Function-oriented ionic polymers having high-density active sites for sustainable carbon dioxide conversion

Article abstract of DOI:10.1039/c8ta00823j

On the basis of the development of function-oriented synthesis (FOS), we presented for the first time an efficient and one-pot construction of functional ionic polymers (FIPs) through the phenol-formaldehyde condensation process (pre-synthetic approach); FIPs had high density of Br?nsted acidic and ionic sites. Considering the electrophilic-nucleophilic dual activation of phenolic hydroxyl groups and bromide anions, the imidazolium-based FIP-Im exhibited high activity for metal-, solvent- and additive-free synthesis of cyclic carbonates from CO₂ and epoxides under mild conditions. Then, to obtain higher ionic density and a more flexible skeleton, FIP-Im@QA was also prepared by implanting quaternary ammonium (QA) in the framework of FIP-IMvia the Williamson ether synthesis (post-synthetic modification), which demonstrated high efficiency in the N-formylation reaction of multitudinous secondary amines with CO₂ and PhSiH₃ at ambient temperature. More interestingly, these function-oriented catalysts were compatible with the target transformation under low CO₂ concentration (15% in 85% N₂, v/v) and were also reused for more than six times without a significant loss of activity and selectivity. Therefore, this study could not only facilitate the design and construction of FIPs, but also provide sustainable protocols for efficient production of value-added chemicals from CO₂ under mild conditions.

Full text of DOI:10.1039/c8ta00823j

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PAPER
Kun Chang, Zhaorong Chang et al.
Bubble-template-assisted synthesis of hollow fullerene-like
MoS nanocages as a lithium ion battery anode material
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Function-oriented ionic polymers featuring high-density active
sites for sustainable carbon dioxide conversion
a
b
a
a
a
c
a
Yaju Chen, Rongchang Luo,* Junhui Bao, Qihang Xu, Jun Jiang, Xiantai Zhou and Hongbing Ji*
Received 00th January 20xx,
Accepted 00th January 20xx
On the basis of the development of function-oriented synthesis (FOS), we firstly presented an efficient and one-pot
construction of functional ionic polymers (FIPs) through phenol-formaldehyde condensation process (pre-synthetic
approach), which featured the high density of Brönsted acidic and ionic sites. Considering the electrophilic-nucleophilic
dual activation of phenolic hydroxyl groups and bromide anions, the imidazolium-based FIP-Im exhibited the high activity
DOI: 10.1039/x0xx00000x
www.rsc.org/
2
for the metal-, solvent- and additive-free synthesis of cyclic carbonates from CO and epoxides under mild conditions.
Then, in order to obtain the higher ionic density and more flexible skeleton, FIPs-Im@QA was also prepared by implanting
quaternary ammonium (QA) in the framework of FIP-IM via the Williamson ether synthesis (post-synthetic modification),
which demonstrated the high efficiency in the N-formylation reaction of multitudinous secondary amines with CO
PhSiH at ambient temperature. More interestingly, these function-oriented catalysts were compatible with
the target transformation under low CO concentration (15% in 85% N , v/v) and were also reused for more than six times
without a significant loss of activity and selectivity. Therefore, this work could not only facilitate the design and
2
and
3
2
2
construction of FIPs, but also provide sustainable protocols for efficient production of value-added chemicals from CO
2
under mild conditions.
instance, in 2016, Sun and co-workers revealed urea
derivative-based ionic liquids with dual-functions were
Introduction
2
Recently, carbon dioxide (CO ) capture utilization and storage
successfully employed as efficient catalysts for the
5
(CCUS) has been generally identified as one of the most
CO
2
/epoxides coupling reaction.
Han et al firstly
potential strategies in the global energy transition, enabling
the provision of energy and the production of essential
1
materials, while limiting climate change. To this end, plenty of
demonstrated imidazolium-based ILs were used as both the
catalyst and solvent for the cyclization reaction of CO with
propargylic amines. More recently, He et al reported betaine
catalysis for reductive functionalization of CO with various
2
6
techniques have been developed for the combination of CO2
2
capture and subsequent conversion. Ionic liquids (ILs), known
2
7
amines and diphenylsilane. Despite progress, for these
homogeneous protocols, obvious drawbacks such as the
intricate recycle of catalysts and the purification of products
have greatly limited their widely industrial application.
as sustainable media as well as catalysts in organic reactions,
have been widely applied in cycling carbon resource owing to
their outstanding physicochemical properties. It is worth
mentioning that ILs possess excellent CO solubility, selective
2
3
absorbability and strong CO philicity. Moreover, task-specific
So far, numerous ILs-based heterogeneous catalysts
possessing function-oriented active sites have been developed
8
to realize these catalytic cycles. These ionic polymers were
2
ILs could be directly used or exclusively designed by
introducing different function-oriented groups for catalyzing
4
various CO -involved reactions. Therefore, in the light of
mainly obtained from the classical anchoring method, free
radical polymerization and other condensation/self-assembly
processes. For example, Sawamura et al developed polymer-
2
characteristics of CO -related transformations, the targeted
2
functionalization of ILs has received significantly attention. For
anchored diol functionalized ILs for the cycloaddition of CO
2
with epoxides. Nevertheless, this post-anchored method
could not ensure the complete incorporation of functional IL
9
groups. For free-radical polymerization, the formation of
polymeric ionic martials often promoted in the present of
1
0
initiators
(e.g.
azoisobutyronitrile).
However,
this
polyreaction is sensitive to many active groups (e.g. phenolic
1
1
hydroxyl group),
functionalization of ionic polymers, and thus limit their
application in various CO -related reactions. Moreover, in the
which might impede the oriented
2
polymerization process, co-monomer (e.g. divinylbenzene) was
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generally used for the formation of hyper-cross-linked matrix. strategies, and their catalytic performances were evaluated in
The introduction of inactive monomer often reduced the the targeted CO -involved reactions (Scheme 1). As expected,
2
density of active sites and eventually decreased the catalytic polyphenolic FIPs consisting of ample acidic phenol hydroxyl (-
performance. On these points, the low-cost and practical OH) and IL groups could be employed as cooperative catalysts
2
development of functional ILs-based polymeric catalysts is still for the cycloaddition of CO with epoxides under metal–
highly attractive. In 2018, our group designed and prepared a solvent–additive free conditions. Additionally, since
series of IL-based polymers with intercalated metalloporphyrin quaternary ammonium salts (QAs) were regarded as efficient
through the simple and reversible Schiff-base reactions, which catalysts for the synthesis of formamides from amines and CO
2
1
2
exhibited excellent catalytic performance in the CO
2
/epoxides in the presence of phenylsilane. As designed, the multi-OH
coupling reaction. Even so, in this catalytic system, the metal groups in the framework of FIP-Im were further modified into
center was employed as the active site, which new FIPs containing high-density and flexible QAs FIP-Im@QA
9
(
)
was at variance with the perspective of environment-friendly through the Williamson ether reaction by using post-synthetic
catalysis. Taking into account the above factors, it is still highly approach. Encouragingly, the above function-oriented FIPs
desirable to develop greener methodologies for the displayed excellent catalytic performance, robust recyclability
construction of function-oriented ionic polymers featuring and good substrate expansibility for the corresponding
2 2
high-density active sites, which can be used as efficient and reaction. Notably, the diluted CO (15% in 85% N , v/v) was
sustainable catalysts for various CO
2
-involved reactions.
successfully converted into the desired products by using
above-mentioned sustainable protocols. These results clearly
demonstrated that the designed function-oriented ionic
polymers with high-density active sites could have great
2
potential for CO catalytic fixation from a practical perspective.
Results and discussion
Synthesis of Catalysts
2
According to the dual activation mechanism of CO /epoxide
coupling, bifunctional FIPs were prepared through one-step
phenol-formaldehyde condensation reaction (Scheme 2A).
Owing to the electron-donating resonance effect of hydroxyl
groups, the phloroglucinol exhibited high reactivity for
electrophilic aromatic substitution during the polymerization
process, which could easily attack the carbonyl groups of
1
3
2
dialdehyde. Then, H O molecules were eliminated along with
the generation C–C bonds, thus affording the desired
framework. It is noteworthy that this solvothermal technique
may express the tremendous advantages as follows: 1) the
FIPs synthesis is very facile and green with high yields; 2) the
polymerization reaction is initiated by heating the sample at
room temperature in the absence of any catalysts, thereby
avoiding the complicated separation process; and 3) the
bottom-up synthetic approach endows the FIPs with task-
specific and high-density active sites. Furthermore, the desired
catalyst FIP-Im@QA was also obtained via a post-modified
process from the resultant FIP-Im by substituting OH groups
with the newly-prepared (2-bromobutyl) triethylammonium
Scheme 1 Structure of the synthesized function-oriented ionic polymers
and their applications in heterogeneous catalysis of CO transformation.
2
Inspiringly, the synthetic strategy based on the phenol-
formaldehyde condensation reaction meet the above
requirements. It is facile to obtain functional ionic polymers
(FIPs) with high-density active sites by combining phenols with
IL-modified aldehydes through pre-synthetic method.
Moreover, this approach prevents the metal contamination
from the source (i.e.: no metal catalyst for the preparation of
FIPs and without metal active centre for the follow-up
reaction). More importantly, the as-prepared polymers contain
abundant phenolic hydroxyl groups, thereby can be easily
modified into other catalytic active sites. These advantages
3
bromide ([BrBuNEt ]Br) as shown in Scheme 2B.
2
make the FIPs highly attractive for catalyzing various CO -
related transformations by the purposeful and rational design.
Herein, on the basis of the concept of function-oriented
synthesis (FOS), a series of FIPs with high active-site density
were firstly acquired through both pre- and post-synthetic
2
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1
was attributed to the Ph–C stretching mode. Furthermore, in
8
Figure 1B-c, the spectrum of FIP-Py shows the characteristic
−
1
bands at ṽ = 1635 cm , which was attributed to C=N stretch in
1
the pyridine ring. For the spectra of FIP-Im (Figure 1B-b) and
9
FIP-Im@QA (Figure 1B-d), the peaks appeared at ṽ = 1556 and
1
6
22 cm− might be assigned to the stretching vibration of
1
4,20
imidazole ring.
These vibrational signatures demonstrated
that the IL units had been successfully intercalated into the
networks of polymers.
137.2 128 115-125
(
A)
138.8
108.8
5
2.8
25-36
196.6
153
98.2
d
6
1.5
Scheme 2 Synthesis of the designed function-oriented ionic polymers.
c
Reagents and conditions: (a)A
0
, A
dioxane (5 mL), 70 C for 1 h, then 220 C for 4 d; (b) FIP-Im (0.3 g), QA(2.0
mmol), K CO (3 mmol), dry DMF (15 mL), refluxed for 24 h.
1 2
or A (1.0 mmol), B (1.3 mmol), 1,4-
o
o
2
3
b
a
Characterization of Catalysts
The newly-synthesized ionic materials including FIP-Im, FIP-Py,
250
200
150
100
50
0
FPP and FIP-Im@QA are quite stable in an atmosphere
conditions and insoluble in water and common organic
solvents, suggesting their stably heterogeneous structure of
highly cross-linked matrix. Initially, the formation of them was
revealed by various characterization techniques such as solid-
Chemical shift (ppm)
(B)
d
1100
1510
c
1
3
state
C NMR spectroscopy, FT-IR spectroscopy, X-ray
b
photoelectron spectroscopy (XPS), and elemental analysis. As
shown in Figure 1A, the peaks at 98.2 ppm and 108.8 ppm
could be assigned the unreacted and reacted phloroglucinol
orthocarbons, respectively. A series of peaks approximately at
δ = 105-160 ppm in the NMR spectra are assigned the
1635
622
a
1556
825
9
,14
1611 1458 1216
3413
aromatic carbon atoms in the polymer networks.
4
000 3500 3000 2500 2000 -11 500 1000 500
Specifically, the peak at around 153 ppm might be originated
from the phenoxy carbons, while the resonances at 138.8 ppm
and 128 ppm could correspond to the phenyl carbons next to
the phenoxy carbons and the other phenyl carbons. The peaks
at 137.2 ppm and 115-125 ppm might be attributed to the
carbons in IL groups, which were formed by the condensation
reaction. Resonances observed at around δ = 25-36 ppm could
be attributed to the tertiary carbon atom (-CH-) formed in
Wavenumbers (cm )
1
Figure 1 (A) Solid-state C NMR and (B) FT-IR spectra of FPP (a), FIP-Im (b),
3
FIP-Py (c), and FIP-Im@QA (d).
Then, the composition of FIP-Im and FIP-Im@QA was
further assessed with XPS and elemental analysis. The survey
spectrum of both samples displays four peaks, namely, C 1s, N
1s, Br 3d and O 1s, indicating IL implanting into the polymers
1
3
polymerization process. Meanwhile, the signals at around δ =
1.5 ppm (Figure 1A-c) and 52.8 ppm (Figure 1A-b and d) are
ascribed to the benzylic carbon atom (–CH -) next to the
(
Supporting Information, Figure S1). With respect to the bigger
6
spheres, the peak at 402.35 eV in the N 1s XPS spectrum of
2
14
1
5
FIP-Im is related to the contribution of Imidazolinium cations
21
Figure 2A-a). After the Williamson ether reaction of FIP-Im
pyridiniumiu
and imidazolium IL units , respectively,
(
demonstrating the successful incorporation of charged units
into the frameworks of polymers. Additionally, both the curves
b and d show a peak at δ = 196.6 ppm assigned to the signal of
3
with [BrBuNEt ]Br, the binding energy (BE) of N 1s (402.02 eV)
for FIP-Im@QA shifts to lower value compared to that of the
FIP-Im, and a new peak at 401.28 eV in this spectrum may be
22
1
6
traces of unreacted aldehyde carbonyl carbons. The FT-IR
1
assigned to quaternary ammonium nitrogen (Figure 2A-b),
spectra show a wide peak at ṽ = 3413 cm− corresponded to a
1
7
implying that quaternary ammonium salts were grafted onto
the polymers. This shift might be construed as: the electron
phenolic hydroxy (–OH) stretching vibration in the structure
of FPP FIP-Im or FIP-Py (Figure 1B-a, b and c; whereas the
,
3
donating effect of alkyl chain in -OBuNEt Br resulted in the
disappearance of this signal suggested the successful
formation of O–C bond through the Williamson ether reaction
increase of electron density of nitrogen in imidazolium cation,
thus reducing its BE for FIP-Im@QA. Similarly, the Br 3d
spectra shows the BE value at 68.15 ev (Br in imidazolium IL)
for FIP-Im, as well as two bromine species (67.78 eV, Br in
3
of FIP-Im with [BrBuEt N]Br, which was supported by the
observation of a new and strong absorption peaks at ṽ = 1100
1
cm− (C–O–C stretch) (Figure 1B-d). The peak at ṽ = 1216 cm−
1
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imidazolium IL; 66.79 eV, Br in quaternary ammonium salts) presence of charge interactions and the tendency of
2
3
for FIP-Im@QA (Figure 2B). Notably, the BE value of Br 3d for intermolecular stacking. Additionally, powder XRD patterns
quaternary ammonium salts was lower than that of of these polymers revealed their conventional amorphous
imidazolium IL (Figure 2B-b), indicating that Br species had state (Figure S5). More importantly, FIPs had been widely used
more electrons, and thus led to higher binding ability with as excellent solid sorbent for CO
hydrogen in N-methylaniline via hydrogen bond. In addition, to their excellent CO selectivity over other light gases and the
the CHNO content were measured by elemental analysis, and outstanding CO affinity. Considering the abundant polar IL
the bromine content was measured by oxygen flask species within our functional polymers, we set out to study
combustion and mercury nitrate titration technique, which CO and N uptake performance up to 1 bar at 273 K. As shown
in Figure 3A, the material FPP with high surface area possessed
2
capture and separation due
2
3
b
2
2
2
−1
revealed 2.51, 2.64, and 4.40 mmol·g of Br for FIP-Im
and FIP-Im@QA, respectively (Table S1). As shown in Figure 2C, the highest reversible CO
the elemental mapping for catalyst FIP-Im, determined by compared to the other as-prepared polymers. The IL
energy-dispersive X-ray spectroscopy (EDS), demonstrated the intercalated polymers exhibited moderate CO capture
homogeneous distributions of O and Br, further directly capacity at 273 K (1.45, 1.27, and 0.90 mmol·g , respectively)
confirming the uniform polymerization of phloroglucinol and in spite of their low surface areas, showing their CO binding
ILs by solvothermal method. Moreover, both FIP-Im and FIP- affinity. For FIP-Im, the uptake capacity of CO was also up to
Im@QA are thermally stable up to 250 C as evidenced by 0.97 mmol·g at ambient conditions (1.0 bar, 298 K).
thermogravimetric analysis in nitrogen flow (Figure 2D). Furthermore, to gain further insight into the interaction
between CO molecule and polymer, the isosteric heat of CO
, FIP-Py,
-1
2
uptake capacity of 2.37 mmol·g
2
-1
2
2
o
-1
2
2
adsorption (Qst) for FIP-Im was calculated based on adsorption
(
A)
N 1s
02.02
(B)
b
Br 3d
401.28
66.79
isotherms at different temperatures (273 and 298 K) through
24
67.78
4
the Clausius–Clapeyron equation. As we can see from Figure
−
1
3
B, the Qst of FIP-Im is about 32.1 kJ·mol at low CO
indicating the strong physical sorption ability of FIP-Im
Moreover, N sorption experiment for FIP-Im was also carried
out at 273 K. and the selectivity ability for CO /N separation
2
coverage,
b
a
2
5
.
68.15
4
02.35
2
a
2
2
was calculated by using Henry’s Law constants according to
4
08 404 400 396 392
75
72
69
66
63
Binding energy (eV)
Binding energy (eV)
many other literatures. As depicted in Figure S6, FIP-Im had
1
00
the satisfactory CO
2 2
-over-N selectivity of 36, which was higher
(C)
(D)
b
8
6
4
0
0
0
than those for the reported polymeric materials such as SYSU-
C
O
9
24b
Zn@IL1 (32) and CPOP-1 (25) . The high CO
selectivity could be attributed to polar IL-units and rich-
nitrogen sites of FIP-Im thereby showing CO
molecules absorption priority through local-dipole-quadrupole
2 2
-over-N
a
,
2
Br
20
0
2
6
interactions. Therefore, the good CO
2 2
uptake ability and CO -
1
50 300 450 600 750
Temperature ( C)
over-N selectivity of FIP-Im might make it potential candidate
2
o
2
for CO capture, separation and conversion under low
Figure 2 (A) N 1s and (D) Br 3d XPS spectra of FIP-Im (a) and FIP-Im@QA (b). (C)
TEM-EDS elemental mapping images of FIP-Im. (D) TG curves of FIP-Im (a) and
FIP-Im@QA (b).
concentration.
8
6
4
2
0
0
0
0
0
50
CO
2
2
273 K for IL-free
273 K for FIP-Im
273 K for FIP-Py
298 K for FIP-Im
273 K for FIP-Im@QA
273 K for FIP-Im
(A)
(B)
FIP-Im
CO
CO
CO
CO
Furthermore, the morphology of the functional FIPs was
investigated by using field emission scanning electron
microscopy (SEM) and transmission electron microscopy (TEM).
From these typical images, the as-prepared FIP-Im showed a
relatively rough morphology (Figure S3-A) and a certain
amount of randomly oriented nanopore (Figure S3-B). To gain
2
2
2
4
3
2
0
0
0
N
2
10
0
0
.0 0.2 0.4 0.6 0.8 1.0
Relative pressure (P/Po)
5
10 15 20 253 30 35
CO uptake (cm /g)
insight into textural information of the polymers,
N
2
2
adsorption-desorption analysis was conducted at 77 K. As
shown in Figure S4, the Brunauer-Emmett-Teller (BET) surface
Figure 3 (A) Gas sorption isotherms for the polymeric catalysts at 273 K and 298 K.
(B) Isosteric heat of CO adsorption of FIP-Im.
2
−
1
2
area of FPP polymer (FPP) was up to 524 m ·g , while that of
FIP-Im FIP-Py and FIP-Im@QA were calculated as less than 10
,
2
−
1
m ·g . This observation of decreased BET surface area is Cycloaddition of epoxides with CO
2
similar to our previous works, and possibly can be
2
The production of cyclic carbonates from epoxides and CO has
accounted for the strong polarity of IL species within the
−
been regarded as an efficient and sustainable strategy for
27
recycling carbon resource. This coupling reaction could
9,14
polymers and the high atomic mass of Br in the nanopores.
The common problems for these porous ionic polymers are the
overcome the thermodynamics of CO
2
to give valuable
4
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2
8
molecules with
a
100% atom economy.
Generally,
Firstly, epichlorohydrin was chosen as a model substrate for
bifunctional catalytic systems including a Lewis acid and a this transformation.
9
A
set of control experiments
o
2
nucleophilic group are often efficient for this transformation.
were designed and performed at 80 C and an initial CO
2
In our previous works, a series of metalloporphyrin polymers pressure of 1.0 MPa under solvent-free conditions. The results
with intercalated ILs were designed and synthesized, and acted revealed that almost no product (4-(chloromethyl)-1,3-
as efficient cooperative catalysts for this reaction under dioxolan-2-one, 2a) was detected without any catalyst (entry 1,
8
a,9,14
additive-free conditions.
It was reported that phenolic Table 1), and FPP showed no activity for catalyzing this
hydroxyl groups (-OH) could be regarded as Brønsted acid sites reaction (entry 2, Table 1). To our delight, when 2.0 mol%
that accelerate the ring-opening rate of epoxides by hydrogen TBAB was employed a co-catalyst, quantitative epichlorohydrin
bonding, thus making the nucleophilic attack of halogen anion was coverted into the corresponding cyclic carbonate under
3
0
much easier to form the crucial intermediate. With the the same conditions (entry 3, Table 1). As expected, the
advantage of bifunctional catalytic system understood, we bifunctional catalyst FIP-Im (bearing imidazole ILs group)
chose this cycloaddition reaction as the model reaction to showed excellent catalytic performance with a yield of 99% in
exploit the catalytic potential of our bifunctional catalysts the absence of any additives owing to the molecularly
bearing multi-acidic sites and IL groups. As expected, the cooperative effect among phenolic hydroxyl groups,
prepared FIP-Im was found to exhibit good catalytic activity for imidazolium cations and nucleophilic haloid anions (entry 4,
the metal-solvent-additive free production of cyclic carbonates Table 1). This result was superior to those previously reported
2
via CO /epoxides coupling under milder conditions, which was for FIPs and comparable to those for the efficient metal-based
illustrated in Table 1.
polymeric catalysts (Table S2). However, only a carbonate yield
of 72% was achieved for FIP-Py (bearing pyridiniumium ILs
group) (entry 5, Table 1), which was far lower to the
corresponding value for FIP-Im. This difference could be
2
Table 1 Results of the cycloaddition reaction of CO with epichlorohydrin
a
over various catalysts
–
explained as the poor nucleophilicity of the halide ion (Br ) of
the relatively tight ion pair in the pyridiniumium ILs group,
which was also supported by the previous XPS analysis of Br
9
3d. Furthermore, in an effort to prove the contribution of the
b
b
CO
2
T
(°C)
80
80
80
80
80
80
80
80
80
80
60
25
t
Conv.
(%)
<1
Yield
(%)
<1
Entry
Catalyst
(
MPa)
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
0.5
1.0
0.1
(h)
10
10
10
10
10
10
10
10
10
10
10
72
–OH groups, we protected them through the Williamson ether
reaction of FIP-Im with methyl bromide to give substituted
product (denoted as FIP-Im@M). Under the same reaction
process, FIP-Im@M gave a relatively low yield (entry 6, 42%).
Even using the high-density IL-based catalyst FIP-Im@QA, the
tinily improved yield was obtained (entry 7, 56%). Then, the
1
2
Blank
FPP
<1
<1
c
3
FPP/TBAB
FIP-Im
99
99
99
72
42
56
99
67
74
32
86
4
5
6
7
8
>99
73
FIP-Py
addition of phloroglucinol (B, as acid centers) gave a
FIL-Im@M
FIP-Im@QA
FIP-Im@M/B
FIP-Im
42
significantly improved yield of 2a of up to 99% and high
selectivity (entry 8, Table 1). These results revealed the
importance of Brønsted acidic –OH group, further suggesting
the cooperative effect in this carbonate formation reaction.
After that, the effect of reaction parameters such as catalyst
56
99
d
9
67
e
1
0
FIP-Im
75
1
1
FIP-Im
32
f
2
loading, reaction temperature and pressure of CO , was also
1
2
FIP-Im
86
a
studied briefly. The use of a half amount of FIP-Im gave the
o
low yield at 80 C and 1.0 MPa pressure within 10 h (entry 9,
Reaction conditions: epichlorohydrin (1.0 mmol), catalyst (5.0 mol%,
b
catalyst amount equal to the amount of OH), initial CO
2
pressure 1.0 MPa.
c
67%). When the CO
MPa, the product yield of 2a decreased from 99 to 75% (entry
0). Similarly, with the decrease of reaction temperature, FIP-
Im exhibited the poorly catalytic performance with a yield of
2% (entry 11). Moreover, the catalytic activity of the catalyst
2
pressure was decreased from 1.0 to 0.5
Determined by GC using biphenyl as an internal standard. TBAB (2.0 mol%).
d
e
f
Catalyst (2.5 mol%). Keeping CO
2
pressure at 0.5 MPa. Keeping CO
2
1
pressure at 0.1 MPa.
3
100
100
(B)
(A)
FIP-Im was also strongly affected by the reaction time as
presented in Figure 4A. It can be clearly seen that the
carbonate yield increased gradually within 8 h and then slowly
increased in the following time. On the basis of the above
observations and in combination with the demand of practical
80
60
40
20
0
80
60
40
20
0
FIP-Im
FIP-Py
application, the optimized condition toward the conversion
o
20 40 60 80 100 were the use of FIP-Im (5.0 mol%) at 80 C and a CO
0
2
4
6
8
10 12 14 16
0
2
pressure
Time (h)
Time (h)
of 1.0 MPa under solvent-free conditions. Moreover, a high
yield of 2a (86%) was still achieved by prolonging the reaction
time, and no byproduct was detected during the reaction
process (72 h, entry 12 in Table 1; Figure 4B).
Figure
2
4 Kinetic curve for the cycloaddition reaction between CO and
epichlorohydrin catalysed by FIP-Im (5.0 mol%) at (A) 80 °C and 1.0 MPa,
compared with FIP-Py and (B) 25 °C and 0.1 MPa.
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ARTICLE
Journal Name
advantage of heterogeneity (easy to separate and recycle). To
our delight, this approach was demonstrated to be effective
for this transformation under solvent-additive-metal free
conditions as summarize in Table 2.
Table 2 Screening of the reaction conditions in the N-formylation reaction of
a
2 3
N-methylaniline with CO and PhSiH
Figure 5 Substrate scope using FIP-Im as catalyst for the cycloaddition reaction.
b
b
CO
MPa)
2
T
(°C)
t
(h)
Conv.
(%)
Yield
(%)
Reaction conditions: substrate (1.0 mmol), catalyst (5.0 mol%), CO
2
initial
Entry
Catalyst
(
pressure 1.0 MPa, 80 °C. Yields of products are shown (determined by GC).
c
d
1
2
3
4
5
−
1.0
1.0
1.0
1.0
1.0
1.0
0.5
0.1
35
35
35
80
35
35
35
25
24
24
24
24
14
14
14
72
n.d.
n.d.
7
FIP-Im
7
8
FIP-Im@M
FIP-Im@M
FIP-Im@QA
FIP-Im@QA
FIP-Im@QA
FIP-Im@QA
8
With the optimized conditions in hand, we further studied
the scope of the selected catalyst FIP-Im for the coupling
86
>99
75
84
82
85
99
75
84
82
reaction of CO with various epoxides (1a-1h). From the results
2
illustrated in Figure 5, it can be seen that the present protocol
was widely applicable to produce a variety of terminal cyclic
e
6
7
carbonates (2a-2h) with a good to high yields (76-99%) under
8
solvent/additive-free conditions. Clearly, the catalytic activity
was strongly dependent on the structure of substrate. The
activity decreased in sequence when increasing the length of
alkyl substituent. We suspected that the steric hindrance from
the long-chain substituent might lead to the decrease of the
reaction activity. When the conjugated benzene group
substituted epoxide (2g) was employed as a substrate, a
relatively lower yield (88%) was achieved under similar
a
Reaction conditions: amine (1.0 mmol), phenylsilane (1.0mmol), catalyst (6.0
b
mol%, catalyst amount equal to the amount of Br). Yields of 4a (determined
c
d
by GC using naphthalene as an internal standard). No catalyst . Not
e
detected. Catalyst (3.0 mol%).
Having prepared functional catalysts, they were tested for
conditions. This decrease might be explained as the steric the conversion of N-methylaniline 3a into N-methyl-N-
hindrance of benzene group and the conjugated effect phenylformamid 4a in the present of PhSiH (1.0 eq.) under 1.0
3
1
6a
o
2
between the benzene ring and epoxy group. Furthermore, it MPa of pure CO at room temperature (35 C). Initially,
was found that the internal epoxide (2h) was unsuitable for methylation did not occur in the absence of any catalyst (entry
this catalytic system to give a low yield of 21% within a 1, Table 2). The use of bifunctional FIP-Im or –OH protected
relatively longer reaction time (48 h) possibly as a result of the FIP-Im@OMe catalyst proved to be a less efficient catalytic
steric-hindrance. Notably, high selectivities (>99%) was system to give a very low yield of desired product (7% and 8%,
obtained for the target carbonates with no byproduct entries 2 and 3, respectively) under similar conditions.
o
formation throughout the reaction process.
Interestingly, increasing the temperature (80 C, entry 4 in
Table 2) gave a remarkably improved yield (up to 85%) of N-
methyl-N-phenylformamide with high selectivity (99 %)
pointing to the adjustability of activity for ILs-based catalyst.
Considering the insufficiently utilization of active centers in the
polymer under low reaction temperature, we further grafted
high-density active sites on the surface of FIP-Im by
substituting OH with quaternary ammonium salt through
Williamson ether reaction to afford FIP-Im@QA. During the
reaction process, the insider bromide ion could potentially
N-formylation of amines with CO and PhSiH3
2
Another important way to recyle the atmospheric carbon
dioxide is to combine both CO reduction and the construction
2
31
of C–C, C–N or C–O bond.
For instence, reductive
functionalization of CO with amines and phenylsilane to
2
selectiviely afford formamide has attracted increasingly
3
2
attention, thus yielding numerous catalytic systems. Despite
the tremendous progress noted in this reaction, most of the
reported catalytic methodologies for the selective synthesis of
formamide stiil remain at homogeneous catalysis in the
present of solvent. There is still much room for improvement
to avoid the problem from the complicated synthesis of
catalyst and the tedious separation and purification of product,
as well as the use of organic solvent. Herein, we developed a
new heterogeneous catalyst with high-density and flexible
active sites that combined the high reactivity of ILs and the
–
supplement the outsider active Br , thereby promoting the
catalytic performance. As expected, FIP-Im@QA showed
excellent catalytic activity with a formamide yield of 99%
(
entry 5, Table 2), outperforming many other protocols
reported under similar reaction conditions (Table S3). Not
surprisingly, the catalysis was weakened with a half of catalyst
loading (3.0 mol%; 75% yield; entry 6) or a lower CO
2
pressure
(
0.5 MPa; 84% yield; entry 7) under identical conditions.
6
| J. Name., 2012, 00, 1-3
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ARTICLE
Furthermore, we also investigated on this N-formylation (1.0 mmol), catalyst (6.0 mol%), CO
2
initial pressure 1.0 MPa, r.t. (35 °C), 14h.
o
reaction at 25 C under 0.1 MPa CO
2
over FIP-Im@QA
.
Yields of products are shown (determined by GC).
Encouragingly, this protocol was well applicable to N-
methylaniline to provide promising yield of N-methyl-N-
phenylformamide (82%, entry 8 in Table 2). It was worth
mentioning that no byproduct (N, N-dimethylaniline, 4b) was
observed in these screening reactions.
Catalytic conversion of diluted CO
Considering the certain CO
2
2
2 2
capture ability and CO -to-N
selectivity of FIP-Im and FIP-Im@QA, we further investigated
their catalytic performance in the corresponding reaction
under low CO
transformation of CO
CO /N = 15/85, v/v) is more meaningful and attractive than
from highly pure and compressed CO , which could largely
reduce the global CO emissions and afford various essential
chemicals. In this context, the diluted CO (15% CO in N ) was
2
concentration. In addition, the direct
Inspired by the above encouraging results, we further
exploited the generality of the developed catalytic protocol by
varying the amine substrate including electron donating
2
from flue gas (the main component:
2
2
2
substituents (–OCH
3 3
, –CH ), electron withdrawing substituents
2
(–Cl and –NO ), and other variously functionalized substituents.
2
2
2
2
As summarized in Figure 6, the catalyst FIP-Im@QA exhibited
excellent catalytic performance for producing the
corresponding formamides as sole products under the
optimized conditions. Clearly, electron- and size-dependent
catalysis was observed in this catalytic system (4a-4g, Figure 6).
used as the raw materials in the above model reactions, as
presented in Table 3. As a consequence, nearly all of
epichlorohydrin was converted into the corresponding
o
carbonate (2a) with high selectivity at 80 C and 2.0 MPa using
the catalyst FIP-Im under such a low CO
, Table 3). Then, this protocol was applied in this reaction
under atmospheric pressure (0.15 bar CO + 0.85 bar N , total
.1 MPa) and room temperature. Excitingly, when the reaction
time was prolonged to 96 h, an 86% yield of 2a was achieved
entry 2). Additionally, experiments were also done in N-
methylaniline(3a)-to-N-methyl-N-phenylformamide(4a
2
concentration (entry
Specifically,
N-methylaniline
–CH
with
electron-donating
1
substituents (–OCH
3
,
3
)
gave enhanced yields of
2
2
corresponding products (4b and 4c), while halogen (–Cl) group
suppressed the reaction activity of the substrate (4d). The N-
methylaniline with a strong electron-withdrawing substituent
0
(
2
(–NO ) could not undergo this N-formylation, giving no desired
)
product (4e). When secondary amine was substituted with
conversion by using FIP-Im@QA as a catalyst under similar
conditions, and this catalytic system was still efficient in the
corresponding transformation (entries 3 and 4, Table 3).
Therefore, the above inspiring results made the present
catalytic systems highly attractive for recycling the real-world
carbon resource as well as producing valuable chemicals.
ethyl or isopropyl group, the corresponding product was
obtained in a relatively lower yield (93%, 4f; 81%, 4g
respectively) than that of the methyl group substituted amine
99%, 4a), possibly owing to the steric effect. Encouragingly,
,
(
we found that this catalytic system was also compatible with
functionally aliphatic amines such as dibutylamine,
diallylamine, piperidine-1-carbaldehyde, morpholine and 1-
methylpiperazine (4h-4l, Figure 6). Therefore, the current
Table 3 Catalytic activities of FIP-Im and FIP-Im@QA in capture and
protocol showed a wide substrate scope, ranging from
functionally aromatic amines to aliphatic amines with high
selectivities.
a
conversion of diluted CO
2
b
b
Yield
%)
Entry
CO
2
(MPa)
T (°C)
t (h)
Conv. (%)
(
O
H
PhSiH3
FIP-Im@QA
C
N
H
N
+ CO2
R1
R2
a-3l
R1
4a-3l
R2
solvent-additive free, r.t.
3
c
c
1
2
2.0
0.1
80
25
15
96
>99
86
98
86
N
C O
H
O
N
C O
N
C O
H
Cl
N
C O
H
H
4
a, 99%
4b, 99%
4c, 99%
4d, 87%
H
O
C
N
O2N
N
N
C O
H
N
O
C O
H
H
d
d
4
e, <1%
4f, 93%
4g, 81%
4h, 99%
3
4
2.0
0.1
35
25
24
96
81
80
81
80
H
O
O
H
O
C
H
O
C
H
C
N
N
O
N
N
N
C
a
b
Diluted CO (15 % N in 85% N , v/v, sImulation of flue gas). Conversions
2
2
2
c
and yields of product (determined by GC). 1a (1.0 mmol), catalyst (5.0
4
i, 92%
4j, 99%
4k, 99%
4l, 99%
d
mol%). 3a (1.0 mmol), PhSiH
3
(1.0mmol), catalyst (6.0 mol%).
Figure 6 Investigated scope the formation of substituted formamides (4a-4l)
catalyzed by FIP-Im@QA. Reaction conditions: substrate (1.0 mmol), phenylsilane Recycling Experiments
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Admittedly, the recyclability of a catalytic system is one Finally, the intramolecular cyclization via a nucleophilic attack
of the most important criteria from a practical perspective. resulted in release of the product and regeneration of the
Owing to the heterogeneous nature of the current polymeric catalyst.
catalysts, recycling experiments for the cycloaddition of CO
2
2
O
CO
2
with epichlorohydrin over FIP-Im and the N-formylation of CO
OH
OH
OH
R
O
O
O
R
O
with N-methylaniline and phenylsilane over FIP-Im@QA were
conducted under the optimal conditions, respectively.
Fortunately, after the reaction, both of the solid catalyst could
be easily recovered by filtration, washing with acetone and
R
O
Br
Br
R
Br
O
O
(A)
O
R
o
FIP-Im:
OH
FIP-Im@QA:
drying in a vacuum at 60 C, and then used directlly for the
O
C
O
next run. As presented in Figure 7, after six runs, the yield of
the desired product (4-(chloromethyl)-1,3-dioxolan-2-one or
N-methyl-N-phenylformamide) for the corresponding tested
reaction did not decrease obviously, and the selectivity
remained almost the same (>98%) during the recycling process.
The FT-IR spectrum and elemental analysis did not remarkably
change in the composition of the polymeric catalysts after
recycling 6 times (Figure S8 and Table S1), demonstrating their
excellent stability.
O
Br
O
H
(B)
Br
C
N
R1
R2
R
1
NH
O
C O
O
O
C
H
C
R
2
PhH
2
Si
H
O
SiH
Ph
2
O
PhSiH
3
H
O
Br
R1
H
N
O
Br
SiH
2
Ph
R2
Scheme 3 Proposed reaction mechanism for the cycloaddition of CO
epoxide over FIP-Im (A) and N-formylation of amines with CO and PhSiH
FIP-Im@QA (B).
2
with
over
2
3
To gain insight into the N-formylation reaction of amines
1
with CO and PhSiH catalyzed by FIP-Im@QA, H NMR analysis
2
3
1
was carried out as depicted in Figure S9. In the H NMR spectra
of PhSiH and its mixture with catalyst in DMSO-d6, as well as
3
N-methylaniline and its mixture with catalyst in DMSO-d6, a
shift of the signal assigning to Si–H of PhSiH or N–H of N-
3
methylaniline was observed, suggesting the interaction
between PhSiH3 or N-methylaniline and catalyst (see the
supporting information for details). Therefore, the plausible
mechanism for this transformation was proposed (Scheme 3B),
3
2d,32g,34
which is in accordance with the previous works.
The
catalytic cycle started with the activation of Si−H bond of
phenylsilane by quaternary ammonium bromide in the catalyst
FIP-Im@QA, thus making the CO insertion more favorable to
2
Figure 7 Catalytic reusability of FIP-Im for the cycloaddition of CO
epichlorohydrin and FIP-Im@QA for the N-formylation of CO with N-
methylaniline and PHSiH under the optimal conditions.
2
with
afford the pivotal silyl formate intermediate. Simultaneously,
amine binds with the quaternary ammonium bromide by
formation of hydrogen bond, affording an activated substrate
containing a nucleophilic N atom. At last, a nucleophilic attack
on the carbon atom of silyl formate species leads to the
formation of new C−N bond, thus furnishing the desired
formamide accompanied with the release of a silanol and the
regeneration of catalyst.
2
3
Reaction mechanism
1
6a,30b,33
According to the previous works
and in combination
with the experimental results, the plausible mechanism of the
catalytic cycle for the cycloaddition or N-formylation reaction
was deduced as described in Scheme 3. Firstly, for the FIP-Im
-
Conclusions
catalyzed CO /epoxide cycloaddition reaction (Scheme 3A), the
2
dual activation of epoxides begins with the hydrogen bonding Various new function-oriented ionic polymers featuring high-
interaction between the oxygen atom of the epoxide and the density active sites were synthesized, and then employed as
hydrogen atom of phenolic hydroxyl group (-OH) in the efficient heterogeneous catalysts for CO2 sustainable
bifunctional catalyst FIP-Im. Concurrently, the ring opening transformation. Firstly, we described a one-pot pre-synthetic
occurs through a nucleophilic attack of bromide ion on the method for novel polyphenolic ionic polymers (FIPs) from a
less-hindered carbon atom of epoxide, affording a highly active facile phenol-formaldehyde condensation reaction between
OH…O intermediate that made the insertion of a carbon phloroglucinol
and
IL-modified
dialdehydes
under
dioxide molecule more favorable. Subsequently, an OH- solvothermal conditions. Owing to the synergistic effect
binding bromo alkoxide carbonate intermediate is formed. among phenolic hydroxyl groups, imidazolium cations and
8
| J. Name., 2012, 00, 1-3
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ARTICLE
nucleophilic haloid anions, the bifunctional catalyst FIPs Synthesis of FIP-Im@M. FIP-Im@M was prepared through the
exhibited good catalytic activity for the metal–solvent– Williamson ether reaction between the phenol group in FIP-Im
additive-free production of extensive cyclic carbonates from and methyl bromide. Specifically, a mixture of FIP-Im (100 mg),
2 3 2 3
CO and epoxides under milder conditions. To obtain higher CH Br (0.73 mL, 11.7 mmol), and K CO (1.19 g, 10 mmol) in
density and more flexible IL active sites, we further dry DMF (15 mL) was stirred at reflux for 24 h. After cooling,
intercalated the quaternary ammonium into the framework of the solid was obtained by filtration, washed with methanol
FIP-Im through the Williamson ether reaction by using a post- and acetone for several times, and then dried at 100 °C under
synthetic method. The resultant FIP-Im@QA was also efficient vacuum for 12 h.
for the N-formylation reaction of multitudinous amines with
Synthesis of FIP-Im@QA. A mixture of FIP-Im (0.3 g),
CO
the abilities of CO
function-oriented catalysts could smoothly catalyzed
the above two transformations under low CO concentration
15% in 85% N , v/v). It's also worth mentioning that the
selected catalysts FIP-Im and FIP-Im@QA could be
2 3
and PhSiH at 35 °C and 1.0 MPa. Moreover, on account of
[
3 2 3
BrBuNEt ]Br (2 mmol, 0.61 g), K CO (3 mmol, 0.41g) and dry
2
2 2
capture and CO /N selectivity, these
DMF (15 mL) was refluxed for 24 h. After cooling, the
precipitate was collected by filtration, washed with ethanol
and acetone, and then dried at 100 ºC under vacuum for 12 h
to give FIP-Im@QA quantitatively as a dark yellow solid.
2
(
2
(
)
conveniently recovered and availably reused for more than 6
times in the corresponding reaction. Therefore, to a
certain extent, this research points out a sustainable direction
Conflicts of interest
There are no conflicts to declare.
2
for heterogeneous catalysis of CO fixation into valuable
products based on the concept of function-oriented catalysis.
Acknowledgements
Experimental section
We greatly appreciate the financial support from the National
Natural Science Foundation of China (21425627 and
Materials
2
1676306), the National Key Research and Development
All solvents and reagents, unless otherwise noted, were
available from local suppliers with the highest purity and used
as received. Deionized water was commonly used in our
laboratory. Epoxides, amines, and phenylsilane were
purchased from J&K Scientific Ltd. Phloroglucinol, 4,4'-
bipyridine, N,N-dimethylglycine, 1H-imidazole, copper iodide,
Program of China (2016YFA0602900), the Natural Science
Foundation of Guangdong Province (2016A030310211), and
the Characteristic Innovation Project (Natural Science) of
Guangdong Colleges and Universities (2016KTSCX004).
4,4’-biphenyldicarboxaldehyde,
1,4-dioxane,
1,4-
Notes and references
dibromobenzene and 4-(bromomethyl) benzaldehyde were
purchased from Energy Chemical or Beijing HWRK CHEM.
Methyl bromide was obtained from Aladdin. IL-functionalized
dialdehydes and (2-bromobutyl)triethylammonium bromide
were synthesized according to the reported literature (see the
Supporting Information).
1
(a) A. M. Appel, J. E. Bercaw, A. B. Bocarsly, H. Dobbek, D. L.
DuBois, M. Dupuis, J. G. Ferry, E. Fujita, R. Hille, P. J. Kenis, C.
A. Kerfeld, R. H. Morris, C. H. Peden, A. R. Portis, S. W.
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2
c) Q. Liu, L. Wu, R. Jackstell and M. Beller, Nat. Commun.,
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Synthesis of catalysts
2
(a) J. Klankermayer, S. Wesselbaum, K. Beydoun and W.
Leitner, Angew. Chem. Int. Ed., 2016, 55, 7296; (b) Q.-W.
Song, Z.-H. Zhou and L.-N. He, Green Chem., 2017, 19, 3707;
Synthesis of FIP-Im, FIP-Py and FPP. Typically, a mixture of A
608 mg, 1.0 mmol) and phloroglucinol (B, 168 mg, 1.3 mmol)
1
(
(
2
c) C. Maeda, Y. Miyazaki and T. Ema, Catal. Sci. Technol.,
014, , 1482; (d) T. Sakakura, J. C. Choi and H. Yasuda,
and 1, 4-dioxane (5 mL) were added into a 25 mL round-
bottom flask. After heated to 70 °C for 1 h, the reaction
mixture was transferred into a 25 mL autoclave with a Teflon
lining. Then, the autoclave was then sealed and heated in a
temperature programmed oven at 220 °C for 4 days. After
cooling to room temperature, the resulting precipitate was
collected by filtration, washed with DMF, ethanol, water, THF,
and acetone for several times. Then the target polymer was
4
Chem. Rev., 2007, 107, 2365; (e) M. Aresta, A. Dibenedetto
and A. Angelini, Chem. Rev., 2014, 114, 1709; (f) A.
Goeppert, M. Czaun, J.-P. Jones, G. K. Surya Prakash and G.
A. Olah, Chem. Soc. Rev., 2014, 43, 7995; (g) A. W. Kleij, M.
North and A. Urakawa, ChemSusChem, 2017, 10, 1036.
3
4
(a) W. Qian, J. Texter and F. Yan, Chem. Soc. Rev., 2017, 46
1124; (b) S. Zulfiqar, M. I. Sarwar and D. Mecerreyes, Polym.
Chem., 2015, , 6435; (c) X. Wang, Y. Zhou, Z. Guo, G. Chen,
J. Li, Y. Shi, Y. Liu and J. Wang, Chem. Sci., 2015, , 6916; (d)
,
6
6
3
extracted with CH OH and dried at 120 °C under vacuum for 24
Q.-W. Song, L.-N. He, J.-Q. Wang, H. Yasuda and T. Sakakura,
Green Chem., 2013, 15, 110; (e) Y. Zhang, B. Wang, E. H. M.
Elageed, L. Qin, B. Ni, X. Liu and G. Gao, ACS Macro Lett.,
h to obtain FIP-Im as dark yellow powder in 92 % yield.
Additionally, the synthesis of FIP-Py was carried out following
the same protocol, by replacing the A
mmol). As a comparison, the FPP polymeric analogue FPP was
also prepared by using A (210 mg, 1.0 mmol) and B (168 mg,
.3 mmol) as the reactants according to a similar procedure.
1
with A
2
(554 mg, 1.0
2016, 5, 435.
(a) Z.-Z. Yang, Y. Zhao, G. Ji, H. Zhang, B. Yu, X. Gao and Z. Liu,
Green Chem., 2014, 16, 3724; (b) Y. Xie, Q. Sun, Y. Fu, L.
Song, J. Liang, X. Xu, H. Wang, J. Li, S. Tu, X. Lu and J. Li, J.
0
1
Mater. Chem. A, 2017,
5
, 25594; (c) A. Dani, E. Groppo, C.
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Page 11 of 11
Journal of Materials Chemistry A
View Article Online
DOI: 10.1039/C8TA00823J
Graphical Abstract
Function-oriented ionic polymers featuring high-density
active sites for sustainable carbon dioxide conversion
a
b
a
a
a
c
Yaju Chen, Rongchang Luo,* Junhui Bao, Qihang Xu, Jun Jiang, Xiantai Zhou,
a
and Hongbing Ji*
a
Fine Chemical Industry Research Institute, Key Laboratory of Low-Carbon Chemistry & Energy
Conservation of Guangdong Province, School of Chemistry, Sun Yat-sen University, Guangzhou,
Guangdong 510275, P.R. China.
b
School of Chemical Engineering and Light Industry, Guangdong University of Technology,
Guangzhou, Guangdong 510006, P.R. China.
c
School of Chemical Engineering and Technology, Sun Yat-sen University, Zhuhai, Guangdong
5
*
19000, China
Correspondence: luorch@gdut.edu.cn (R.C. Luo); jihb@mail.sysu.edu.cn (H.B. Ji)
Based on the concept of function-oriented synthesis, we pertinently developed a series
of new functional ionic polymers, which exhibited good catalytic performance, robust
constancy, and excellent substrate expansibility for sustainable catalysis of
CO -involved reactions.
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