Coordination-Supported Imidazolate Networks: Water- and Heat-Stable Mesoporous Polymers for Catalysis

Article abstract of DOI:10.1002/chem.201702430

The poor water stability of most porous coordination polymers (PCPs) or metal-organic frameworks (MOFs) is widely recognized as a barrier hampering their practical applications. Here, a facile and scalable route to prepare metal-containing polymers with a good stability in boiling water (100 °C, 24 h) and air (up to 390 °C) is presented. The bifunctional 1-vinylimidazole (VIm) with a coordinating site and a polymerizable organic group is introduced as the building block. This core strategy includes the synthesis of a rigid monomer with four VIm branches through a coordination process at room temperature, followed by a radical polymerization. We refer to this material as coordination-supported imidazolate networks (CINs). Interestingly, CINs are composed of rich mesopores from 2–15 nm, as characterized by low-energy (60 kV) STEM-HAADF images. In particular, the stable CINs illustrate a high turnover frequency (TOF) of 779 h^?1 in the catalytic oxidation of phenol with H₂O as the green solvent.

Full text of DOI:10.1002/chem.201702430

A Journal of
Accepted Article
Title: Coordination-supported Imidazolate Networks: Water- and
Thermally Stable Mesoporous Polymers for Catalysis
Authors: Pengfei Zhang, Shize Yang, Matthew F Chisholm, Xueguang
Jiang, Caili Huang, and Sheng Dai
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To be cited as: Chem. Eur. J. 10.1002/chem.201702430
Link to VoR: http://dx.doi.org/10.1002/chem.201702430
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Chemistry - A European Journal
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COMMUNICATION
Coordination-supported Imidazolate Networks: Water- and
Thermally Stable Mesoporous Polymers for Catalysis
Pengfei Zhang,[a,b], #,* Shize Yang,[b], # Matthew F. Chisholm, Xueguang Jiang , Caili Huang and
[b]
[c]
[b]
Sheng Dai*[b,c]
Abstract: The poor water stability of most porous coordination
polymers (PCPs) or metal-organic frameworks (MOFs) is widely
recognised as a barrier hampering their practical applications.
Herein, a facile and scalable route to prepare metal-containing
hydrolysis of metal ions can happen in moist conditions, thus
significantly lowering or even destroying the molecular scale
porosity.[4] To date, the design of water- and thermally stable
PCPs is still of great difficulty and highly pursued.
In this contribution, we introduce several robust porous
materialsCoordination-supported Imidazolate Networks (CINs)
with preferred chemical stability in refluxing water and high
thermal stability (up to 390°C) in air. The synthesis of CIN-1
started with the coordination between 1-vinylimidazole (VIm) and
zinc nitrate at room temperature (Scheme 1). This coordination
o
polymers with a good stability in boiling water (100 C, 24 h) and air
o
(
up to 390 C) is presented. The bifunctional 1-vinylimidazole (VIm)
with both a coordinating site and a polymerizable organic group is
introduced as the building block. This core strategy includes the
synthesis of
a rigid monomer with four VIm branches via a
coordination process at room temperature, followed by a radical
polymerization. Here we call this material Coordination-supported
Imidazolate Networks (CINs). Interestingly, CINs are composed of
rich mesopores from 2 to 15 nm, as characterized by low-energy (60
kV) STEM-HAADF images. Especially, the stable CINs illustrate a
behavior with the formation of ionic [Zn(C
n
-Im)
4
][NO
3
]
2
complex
3 2
][NO ]
has been well studied.[ In current synthesis, a [Zn(VIm)
5]
4
complex with four vinyl groups was used as a reactive building
block.
Subsequently,
the
radical
polymerization
of
-
1
high turnover frequency (TOF) of 779 h in the catalytic oxidation of
phenol with H O as the green solvent.
[Zn(VIm)
4
][NO complex was carried out under solvothermal
3 2
]
[6]
2
conditions, in order to gain a higher degree of cross-linking.
The complete polymerization of the [Zn(VIm) ][NO monomer
was indicated by the disappearance of the characteristic peak
for vinyl group (1650 cm ) in FTIR spectra (Figure S1). Finally,
a polymer monolith was observed, and it was washed and dried
to give CIN-1 powder.
4
3 2
]
Porous coordination polymers (PCPs) have been recognized as
an interesting class of highly porous materials with many
promising applications, such as gas storage, separation, and
catalysis.[ Especially, PCPs with two
−1
1]
or
three-dimensional
crystalline
frameworks are attracting increasing
attention because of their rich porosity,
uniform
pore
size,
prescribed
[
2]
structural features, and so on. One
of the most important challenges in
the PCP community is to overcome
the poor stability of many PCPs in
water.[3] Because water vapor is
ubiquitous in real-world processes
(
e.g., industrial flue gas), the
instability of PCPs under water-
containing conditions limits their
practical applications. The collapse of
the
framework
by
competing
Scheme 1. The reaction pathway to prepare coordination-supported imidazolate networks.
The investigation of the reaction parameters is summarized
in Table 1. Solvent used in the synthetic process is an important
issue, and DMF is a preferred solvent for a higher surface area.
The different solubility and affinity of solvents affect the
precipitating of oligomer and the formation textural structure.[
[
[
a]
b]
Dr. P. F. Zhang
School of Chemistry and Chemical Engineering,
Shanghai Jiao Tong University
Shanghai 200240, P. R. China
E-mail: chemistryzpf@sjtu.edu.cn
Dr. P. F. Zhang, Dr. S. Z. Yang, Dr. M. F. Chisholm, Dr. C. Huang,
Dr.. S. Dai
Oak Ridge National Laboratory
6a]
Various molar ratios of zinc nitrate/VIm (1:2, 1:3, 1:4, 1:5, 1:6)
3 2
were then investigated. The formation of [Zn(VIm) ][NO ]
4
Oak Ridge, TN 37830, United States
E-mail: dais@ornl.gov
Dr. X. G. Jiang and Prof. S. Dai
Department of Chemistry, University of Tennessee
Knoxville, TN 37996, United States
Those authors contribute equally to this work.
intermediate with a molar ratio of 1:4 is appropriate without extra
metal salts or VIm molecules. In addition, the product yield
gained ~15% in a long reaction time of 72 h. This synthetic
process is scalable, and ~5.5 g CIN-1 product can be obtained
per batch with treble amount of starting materials. Respecting to
the porosity control and product yield, the optimized condition
[
c]
#]
[
Supporting information for this article is given via a link at the end of
the document.
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Chemistry - A European Journal
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COMMUNICATION
Figure 1. a) Solid-state 13C CP/MAS NMR analysis of CIN-1, b) FTIR spectra
3 2
entails Zn(NO ) (3 mmol) and VIm (12 mmol) in DMF for a
of CIN-1 and CIN-2, c) TGA curve of CIN-1 and CIN-2 in air, heating rate:
polymerization time of 24 h. (Figure S2-4).
o
-1
1
0 Cmin .
The formation of CIN-1 structure was then studied by the
1
3
solid-state C NMR spectra (Figure 1a). Peaks A-B are
attributed to the aliphatic carbons on the cross-linked chain. The
electron-withdrawing effect from the nitrogen atom on the
imidazole ring makes the -C (= 53.3 ppm) exhibit a higher shift
than -C (= 42.4 ppm). The signals at = 136.8, 128.1, and
2
+
Although CIN-1 is an ionic polymer with a positive Zn -
supported backbone and NO -
anions on the neighborhood, it is
3
hydrophobic. The contact angle was 132°, when a water droplet
fell on the CIN-1 surface. The highly cross-linked poly(VIm)
network may contribute to this feature.[ The X-ray diffraction of
1
20.7 ppm are assigned to the imidazole carbons. The peak for
C-2 of imidazole locates at 136.8 ppm, while peaks at 128.1 and
20.7 ppm are induced by the C-4 and C-5 of imidazole,
6c]
o
CIN-1 shows a broad peak around 22 , revealing its amorphous
1
structure (Figure S5). The charged network is highly functional,
which offers an opportunity to attach different anions with a
specific task.[7] As an example, the introduction of thermally
stable bis(trifluoromethane)sulfonimide(TFSI) anions into CIN-1
was then carried out in 20wt% LiTFSI aqueous solution and the
powder product noted as CIN-2. The anion-exchange process
was suggested by FTIR spectra, in which four characteristic
respectively. The structure of CIN-1 and monomer is also
confirmed by elemental analysis (See Experimental Section).
Table 1. Summary of reaction parameters in the synthesis of CINs.
VIm
mmol)
Time
(h)
Yield
(g)
Metal Salt
Solvent
S
BET
(
−
1
peaks (1345, 1185, 1131, and 1053 cm ) relating to the
vibrational bands of TFSI anions (ν (SO ), ν (CF ), ν (SO ), and
(S–N–S), respectively) were observed (Figure 1b). Meanwhile,
a
2
a
3
s
2
Zn(NO
3
)
2
, 3 mmol
12
12
12
12
6
DMF
24
24
24
24
24
24
24
24
72
24
24
24
24
1.47
1.90
1.76
1.58
1.02
1.32
1.85
2.01
1.70
5.55
0
122
55
77
43
22
38
79
80
106
119
-
ν
a
Zn(NO
Zn(NO
Zn(NO
Zn(NO
Zn(NO
Zn(NO
Zn(NO
Zn(NO
Zn(NO
3
)
)
)
)
)
)
)
)
)
2
, 3 mmol
2
, 3 mmol
2
, 3 mmol
2
, 3 mmol
2
, 3 mmol
2
, 3 mmol
2
, 3 mmol
2
, 3 mmol
2
, 9 mmol
Ethanol
the chemical composition of CIN-2 was also confirmed by
elemental analysis (See Experimental Section).
3
3
3
3
3
3
3
3
3
CH CN
As shown in the thermal gravimetric analysis (TGA) curves,
both CIN-1 and CIN-2 exhibit a good thermal stability in air and
NMP
DMF
DMF
DMF
DMF
DMF
DMF
DMF
DMF
DMF
o
the decomposition occurs at the temperature up to 390 C
-
(
1
Figure 1c). It is clear that the replacement of NO
3
anion in CIN-
-
by TFSI anion can increase the thermal stability of the whole
9
network. In addition, the weight percentage of the residues
matches well with the theoretical one if ZnO is considered as the
residue (CIN-1, Calculated: 14.4%, Found: 14.3%; CIN-2,
Calculated: 8.3%, Found: 8.9%). The neutral imidazole network
may contribute to the outstanding thermal stability in air.
15
18
12
36
12
12
12
The porous architecture of CINs is evaluated by
adsorption-desorption measurement at 77 K. The adsorption
branch of CIN-1 shows an increasing N uptake as the increase
of relative pressure from 0.1, while only limited N uptake is
N
2
2
Zn(OAc)
Co(NO
Ni(NO
2
, 3 mmol
2
3
)
2
, 3 mmol
1.77
1.65
91
77
observed at a low relative pressure (e.g., <0.1), indicating the
mesoporous texture (Figure 2a). The sorption isotherm of CIN-1
is a characteristic type IV profile with a H3 hysteresis loop and a
3
)
2
, 3 mmol
0
capillary condensation step at P/P =0.4–0.6, as a result of
irregular mesopores. Meanwhile, a wide pore size distribution
from 2 to 15 nm was observed by the BJH model (Figure 2b).
The specific surface area of CIN-1 by Brunauer-Emmett-Teller
2
-1
(
BET) method is 122 m g . Thus, CIN-1 possesses the sorption
feature of mesoporous material.
The resistance of CIN-1 to water was explored by soaking
the powder in boiling water for 24 h. Interestingly, the weight
recovery is 97% and the N adsorption-desorption isotherm of
2
the treated polymer together with the pore size distribution
maintain the similar profiles with the pristine ones (Figures 2a-
2
-1
2
b). The specific surface area decreases a little to 107 m g .
Base on those observations, it seems fair to say that CIN-1 is
quite stable in water. We reason the water stability of CIN-1 from
two points: i) The metal center is in fact surrounded by
hydrophobic poly(VIm) network, which can prevent the attacking
by water molecules to some content; ii) The network
backbonesupported by neutral VIm coordinating is stable no
matter the hydrolysis occurs or not. In other words, the possible
-
-
hydrolysis would replace the NO
3
anion by OH anion, while it
2
+
do not destroy the Zn -VIm coordination.
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Chemistry - A European Journal
10.1002/chem.201702430
COMMUNICATION
Moreover, this strategy can be easily extended to the
2
+
2+
synthesis of Co - or Ni -supported network (CIN-3 and CIN-4),
in the presence of Co(NO or Ni(NO (Table 1).
3
)
2
3
)
2
N
2
adsorption-desorption measurements for both polymers showed
type-IV isotherms with clear hysteresis loops at relative
pressures
Figure 3. STEM-HAADF image of CIN-1 at 60 kV. Red circles in the figure left
highlight several surface pores.
By coupling the attractive properties of the transition-metal
catalyst (e.g., redox metal center) and the unique features of
mesoporous supports (e.g., large pore size and good stability),
CINs are interesting catalyst candidates for selective oxidations.
Catalytic oxidation of phenol to catechol (CAT) and
hydroquinone (HQ) is a key process in the fine-chemical industry,
while an efficient heterogeneous catalyst is preferred for this
process.[ In the subsequent study, CINs were applied in phenol
8]
oxidation with water as solvent and H
2 2
O as oxidant. No
products were observed in the blank run (Entry 1, Table 2). The
2
+
Zn -centered CIN-1 cannot promote this oxidation either (Entry
Table 2). Interestingly, the CIN-3 with Co2 centers
+
2,
coordinated by imidazole ligand showed a good activity in the
Figure 2. a-b) N
size distribution, c-d) N
CIN-4 and the pore size distributions.
2
adsorption-desorption isotherm (77 K) of CIN-1 and the pore
adsorption-desorption isotherms (77 K) of CIN-3 and
oxidation of phenol, and a high turnover frequency (TOF) of 779
h-1 was achieved (Entry 3, Table 2). While the Ni2+-based CIN-4
2
only offered a moderate activity (Entry 4, Table 2). As a solid
catalyst, CIN-3 can be easily recovered by centrifugation and
reused three times with a slight loss of efficiency (Entries 5-7,
Table 2). An Inductively coupled plasma atomic emission
spectroscopy (ICP-AES) study showed that ~2.7% cobalt of
the total catalyst was left in the solution. Hence, CIN-3 could
be considered as a promising catalyst in the catalytic
oxidation of phenol.
between 0.4 and 0.8, indicating the characteristic of mesoporous
structure (Figure 2c). The pore size distribution of CIN-3 locates
in 2-15 nm, while CIN-4 possesses the mesopores in a narrower
range (2-10 nm) (Figure 2d). The BET surface areas for CIN-3
and CIN-4 are 91 and 77 m g , respectively. Hence, current
strategy is a general method to construct transition-metal-
supported polymer networks.
The network morphology was then studied with CIN-1 as a
typical sample. CIN-1 is composed of irregular particle
aggregations with their diameters in several hundred
nanometers, as seen in the scanning electron microscopy (SEM)
2
-1
In summary, we introduced a series of mesoporous CINs with
an exceptional water- and thermal stability. A simple and
scalable route by the combination of coordination and radical
polymerization is presentedstarting from abundant and
inexpensive VIm, which is different from imidazole series
containing two nitrogen coordinating cites for zeolitic imidazolate
framework (ZIFs). The key points of this stable CINs include: a)
Hydrophobic poly(VIm) network to resist the hydrolysis of metal
centers; b) The backbone by coordinating metal ions to neutral
VIm is stable even though the hydrolysis-induced anion-
exchange somewhat occurs; c) The outstanding thermal stability
of heteroatom-containing imidazole ring. As expected, the CINs
as catalysts for selective oxidation of phenol showed a high TOF
(
Figure S6). Because of the rapid decomposition of polymer
materials under a strong electron beam (e.g., 200 kV), the local
structure of CIN-1 was observed by scanning transmission
electron microscopy in high angle annular dark field mode
(
STEM-HAADF) at 60 kV. Figure 3a displays the abundant
pores within a large domain of CIN-1. Wormhole-like mesopores
staying side by side are observed in a high-resolution image,
and the apparent pore sizes are in the range of 4-7 nm, which
-1
2
up to 779 h , while their water stability allows the use of H O as
2
agrees well with the pore size distribution by N adsorption
green solvent. We believe that the current finding will inspire a
number of stable metal-supported porous polymers by careful
selection of ligands, thus opening up a new pathway to porous
inorganic-organic materials.
measurement (Figure 3b). The formation of such porosity
should be the result of interstitial space inside the highly cross-
linked and rigid network. Meanwhile, the rapid and uncontrolled
radical polymerization may lead to the amorphous network with
a broad pore size.
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Chemistry - A European Journal
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COMMUNICATION
Table 2. Catalytic oxidation of phenol by CINs.[a]
Catalytic oxidation of phenol: In a typical oxidation, 100 mmol phenol (9.4
g), 10 mL water and 20 mg CIN catalyst were added into a 100 mL glass-
reactor, which was fitted with a reflux condenser. The reaction was
o
performed at 60 C in a water bath with magnetic stirring (stirring rate:
2 2
1000 rpm). 100 mmol 30%H O was added to the reaction drop by drop
(~10 min). After completion of the reaction (1 h), the reaction mixture was
weighed, and the liquid phase of the reaction mixture was collected by
filtration for GC analysis (diluted by ethanol) with internal standards
(anisole).
Sel. (%)
Conv.
%)
TOF
(h )
Entry
Catalyst
T(°C)
-
1
(
CAT
-
HQ
-
BQ
-
1
2
3
-
60
60
60
60
60
60
60
<0.1
<0.1
26.4
5.8
-
Acknowledgements
CIN-1
CIN-3
CIN-4
CIN-3
CIN-3
CIN-3
-
-
-
-
This work was sponsored by Shanghai Pujiang Program
58
62
55
61
63
15
35
16
16
13
17
-
779
171
758
658
608
(
17PJ1403500). The electron microscopy at ORNL (S. Z. Y. and
4
M. F. C.) was supported by the U.S. Department of Energy,
Office of Science, Basic Energy Sciences, Materials Sciences
and Engineering Division.
5 [b]
25.7
22.3
20.6
19
13
20
6 [c]
7 [d]
Keywords: Mesoporous Materials • Mesoporous Polymers •
Porous Poly(ionic liquid)s • Porous Coordination Polymers •
Phenol Oxidation
[
a]
Reaction condition: phenol 100 mmol, catalyst 20 mg, 30% H
2
O
2
100 mmol,
1
h, TOF = [reacted mol phenol] / [(total mol metal) × (reaction time)], Conv.:
[
b]
[c]
conversion, Sel.: selectivity.
third run with recycle catalyst. [d] The fourth run with recycled catalyst.
The second run with recycled catalyst.
The
[1]
[2]
[3]
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3 2 2
Synthesis of CIN-1: In a typical process, 3 mmol Zn(NO ) •6H O (900
mg) and 20 mL DMF were added into a glass-reactor (50 mL) under
stirring. After the dissolution of Zn salt at room temperature, 12 mmol 1-
vinylimidazole (1.12 g) was added into the solution and the mixture was
stirred for 4 h with argon flowing. Then, 50 mg AIBN was added into the
mixture and the solution was transferred into an autoclave (45 ml, PARR
INSTRUCMENT). The reactor was sealed and put into air oven for the
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o
solvothermal treatment at 120 C (24 h). After cooling down, the polymer
monolith was washed with DMF, D.I. water and ethanol. Final product
(
[
CIN-1) was got as a white powder. Elemental analysis of CCN-1:
theoretic data; C: 42.4%, H: 5.6%, O: 17.0% and N: 24.7%], [Found
data; C: 40.4, H: 5.1, O: 17.1 and N: 21.6].
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Synthesis of CIN-1 monomer ([Zn(VIm)
mmol Zn(NO •6H O (900 mg), 12 mmol 1-vinylimidazole (1.12 g) and
0 mL THF were added into a glass-reactor (50 mL). The mixture was
4 3 2
][NO ] ): In a typical process, 3
3
)
2
2
2
stirred at room temperature for 1 h. The precipitation was separated and
washed twice by THF (20 mL). The product was dried at room
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temperature in vacuum. Elemental analysis: [theoretic data; C: 42.4, H:
1
4
.2 and N: 24.8], [Found data; C: 40.9, H: 4.6 and N: 23.2]. H NMR (ppm,
2 2 2
D O):  = 7.14-7.16 (d, -CH , 1H), 7.74-7.78 (d, -CH , 1H), 9.24 (s, -CH-,
1H), 9.39-9.45 (q, -N-CH-), 9.89 (s, -CH-, 1H), 10.23 (s, -CH-, 1H).
Synthesis of CIN-2: The anion-exchange from NO -
to TFSI was carried
-
3
out in LiTFSI aqueous solution. Briefly, 300 mg CIN-1 powder was added
into 25 g LiTFSI (20 wt%) aqueous solution and stirred at 50 C for 24 h.
Then, the solid was filtered and 25 g fresh LiTFSI (20 wt%) aqueous
solution was added to repeat the anion-exchange process. Finally, the
solid product was washed with water and ethanol, giving CIN-2 as the
white powder. Elemental analysis: [Theoretic data; C: 28.7, H: 3.2%, O:
[5]
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o
12.8 and N: 14.0], [Found data; C: 29.6, H: 3.1, O: 14.1 and N: 14.5].
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Chemistry - A European Journal
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2
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2
5
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Chemistry - A European Journal
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COMMUNICATION
Entry for the Table of Contents
COMMUNICATION
Stable Metal-containing Polymers are
designed from versatile 1-vinyl-
imidazole (VIm) with both coordinating
sites and reactive organic groups. The
synthetic strategy includes the
Pengfei Zhang,* Shize Yang, Matthew
F. Chisholm, Xueguang Jiang, Caili
Huang, Sheng Dai*
Page No. – Page No.
coordination between VIm and metal
Coordination-supported Imidazolate
Networks: Water- and Thermally
Stable Mesoporous Polymers for
Catalysis
2
+
2+
2+
ions (Zn , Co , Ni ), followed by a
radical polymerization. This concept
enables porous metal-based polymers
with exceptional stability in water
o
o
(
100 C, 24 h) and air (up to 390 C).
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