b
resultant Pd-immobilized Imine-POP (Imine-POP@Pd) showed good
‡
catalytic activity together with high stability and easy recyclability for
o
the N-formylation of amines with CO /H at 100 C.
Electronic Supplementary Information (ESI) available: Supplementary
experimental details, data and figures. See DOI: 10.1039/b000000x/
2
2
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absorption bands of the aromatic ring were located in the range of
Cl H3N
Cl H3N
NH3 Cl
NH3 Cl
-
450-1600 cm , and the characteristic band at 1697 cm belonged to
1
-1
1
the imine group within the backbone. The two bands at 3159 and 3346
-
cm were probably ascribed to the unreacted amino/ammonium
1
+
N
N
N
N
CHO
catalyst free
H2O
(A)
groups and the formed hydroxyl groups during the hydrothermal
13
procedure, respectively. In the CP/MAS C NMR spectrum (Figure S2,
ESI), the chemical shifts in the range of 133.2~141.3 ppm were
attributed to the aromatic carbons in the backbone. The signal at
151.9 ppm belonged to the carbon of imine bond. The powder X-ray
diffraction (PXRD) pattern exhibited amorphous nature of the
polymer (Figure S3, ESI). The morphology of the material was
observed by field-emission scanning electron microscopy (SEM) and
transmission electron microscopy (TEM) (Figure S4, ESI), which
showed that the sample was composed of tiny particles with irregular
shapes and sizes. The thermogravimetric analysis (TGA) results
OHC
CHO
Imine-POP
7
6
5
4
3
2
1
00
00
00
00
00
00
00
0
Imine-POP Adsorption
(B)
(C)
Imine-POP
Imine-POP@Pd
Imine-POP Desorption
Imine-POP@Pd Adsorption
Imine-POP@Pd Desorption
o
indicated that the material was stable in air up to 350 C, which meets
0
.0
0.2
0.4
0.6
Relative pressure P/P
0.8
0
1.0
0
5
10
15
20
Pore width/nm
25
30
35
the demand for potential applications in catalytic CO
Figure S5, ESI).
Textural information on Imine-POP was obtained by N
analysis. The N sorption isotherms of the polymer exhibited
combined features of type I and type IV with two evident steep steps
in the regions of P/P =o~0.01 and 0.80~0.98, suggesting the
2
conversion
(
2
sorption
2
0
coexistence of micro- and mesopores (Figure 1B). Based on the
calculated result of the non-local density functional theory method
(
NLDFT), it is clear that micropores with size around 1.4 nm and
mesopores with pore diameters in the range of 2–30 nm were existent
in Imine-POP (Figure 1C). The BET surface area of Imine-POP was
2
-1
3
-1
estimated to be 194 m g with pore volume of 0.608 cm g (For BET
plot, see Figure S6, ESI). Notably, mesopore played the dominant role
in the pore structure of Imine-POP, contributing ~99% of the total
3
pore volume (Vmicro = 0.0028 cm g , calculated by t-plot method).
-1
2
2
Since imine bond can chelate with metal ions, Imine-POP was
taken as the support for further metal immobilization. Imine-
POP@Pd was prepared by treating the polymer with Pd(OAc)
CH Cl (for experimental details, see ESI). The content of Pd species
Figure 1 (A) Synthetic route for Imine-POP. (B) Adsorption and desorption decorated onto Imine-POP was 8.30 wt%, as determined by
2
in
2
2
2
isotherms of N at 77 K. (C) pore size distributions based on the calculation
inductively coupled plasma-optical emission spectroscopy (ICP-OES)
analysis. (HR)TEM examination indicated that the Pd species were
results of the NLDFT method for Imine-POP and Imine-POP@Pd. (D) (HR)TEM
image of Imine-POP@Pd. Map of Pd particle size distribution was obtained by
counting 100 particles. Scale bar 25 nm (E) XPS spectra of C1s, (F) N1s and (G) present in the form of particles with size around 2.84 nm, which were
Pd3d for Imine-POP@Pd
.
uniformly distributed on the polymer support (Figure 1C and Figure S7
in ESI). The energy dispersive spectroscopy (EDS) profile obtained
during TEM observation indicated the coexistence of Pd, C, and N in
the material (trace amounts of O, Cu were induced by lacey support
films) (Figure S8, ESI), and compositional EDS mapping of Imine-
POP@Pd exhibited homogeneous distribution of C, N, and Pd
elements (Figure S9, ESI).
As illustrated in Figure 1A, Imine-POP was synthesized via the
reaction of 1,2,4,5-benzenetetramine tetrahydrochloride and
benzene-1,3,5-tricarbaldehyde under hydrothermal condition without
any catalyst or additive (For detailed synthetic procedure, see ESI).
The resultant sample was in the form of loose brown powder, and did
2
not dissolve in common solvents, such as H O, ethanol, DMF,
To explore the oxidation stated of Pd species, X-ray photoelectron
spectroscopy (XPS) analysis was performed on Imine-POP@Pd. In
the C1s XPS spectrum (Figure 1E), three peaks with the bonding
energies (BEs) at 284.7, 286.5 and 289 eV can be deconvoluted, which
can be ascribed to carbons of aromatic C, C=N bond and a small
tetrahydrofurane (THF) and so on. To verify the chemical structure of
Imine-POP, a model reaction was firstly conducted using 1,2-
benzenediamine dihydrochloride and benzaldehyde as substrates
under hydrothermal condition, and N,N-dibenzylidenebenzene-1,2-
diamine was obtained (for details, see ESI), indicating the formation
of imine bond. The successful formation of the imine frameworks in
Imine-POP was further confirmed by Fourier-transformed infrared
quantity of C=O bond
presence of C=N bond with BE=398.3 eV in the backbone, and the
residual –NH Cl group with C-N BE=399.9 eV. Correspondingly, Pd3d
. N1s spectrum (Figure 1F) mainly showed the
3
(
FT-IR) analysis and cross-polarization magic-angle spinning (CP/MAS)
2+
spectrum (Figure 1G) indicated the presence of Pd with BEs at 337.8
0
and 343.1 eV together with metallic Pd particles with BEs at 335.6
1
3
C NMR analyses. In the FT-IR spectrum (Figure S1, ESI), the
2
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0
a
and 340.9 eV. The presence of Pd particles suggest that Imine-POP Table 2 Formylation of amines with CO /H catalyzed by Imine-POP@Pd
2
2
2
can reduce Pd species.
+
The immobilization of Pd did not impact the thermal stability of
o
Imine-POP, which was still stable in air up to 350 C, confirmed by
TGA analysis (Figure S5, ESI). The BET surface area of Imine-
2
POP@Pd decreased to 180 m g (Figure S6, ESI) with pore volume of
-1
Entr
y
b
3
.514 cm g , slightly lower than that of Imine-POP. The pore size
-1
0
Substrate
Product
Yield/%
97
distribution curve obtained from the calculation results of NLDFT still
showed the dominant existence of mesopores (Figure 1C).
1
2
3
4
1
a
2
a
92
94
84
a
Table 1 Formylation of morpholine (1a) with CO
/H
2 2
over Imine-POP@Pd
1b
2
b
1
c
2c
b
Entry Change from the standard conditions
Yield/%
1
2
3
4
5
6
7
8
9
1
None
97
1d
2d
2
Pd(OAc) 2.3 mol% instead of Imine-POP@Pd 93
Imine-POP instead of Imine-POP@Pd
PO 0.2 mmol
0
5
6
2 N
H
2
70
K
3
4
88
47
85
60
81
58
95
1
1
e
f
No base
2e
o
80 C
o
60 C
c
5 N
H
5
84 (69 )
reaction time 12 h
CO
2
2 MPa + H
2
2 MPa
2f
c
0
None
c
7
8
9
99 (79 )
a
Reaction condition: 1a, 1 mmol; Imine-POP-Pd, 30 mg (Pd was 2.3 mol%
1
g
2g
o
based on 1a); K
2
3
PO
4 2 2
, 0.3 mmol; CO 3 MPa, H 3 MPa; DMI, 4 mL; 100 C,
b
c
4 h. Determined by GC using dodecane as the internal standard. Imine-
71
77
POP-Pd was reused for five times.
1
h
2h
1
i
2i
The catalytic activity of Imine-POP@Pd was examined by
2 2
catalysing formylation of amines with CO /H . The formylation of
1
1
0
1
64
morpholine (1a) was taken as a model reaction to optimize the
reaction conditions (Table 1 and Table S1 in ESI). After a careful survey
of the reaction parameters, N-formylmorpholine (2a) was obtained in
1j
2
j
c
78 (62 )
a
yield of 97% using 1,3-dimethyl-2-imidazolidinone (DMI) as the
o
at 100 C (Table 1, entry 1). Notably,
1
k
2k
solvent in the presence of K
3
PO
4
this result was even higher than that obtained over Pd(OAc)
2
as the
c
1
1
2
3
4
92 (74 )
catalyst (2a yield: 93%) (entry 1 vs 2) , and much higher than that
1l
2
l
obtained over the Pd heterogeneous catalysts decorated on other
69
48
2 3 2
supports including Al O , TiO , activated carbon under otherwise
1
m
2m
2n
identical reaction conditions (Table S1, ESI). These results indicate
that the Imine-POP support enhanced the activity of the Pd catalyst,
4
probably due to its mesoporous structure and the CO -philic nature,
2
1
2
1
n
though it showed no catalytic activity (entry 3). In addition, both the
solvent and base also impacted the reaction activity. DMI was used as
a
Reaction condition: 1, 1 mmol; Imine-POP-Pd, 30 mg (Pd was 2.3 mol%
o
based on 1a); K
3
PO
4 2 2
, 0.3 mmol; CO 3 MPa, H 3 MPa; DMI, 4 mL; 100 C,
b
the reaction medium owing to its Lewis basic property and CO
2
-philic 24 h. Yields were determined by NMR using CH NO as an internal
3
2
2
3
c
standard. Isolated yield. For details, see ESI.
nature. Among the tested bases including K
Cs CO , DBU, K PO
influenced the product yields(Table S1, ESI). For example, the yield of
decreased to 88% as the amount of K PO decreased to 0.2 mmol
Table 1, entry 4), while it further decreased to 47% in the absence of
PO (entry 5). The reaction could also proceed at lower reaction
3
PO
4
,
t
-BuOK, KOH,
2
3
3
4
showed the best performance, and its amounts
reusability, confirmed by the fact that a 95% yield of 2a was still
achieved after the catalyst was reused for five times (Table 1, entry 10;
Figure S10, for experimental details, see ESI). Moreover, no Pd species
were detected in the filtrate of the reaction mixture by ICP-OES,
indicating the strong coordination ability of the polymer with Pd
2
a
3
4
(
K
3
4
o
temperatures (e.g., 80 and 60 C), affording moderate yields of 2a (85%
species and thus good stability of Imine-POP@Pd
.
and 60%, respectively) (entries 6 and 7). In addition, shorter reaction
Under the optimal reaction conditions, N-formylation of other
amines was investigated, and the results are shown in Table 2. The N-
time (e.g., 12 h) or lower CO
2 2
/H pressures led to declined 2a yields
(
entries 8 and 9). Importantly, Imine-POP@Pd showed good
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formylation reactions proceeded smoothly for primary and secondary
aliphatic amines, selectively affording the corresponding formamides
7
8
9
X. Cui, Y. Zhang, Y. Deng and F. Shi, Chem. Commun., 2014, 50, 189-
191.
2
a
~
2n in moderate to excellent yields (48%~97%). Besides 1a, other
cyclic aliphatic amines also performed well, producing the
corresponding formamides 2b 2d in yields higher than 84%. Linearly
aliphatic amines, di-n-propylamine 1e and di-n- hexylamine 1f,
showed good reactivity, affording 70% and 84% yields of 2e and 2f
respectively. The reactivity of N-methylbenzylamine was also good,
with 99% yield of 2g. However, its derivatives with electro-donating 11 Z. Yang, H. Wang, G. Ji, X. Yu, Y. Chen, X. Liu, C. Wu and Z. Liu,
or electro-withdrawing groups (e.g. –Me or -F) showed inferior New J. Chem., 2017, 41, 2869-2872.
reactivities, leading to 71% yield of 2h and 77% yield of 2i. Formylation 12 (a) Y. Zhao, K. X. Yao, B. Teng, T. Zhang and Y. Han, Energy
T. Mitsudome, T. Urayama, S. Fujita, Z. Maeno, T. Mizugaki, K.
Jitsukawa and K. Kaneda, ChemCatChem, 2017,
P. Ju, J. Chen, A. Chen, L. Chen and Y. Yu, ACS Sustainable Chem.
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10 Y. Zhang, H. Wang, H. Yuan and F. Shi, ACS Sustainable Chem.
Eng., 2017, , 5758-5765.
9, 3632-3636.
~
5
,
5
of primary amines with linear chains gave 2j in 64% yield.
Cyclohexylamine also showed good reactivity, affording 2k in 78%
yield. Formylation of benzylamine performed well, producing 2l in
Environ. Sci., 2013,
Zhao, L.-M. Zhang, A.-D. Qi and B.-H. Han, ACS Macro Lett., 2013,
, 522-526; (c) Z.-Z. Yang, Y. Zhao, H. Zhang, B. Yu, Z. Ma, G. Ji
and Z. Liu, Chem. Commun., 2014, 50, 13910-13913.
donating or electro-withdrawing groups (e.g. –Me or -F) decreased, 13 (a) Z. Dai, Q. Sun, X. Liu, L. Guo, J. Li, S. Pan, C. Bian, L. Wang, X.
6, 3684-3692; (b) D.-P. Liu, Q. Chen, Y.-C.
2
9
2% yield, while the reactivities of its derivatives with electro-
affording moderate yields of 2m (69%) and 2n (48%).
Hu, X. Meng, L. Zhao, F. Deng and F.-S. Xiao, ChemSusChem,
The formylation mechanism of amines with CO2/H2 was explored.
Control experiments showed that HCOOH was formed via the CO2
hydrogenation over Imine-POP@Pd in the absence of amine (Figure
2017, 10, 1186-1192; (b) Q. Chen, M. Luo, P. Hammershøj, D.
Zhou, Y. Han, B. W. Laursen, C.-G. Yan and B.-H. Han, J. Am.
Chem. Soc., 2012, 134, 6084-6087; (c) Q. Song, S. Jiang, T. Hasell,
M. Liu, S. Sun, A. K. Cheetham, E. Sivaniah and A. I. Cooper, Adv.
Mater., 2016, 28, 2629-2637; (d) Y. Zhu, H. Long and W. Zhang,
Chem. Mater., 2013, 25, 1630-1635; (e) H. A. Patel, S. Hyun Je, J.
Park, D. P. Chen, Y. Jung, C. T. Yavuz and A. Coskun, Nat.
S11, ESI), which could further react with amine to form 2a in a yield of
5
3% (Scheme S1, ESI). Based on previous reports and results
9
obtained in this work, it was deduced that the N-formylation product
was obtained via the Imine-POP@Pd-catalyzed CO hydrogenation
to HCOOH and the subsequent reaction of HCOOH with amine
2
Commun., 2013, 4, 1357.
(
Scheme S2, ESI).
14 (a) X.-Y. Yang, L.-H. Chen, Y. Li, J. C. Rooke, C. Sanchez and B.-L.
In summary, mesoporous imine-functionalized POP was
Su, Chem. Soc. Rev., 2017, 46, 481-558; (b) W. Wang, M. Zhou and
synthesized in water without any catalyst or template. The integration
of imine group gave the polymer strong coordination ability with the
Pd species, and the resultant Pd metalated material exhibited good
D. Yuan, J. Mater. Chem. A, 2017,
5, 1334-1347; (c) L. Tan and B.
Tan, Chem. Soc. Rev., 2017, 46, 3322-3356; (d) N. Chaoui, M.
Trunk, R. Dawson, J. Schmidt and A. Thomas, Chem. Soc. Rev.
2017, 46, 3302-3321.
,
,
2 2
catalytic performance for the N-formylation of amines with CO /H at
relatively low temperature, together with high stability and easy 15 Q. Sun, Z. Dai, X. Meng and F.-S. Xiao, Chem. Soc. Rev., 2015, 44
recyclability. 6018-6034.
We thank the National Natural Science Foundation of China (No. 16 M.-H. Sun, S.-Z. Huang, L.-H. Chen, Y. Li, X.-Y. Yang, Z.-Y. Yuan
2
1673256, 21533011), and the Chinese Academy of Sciences (QYZDY-
and B.-L. Su, Chem. Soc. Rev., 2016, 45, 3479-3563.
SSW-SLH013-2) for the financial supports.
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Nelson and S. Dai, Angew. Chem. Int. Ed., 2015, 54, 4582-4586.
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Page 5 of 5
ChemComm
View Article Online
DOI: 10.1039/C8CC03346C
Mesoporous imine-functionalized organic polymer was prepared in water under
catalyst- and template-free condition. After Pd species coordination, the resultant
material exhibited high catalytic efficiency in the N-formylation of amines with
CO /H .
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2