Synthesis of anion-functionalized mesoporous poly(ionic liquid)s: Via a microphase separation-hypercrosslinking strategy: Highly efficient adsorbents for bioactive molecules

Article abstract of DOI:10.1039/c7ta01986f

The synthesis of porous materials with a well-defined pore structure and functionality is centrally important for the development of advanced adsorbents and sensors. In this study, we explore a direct and facile methodology combining microphase separation and hypercrosslinking, and prepare anion-functionalized mesoporous poly(ionic liquid)s (MPILs) with well-developed mesopores. This methodology involved a copolymerization of IL monomers and crosslinkers to create mesopores via microphase separation. Additionally, the MPILs were texturally engineered by hypercrosslinking to stabilize/rebuild labile collapsed mesoporous networks and generate microporosity. Thus, a new family of anion-functionalized MPILs containing amphiphilic long-chain carboxylate ionic liquids (LCC-ILs) were synthesized. These anion-functionalized MPILs exhibited extraordinarily high adsorption capacity (211.45 mg g^-1 for tocopherols) and excellent selectivity (S_δ/α, 8.65; S_βγ/α, 4.20) for bioactive tocopherol homologues and organic phenolic compounds with high structural similarity, significantly better than those of commercial adsorbents or common MPILs. Additionally, anion-functionalized MPILs demonstrated enhanced carbon dioxide (CO₂) capture performances (28.18 mg g^-1 at 0 °C and 1 bar). This study demonstrates the great potential of anion-functionalized MPILs as advanced adsorbents, and facilitates a textural engineering approach to the development of novel porous ionic materials for other applications.

Full text of DOI:10.1039/c7ta01986f

View Article Online
View Journal
Journal of
Materials Chemistry A
Accepted Manuscript
This article can be cited before page numbers have been issued, to do this please use: X. Suo, L. Xia, Q.
Yang, Z. Zhang, Z. Bao, Q. Ren, Y. Yang and H. Xing, J. Mater. Chem. A, 2017, DOI: 10.1039/C7TA01986F.
This is an Accepted Manuscript, which has been through the
Volume
4 Number 1 7 January 2016 Pages 1–330
Royal Society of Chemistry peer review process and has been
accepted for publication.
Journal of
Materials Chemistry A
Accepted Manuscripts are published online shortly after
Materials for energy and sustainability
www.rsc.org/MaterialsA
acceptance, before technical editing, formatting and proof reading.
Using this free service, authors can make their results available
to the community, in citable form, before we publish the edited
article. We will replace this Accepted Manuscript with the edited
and formatted Advance Article as soon as it is available.
You can find more information about Accepted Manuscripts in the
author guidelines.
Please note that technical editing may introduce minor changes
to the text and/or graphics, which may alter content. The journal’s
standard Terms & Conditions and the ethical guidelines, outlined
in our author and reviewer resource centre, still apply. In no
event shall the Royal Society of Chemistry be held responsible
for any errors or omissions in this Accepted Manuscript or any
consequences arising from the use of any information it contains.
ISSN 2050-7488
PAPER
Kun Chang, Zhaorong Chang et al.
Bubble-template-assisted synthesis of hollow fullerene-like
MoS2 nanocages as a lithium ion battery anode material
rsc.li/materials-a

Please do not adjust margins
Journal of Materials Chemistry A
Page 1 of 11
View Article Online
DOI: 10.1039/C7TA01986F
Journal Name
ARTICLE
Synthesis of Anion-Functionalized Mesoporous Poly(ionic liquid)s
via a Microphase Separation-Hypercrosslinking Strategy: Highly
Efficient Adsorbents for Bioactive Molecules
Xian Suo, Ling Xia, Qiwei Yang, Zhiguo Zhang, Zongbi Bao, Qilong Ren, Yiwen Yang, Huabin Xing*
The synthesis of porous materials with well-defined pore structure and functionality is centrally important for the
development of advanced adsorbents and sensors. In this study, we explored a direct and facile methodology combining
microphase separation and hypercrosslinking, and prepare anion-functionalized mesoporous poly(ionic liquid)s (MPILs)
with well-developed mesopores. This methodology involved a copolymerization of IL monomers and crosslinkers to create
mesopores via microphase separation. Additionally, the MPILs were texturally engineered by hypercrosslinking to
stabilize/rebuild labile collapsed mesoporous networks and generate a microporosity. Thus, a new family of anion-
functionalized MPILs containing amphiphilic long-chain carboxylate ionic liquids (LCC-ILs) were synthesized. These anion-
functionalized MPILs exhibited extraordinarily high adsorption capacity (211.45 mg g-1 for tocopherols) and excellent
selectivity (Sδ/α, 8.65; Sβ&γ/α, 4.20) for bioactive tocopherol homologues and organic phenolic compounds with high
structural similarity, significantly better than those of commercial adsorbents or common MPILs. Additionally, anion-
functionalized MPILs demonstrated enhanced carbon dioxide (CO2) capture performances (28.18 mg g-1 at 0 °C and 1 bar).
This study demonstrated the great potential of anion-functionalized MPILs as advanced adsorbents, and facilitates a
textural engineering approach to the development of novel porous ionic materials for other applications.
Received 00th January 20xx,
Accepted 00th January 20xx
DOI: 10.1039/x0xx00000x
www.rsc.org/
efficient method for the synthesis of MPILs through a direct radical
copolymerization of IL monomers and crosslinkers in nonreactive
solvents. Several MPILs containing common hydrophobic ILs and
Introduction
Porous polymers with functional surfaces and well-defined pore
structures have attracted immense research interest due to their
importance in separations, catalysis and energy storage.1-5
Mesoporous poly(ionic liquid)s (MPILs) integrate unique properties
of ionic liquids (ILs) and porous polymers,6-8 such as high ionic
conductivity, tunable physical properties, high surface area, and
broad structural diversity, and provide great opportunities for the
development of novel porous adsorbents,9-13 membranes,14-16
catalyst supports,17-19 and stimuli-responsive materials.20-22 The
control of pore structure and pore chemistry in MPILs is critical for
determining their potential applications. To date, several pore
formation strategies have been developed for the fabrication of
MPILs with well-defined pore structures. These strategies include a
hard template method using sacrificial silica nanoparticles12 and a
soft template method using tri-block copolymer assembly.23
Recently, due to the unique ionic character of ILs, a template-free
ionic complexation strategy via acid-base neutralization was
halogen anion-based ILs were successfully prepared using
microphase separation.26-28 This route uses porogenic solvents as
templates and greatly shortens the synthesis period at reduced
costs. The selection of a porogenic solvent is critical to pore
structure and morphology.29-31 However, due to the soft and
organic nature of MPIL frameworks, MPILs prepared with the
aforementioned methods would be confronted with volume
shrinkage and pore collapse after template or solvent removal.32-34
Therefore, there is an urgent need to develop an alternative
solution to avoid or minimize structural shrinkage, maximize the
retention of organic porous matrix, and to realize a textural
engineering of MPILs with stable and well-developed mesoporous
frameworks.
The functionality and performance of MPILs and ionic materials
are dependent on the nature of the ILs, especially on the type of
anions. For example, in the separation of drugs and bioactive
compounds, ILs with long-chain carboxylate anions or amino acid
anions demonstrated superior capacity and molecular selectivity.35-
presented for facile preparation of MPILs with gradient pore
structures was presented.13,
Additionally, polymerization-
has been considered an
14, 20
41
25
Very recently, our group found that the hybrid porous materials
induced microphase separation24,
-
containing the hexafluorosilicate anion (SiF6 ) showed
unprecedented performance for acetylene capture.42 However,
existing MPILs were limited in common IL monomers, such as
hydrophobic ILs and halogen anion-based ILs.19, 26, 27 Furthermore,
the introduction of functional anions has mostly depended on the
post-modification via anion exchange. However, this method often
Key Laboratory of Biomass Chemical Engineering of Ministry of Education,
College of Chemical and Biological Engineering, Zhejiang University,
Hangzhou 310027, China. E-mail: xinghb@zju.edu.cn
† Electronic Supplementary Information (ESI) available. See
DOI: 10.1039/x0xx00000x
This journal is © The Royal Society of Chemistry 20xx
J. Name., 2013, 00, 1-3 | 1
Please do not adjust margins

Please do not adjust margins
Journal of Materials Chemistry A
Page 2 of 11
ARTICLE
Journal Name
resulted in changed pore structures and incomplete ion exchange equimolar levels of DVB and LCC-ILs are herein rVeifeewrArertidcletOonlianes
due to steric hindrance, especially for bulky functional anions.4, 23, 43 P(DVB-EVIMCm)s or HP(DVB-EVIMCm)s. TheDmOoI:le1c0u.1l0a3r9s/tCru7TcAtu0r1e9s86oFf
The limited availability and the difficulty of anion-functionalization LCC-ILs and P(DVB-EVIMCm)s are shown in Figs. S1 and S3, †
for MPILs have restricted their applications to primarily carbon respectively. And the synthetic route is shown in Fig. S2. †
13
19, 27
dioxide (CO2) capture12,
and catalysis.18,
Applications in
The IL monomer was introduced into the polymer framework by
separations of drug and bioactive molecules have rarely been copolymerization with DVB in a selected porogenic solvent. Under
reported.9 Additionally, although many common porous polymers optimized porogenic solvent compositions and solvothermal
3, 44-46
have been prepared for the separation of CO2
and bioactive conditions, microphase separation took place accompanied by
48
molecules,47,
the design of porous materials with both high crosslinking in the process of the polymerization. Through solvent
extraction, MPILs of P(nDVB-EVIMCm)s were produced through the
capacity and selectivity remains challenging.
Herein, we have explored a facile methodology combining shrinkage of a loose network with unstable pores and collapsed
microphase separation and hypercrosslinking to prepare anion- porous structures.
functionalized MPILs. A family of new MPILs containing long-chain
After the copolymerization, some double bonds are inevitably
carboxylate ILs (LCC-ILs) were prepared. These MPILs possessed residual in these polymer frameworks, due to limited polymeric
stable, well-developed mesopores and adequate functional IL activity of the secondary vinyl groups in DVB and steric hindrance in
moieties. This method used the copolymerization of IL monomers dense domains.49 P(nDVB-EVIMCm)s were adequately swollen in a
and crosslinkers to create mesopores via microphase separation suitable good solvent. The porous polymers were hypercrosslinked
after template solvent removal. We subsequently employed a using the Friedel-Crafts reaction with andydrous ferric chloride
textural engineering approach by hypercrosslinking to (FeCl3) as catalysts but without added crosslinking agents. As a
stabilize/rebuild labile collapsed mesoporous networks and produce consequence, unstable pore structures in the P(nDVB-EVIMCm)s
new micropores. The prepared anion-functionalized MPILs were covalently arrested via the formation of methylene bridges
demonstrated extraordinary adsorption capacity and excellent between the pendant vinyl groups and accessible aromatic rings.48-
51
selectivity to bioactive compounds with high structural similarity
In this way, HP(nDVB-EVIMCm)s had improved porosity, more
and were superior to common MPILs and commercial adsorbents. permanent mesopores and new micropores when compared with
The anion-functionalized MPILs also exhibited enhanced CO2 parent polymers, which are vitally important for further application.
adsorption capacity and good CO2/N2 selectivity after
Preparation of P(nDVB-EVIMC12)s
hypercrosslinking treatment.
It is widely accepted that IL units are functional sites in MPILs, and
porosity is considered essential in various application, such as
Results and discussion
Fig. 1 depicts the synthetic route for long-chain carboxylate anion-
adsorption and catalysis. LCC-ILs have demonstrated extraordinary
absorption capacity for acidic gases52 and excellent extraction
performances for various bioactive compounds and phenols, due to
their unique amphiphilic properties and strong hydrogen basicity.35-
functionalized MPILs. Here, porous copolymers of the 1-ethyl-3-
vinylimidazolium-based LCC-ILs and divinylbenzene (DVB)
crosslinker are referred to as P(nDVB-EVIMCm)s, and
hypercrosslinked MPILs are referred to as HP(nDVB-EVIMCm)s,
where n represents the used molar ratio of DVB to LCC-ILs, m
represents the even carbon number of the carboxylate anions and
changes from 2 to 16. Porous copolymers synthesized from
38, 53
However, these properties make the preparation of MPILs
challenging with large surface areas and well-defined mesoporous
structures.
In this work, a solvothermal method was employed to prepare
P(nDVB-EVIMC12)s. The composition of porogenic solvent and
solvothermal condition play crucial roles in generating porous
structures. To act as a pore template, a porogenic solvent should be
a good solvent for monomers and a nonsolvent for the formed
polymers. N,N-Dimethylformamide (DMF), acetone, ethyl acetate,
tetrahydrofuran (THF) and methyl benzene are popular porogenic
solvents for preparing MPILs with hydrophilic or hydrophobic IL
monomers.4, 26-28, 31 However, in the case of amphiphilic LCC-ILs, all
the resultant products using the above mentioned solvents were
shown to be nonporous copolymers (Table S1, entry 5†).
Interestingly, the polar solvent of acetonitrile (MeCN), which is an
appropriate solvent for LCC-ILs in forming non-aqueous lyotropic
ionic liquid crystals,36 could result in a structured porosity. The
sample of P(DVB-EVIMC12) synthesized in MeCN from equimolar
DVB and 1-ethyl-3-vinylimidazolium laurate ([EVIM][C11COO])
exhibited satisfactory surface area (evaluated by BET equation,
denoted as SBET, 247 m2 g-1), large total pore volume (Vtotal, 0.360
cm3 g-1) and adequate IL content (1.01 mmol g-1) (Table1, entry7).
As shown in Fig. 2A, the sample displayed a type IV isotherm with
Fig. 1 Synthetic route for anion-functionalized MPILs (P(nDVB-EVIMCm)s)
and hypercrosslinked MPILs (HP(nDVB-EVIMCm)s).
2 | J. Name., 2012, 00, 1-3
This journal is © The Royal Society of Chemistry 20xx
Please do not adjust margins

Please do not adjust margins
Page 3 of 11
Journal of Materials Chemistry A
ARTICLE
Journal Name
for further exploration.
View Article Online
The ratio of DVB to IL monomer had a siDgnOiIf:ic1a0n.1t03im9/pCa7cTtA0o1n98th6eF
porous structure and composition of MPILs. As shown in Figs. 2C, D,
and S4B, † the equivalent molar ratio of DVB and [EVIM][C11COO]
was an optimal condition to synthesize MPILs with well-developed
mesopores and sufficient IL contents. In the Fig. 2C, the sample of
MPILs prepared with different molar ratios (n) of DVB to
[EVIM][C11COO] is herein named as P(nDVB-EVIMC12)s. At a low
DVB-to-IL ratio, P(0.5DVB-EVIMC12) exhibited
a nonporous
structure. N2 sorption isotherms of P(0.75DVB-EVIMC12) exhibited
a slight hysteresis loop, indicating some mesopores, and displayed a
sharp rise at high P/P0 above 0.80, which is indicative of some
macropores. This polymer exhibited wide pore size distributions
with a mean mesopore size of 16.0 nm (Table S2, entry 2; Fig. S4B †).
At an equivalent molar ratio of DVB and [EVIM][C11COO], well-
developed mesopores were observed in the sample of P(DVB-
EVIMC12). When the molar ratio of DVB-to-IL was increased from
1:1 to 5:1, the SBET values of the MPILs increased from 247 to 393
m2 g-1 (Fig. 2C), whereas the corresponding average pore sizes
dropped from 6.8 to 2.7 nm (Table1, entry7, and Table S2, entries 3
to 5, † respectively ), and the IL content dropped from 1.01 to 0.31
mmol g-1. Additionally, P(2DVB-EVIMC12) showed a type I isotherm
with a faint type IV character, indicating the coexistence of
abundant micropores and few mesopores. P(3DVB-EVIMC12) and
P(5DVB-EVIMC12) presented type I isotherms on typical of
micropores. Furthermore, the reaction temperature, time and the
initiator dosage influenced the textural properties of the prepared
P(DVB-EVIMC12)) (Table S3†). For example, the sample obtained at
60 °C had a very low SBET value of 31 m2 g-1, and a significantly
improved porosity appeared at 80-100 °C. Detailed results are listed
in the Table S3.†
Synthesis and characterization of P(DVB-EVIMCm)s with different
carboxylate anions
Fig.
2 N2 adsorption/desorption isotherms (A, C, E) and pore size
distributions (B, D, F) of prepared polymers. (A, B) P(DVB-EVIMC12)
synthesized in various solvents, (C, D) P(nDVB-EVIMC12)s and (E, F) P(DVB-
The synthesis strategy was successfully applied to the preparation
EVIMCm)s. The isotherms were offset by 80, 160, 240 and 320 cm3g-1, of a family of P(DVB-EVIMCm)s (their molecular structures are
respectively, along with the vertical axis for clarify, except for P(0.75DVB-
shown in Fig. S3†). All P(DVB-EVIMCm)s (m = 2, 4, 6, 8, 10, 12, 14,
EVIMC12); and the pore size distributions were offset by 0.008, 0.016, 0.024,
and 16) demonstrated well-developed mesoporosities and IL
0.032 and 0.040 cm3 g-1 nm-1, and each of them was estimated by BJH model
from a desorption branch of the isotherm.
contents larger than 0.78 mmol g-1 (Figs. 2E and F；Fig. S5 and
Table S4†). The detailed textural parameters are listed in Tables 1
and S4. † For example, P(DVB-EVIMC10) had a high SBET value of 326
m2 g-1 , a large Vtotal value of 0.452 cm3 g-1, and an adequate IL
an evident hysteresis loop of type H2 in the relative pressure (P/P0)
content of 1.02 mmol g-1 (Table 1, entry 5).
range from 0.42 to 0.90, reflecting the existence of mesopores. The
For the preparation of P(DVB-EVIMCm)s with the carbon
corresponding pore size distribution was displayed in Figs. 2B and
number of carboxylate anions larger than 12, we found that EtOH
S4A.† Thus, this type of porous material showed significant
was better porogenic solvent, due to the enhanced hydrophobic
potential for excellent adsorption performance. MPILs of P(DVB-
properties of the corresponding LCC-ILs. When EtOH was used in
EVIMC12) were also obtained using ethanol (EtOH) (SBET, 172 m2 g-1;
the copolymerization, P(DVB-EVIMC14) and P(DVB-EVIMC16)
V
total, 0.386 cm3 g-1) and methanol (MeOH) (SBET, 203 m2 g-1; Vtotal
,
showed well-developed porosities (283 m2 g-1, 0.482 cm3 g-1 and
360 m2 g-1, 0.620 cm3 g-1,respectively, Table S4, entries 4 and 6†).
The scanning electron microscopy (SEM) micrographs (Figs. 3A
and B) of P(DVB-EVIMC12) presented an apparent foam structure
with a morphology of sponge-like aggregations, indicating high
porosity. The primary irregular particles with tens of nanometers in
size were interconnected with each other to form a crosslinked
framework with the pore size, which ranges from several to
0.326 cm3 g-1) as porogenic solvents. The content of 1-ethyl-3-
vinylimidazolium laurate ([EVIM][C11COO]) was moderate (0.83 and
0.74 mmol g-1, Table S1, entries 1 and 2, † respectively).
Additionally, we found that the introduction of water into the
MeCN solution significantly decreased the surface areas and IL
contents of prepared MPILs (Figs. 2A and B; Table S1, entries 3 and
4†). Therefore, pure MeCN was selected as the porogenic solvent
This journal is © The Royal Society of Chemistry 20xx
J. Name., 2013, 00, 1-3 | 3
Please do not adjust margins

Please do not adjust margins
Journal of Materials Chemistry A
Page 4 of 11
ARTICLE
Journal Name
View Article Online
DOI: 10.1039/C7TA01986F
Fig. 4 N2 adsorption-desorption isotherms of P(DVB-EVIMC12) synthesized
in MeCN and corresponding HP(DVB-EVIMC12).
was up to 220 °C as derived from the decomposition of ILs. Above
this temperature, major weight loss roughly started at 350 °C, due
to the degradation of the DVB polymeric framework.31
In brief, we demonstrated a facile and viable synthesis strategy
for the fabrication of P(DVB-EVIMCm)s. Anion-functionalized LCC-
ILs were covalently bound onto a crosslinked polymeric matrix. This
method prevents the occurrence of tedious and incomplete anion
exchange from halogen anions, and prevents the plugging of porous
channel due to the introduction of bulky anions.
Synthesis and textural properties of hypercrosslinked P(DVB-
EVIMCm)s
Fig. 3 (A) and (B) SEM micrographs of P(DVB-EVIMC12), (C) and (D) TEM
images of P(DVB-EVIMC12), (E) FIIR spectra of representative P(DVB-
EVIMCm)s.
Hypercrosslinking is a simple approach to generate micropores and
55
stabilize polymer nanostructures.50,
In recent years, many
hypercrosslinked materials have been prepared.34,
44, 50, 56, 57
hundreds of nanometers. These macropores provided channels for
fast solute diffusion. In accordance with N2 sorption, the presence
of disordered mesopores distributed within the copolymer particles
was confirmed by the transmission electron microscopy (TEM)
images (Figs. 3C and D). Such a hierarchical structure promotes
substrate diffusion and adsorption. Other P(DVB-EVIMCm)s had
similar hierarchical structures and morphologies as P(DVB-EVIMC12)
(Fig. S6†).
The obtained copolymers were chemically characterized by
Fourier transform infrared spectroscopy (FTIR) to identify their
chemical composition. As shown in Fig. 3E, the peak at 1160 cm-1
was the characteristic absorption peak of the C-N covalent bond
corresponding to substituted N3 in imidazolium-based ILs.43 The
peaks at 1654 and 1630 cm-1 were assigned to the imidazole ring
skeleton. Additionally, the -COO- group of carboxylate anions was
observed at 1560 cm-1.54 The peaks at 2922 and 2853 cm-1 were
attributed to the saturated C-H group stretching vibrations of
carboxylate anions and other aliphatic chains.26, 28 Clearly, these
results suggested the successful introduction of the IL moieties into
the polymeric framework. According to the thermogravimetric
analysis (TGA) results shown in Table S5 and Fig. S6,† P(DVB-
EVIMCm)s exhibited apparently higher stability than the
corresponding monomers [EVIM][Cm-1COO], which was attributed
to the crosslinked structure of the copolymer. The onset
decomposition temperature of decomposition of P(DVB-EVIMC12)
However, few examples of hypercrosslinking have involved with IL
systems.58-62 In this work, to produce hypercrosslinked MPILs
(referred to as HP(DVB-EVIMCm)s), the Friedel-Crafts reaction was
conducted with the precursor materials (i.e., P(DVB-EVIMC12)). All
resultant polymers exhibited apparently enhanced micro- and
mesoporosities. As shown in Fig. 4, there were visible differences
between P(DVB-EVIMC12) and HP(DVB-EVIMC12). At a relatively
lower P/P0, the N2 adsorption capacity of P(DVB-EVIMC12) was
significantly enhanced after hypercrosslinking treatment, whereas
the pore size distribution of HP(DVB-EVIMC12) demonstrated
moderate increase in smaller pore sizes compared with P(DVB-
EVIMC12) (Fig. S8†). This was due to the newly developed micro-
and mesoporosities. Detailed textural parameters for P(DVB-
EVIMCm)s and HP(DVB-EVIMCm)s are listed in Table 1. When
compared with P(DVB-EVIMC12), HP(DVB-EVIMC12) showed
increased SBET and Vtotal (SBET: 386 vs. 247 m2 g-1; Vtotal: 0.420 vs.
0.360 cm3 g-1; Table 1, entries 7 and 8). The micropore surface area
(Smicro) and micropore pore volume (Vmicro) values increased several-
fold prominently enlarged from 14 (P(DVB-EVIMC12)) to 58 m2 g-1
(HP(DVB-EVIMC12)) and 0.006 to 0.030 cm3 g-1, respectively. These
results indicated that more micropores were formed in the
hypercrosslinked network. For the mesoporous structures, after
hypercrosslinking treatment on P(DVB-EVIMC12), the external
surface area (Sext) values distinctly improved from 233 to 328 m2 g-1,
and pore volume of the mesopores (derived from BJH model, VBJH
)
4 | J. Name., 2012, 00, 1-3
This journal is © The Royal Society of Chemistry 20xx
Please do not adjust margins

Please do not adjust margins
Journal of Materials Chemistry A
Page 5 of 11
ARTICLE
Journal Name
Table 1 Textural parameters of several P(DVB-EVIMCm)s a and the corresponding HP(DVB- EVIMCm)s b after hypercrosslinking treatment
View Article Online
DOI: 10.1039/C7TA01986F
Smicro
Vmicro
Sext
VBJH
DBJH
nm
SBET
Vtotal
IL content h
c
c
d
e
e
f
g
Entry
Sample
m2 g-1
cm3 g-1
m2 g-1
cm3 g-1
m2 g-1
cm3 g-1
mmol g-1
1
2
3
4
5
6
7
8
P(DVB-EVIMC4)
HP(DVB-EVIMC4)
P(DVB-EVIMC8)
HP(DVB-EVIMC8)
P(DVB-EVIMC10)
HP(DVB-EVIMC10)
P(DVB-EVIMC12)
HP(DVB-EVIMC12)
42
88
34
70
19
77
14
58
0.021
0.044
0.017
0.034
0.009
0.040
0.006
0.030
271
306
318
356
308
355
233
328
0.435
0.430
0.472
0.483
0.412
0.431
0.330
0.349
7.9
7.4
7.4
7.1
6.4
6.2
6.8
5.5
313
393
352
426
326
432
247
386
0.486
0.512
0.525
0.563
0.452
0.514
0.360
0.420
0.90
0.85
1.00
0.91
1.02
1.03
1.01
1.02
a Polymers served as precursors synthesized with 2 wt% AIBN in MeCN at 80 °C for 24 h. b Hypercrosslinked porous polymers via the Friedel-Crafts reaction,
prepared with 5 wt% anhydrous FeCl3 in EtOH at 80 °C for 24 h. c Micropore surface area and volume estimated by t-plot method. d External surface area
derived from t-plot method. e Mesopore volume and mean mesopore diameter calculated from BJH model. f BET surface area evaluated from N2 adsorption
isotherm in relative pressure (P/P0) from 0.05 to 0.30. g Total pore volume at relative pressure (P/P0) = 0.990.h Loading of IL on the polymer and determined
from the elemental analysis.
Table 2 Gas sorption properties of several P(DVB-EVIMCm)s and the corresponding HP(DVB-EVIMCm)s
CO2 uptake a
mg g
N2 uptake a
mg g
IAST selectivity b
(equimolar)
Entry
Sample
-1
-1
1
2
3
4
5
6
7
8
P(DVB-EVIMC4)
HP(DVB-EVIMC4)
P(DVB-EVIMC8)
HP(DVB-EVIMC8)
P(DVB-EVIMC10)
HP(DVB-EVIMC10)
P(DVB-EVIMC12)
HP(DVB-EVIMC12)
20.33
23.10
0.82
0.94
27.18
26.77
21.35
0.90
25.54
23.16
0.97
26.47
20.26
0.85
22.75
25.26
18.98 (28.18) c
0.93
28.72
0.73 (1.52)
1.00 (1.91)
27.63 (22.19)
26.13 (22.87)
24.22 (33.20)
a Measured at 25 °C and 1 bar. b IAST selectivity calculated at 25 °C and 1 bar. c The data in round brackets obtained at 0 °C and 1 bar.
values slightly increased from 0.330 to 0.349 cm3 g-1. Furthermore,
the mean mesopore diameter (DBJH) values declined from 6.8 nm
(P(DVB-EVIMC12)) to 5.5 nm (HP(DVB-EVIMC12)). The enhanced
micro- and mesoporosities of P(DVB-EVIMCm)s were attributed to
the hypercrosslinking treatment. Methylene bridges were formed
between the pendant vinyl groups with neighboring benzene rings
via the Friedel-Crafts reaction. New micropores were generated,
and labile collapsed pores were rebuilt into stable pore networks
(Fig. 1). The P(DVB-EVIMCm)s and HP(DVB-EVIMCm)s had nearly
the same IL contents (Table 1, entries 1 to 8), which verified that
the IL moieties were preserved. And it was not possible to visualize
distinct changes in the sponge-like morphology or abundant
disordered mesoporosity after hypercrosslinking treatment, based
on the SEM and TEM images (Figs. S9 and S10†). Therefore
hypercrosslinking by the Friedel-Crafts reaction provided an easy
and efficient way to prepare MPILs with well-developed micro-
mesoporous structures. Through the textural engineering, new
micropores were created and stable mesopores were rebuilt, which
will enable enhanced sorption capacities for gas separation.
Fig. 5 Gas adsorption isotherms of P(DVB-EVIMC12) and HP(DVB-EVIMC12)
at 25 °C for CO2 and N2.
Many efforts have been devoted to fabricating porous adsorbents
for CO2 capture.63 In this work, the performances of anion-
functionalized P(DVB-EVIMCm)s and HP(DVB-EVIMCm)s for CO2
capture were evaluated. As summarized in Table 2, P(DVB-
EVIMCm)s and HP(DVB-EVIMCm)s with sufficient porosity and
adequate IL contents exhibited enhanced CO2 uptake capacity and
CO2 capture
This journal is © The Royal Society of Chemistry 20xx
J. Name., 2013, 00, 1-3 | 5
Please do not adjust margins

Please do not adjust margins
Journal of Materials Chemistry A
Page 6 of 11
ARTICLE
Journal Name
View Article Online
DOI: 10.1039/C7TA01986F
Fig. 6 (A) Molecular structures of tocopherol homologues. (B) Adsorption capacity and (C) selectivity of mixed tocopherols in heptane by commercial
adsorbents, P(nDVB-IL)s with common ILs and P(DVB-EVIMCm)s at 25 °C for 24 h. Adsorbents: A. Amberlite XAD-4 B. Amberlite 717 C. P(2DVB-EVIMTf2N) D.
P(2DVB-EVIMBr) E. P(2DVB-EVIMPF6) F. P(2DVB-EVIMBF4) G. P(DVB-EVIMC2) H. P(DVB-EVIMC4) I. P(DVB-EVIMC6) J. P(DVB-EVIMC8) K. P(DVB-EVIMC10) L.
P(DVB-EVIMC12) M. P(DVB-EVIMC14) N. P(DVB-EVIMC16). All values are mean of three measurements.
good CO2/N2 selectivity. At 1 bar, the CO2 uptakes by P(DVB- and δ-tocopherols). Therefore a key step in the production of high-
EVIMC12) reached 18.98 mg g-1 (25 °C) and 28.18 mg g-1 (0 °C) with purity α-tocopherol is the selective separation of α-tocopherol from
remarkable CO2/N2 selectivities (22.19-27.63) for equimolar CO2/N2 these homologues.64-67 However this separation is very challenging
mixture based on ideal adsorbed solution theory (IAST) calculation due to their high structural similarities as displayed in Fig. 6A.
(Table 2, entry 7). Moreover, the regeneration experiments Encouragingly, the distinct hydrogen-bond acidities follow the
indicated a good reusability of P(DVB-EVIMC10) at six cycles of CO2 ascending order α-tocopherol < β- and γ-tocopherol < δ-tocopherol,
uptake (Fig. S11 †). After hypercrosslinking treatment, HP(DVB- which are expected to guide the difficult separation process.
EVIMCm)s with well-developed porous structure demonstrated a
The adsorption performance of P(DVB-EVIMCm)s was
significantly enhanced CO2 uptake capacity compared with P(DVB- investigated by batch experiments with tocopherol homologues as
EVIMCm)s (24.22 vs. 18.98 mg g-1 at 25 °C and 33.20 vs. 28.18 mg typical bioactive solutes. As presented in Figs. 6B and C, all P(DVB-
g-1 at 0 °C and 1 bar, Table 2, entries 7 and 8). The adsorption EVIMCm)s showed large adsorption capacities for tocopherols and
isotherms of CO2 on both MPILs are shown in Fig. 5, and an high selectivities to homologues. Their performances were
improved capture ability is observable by comparing P(DVB- significantly superior to commercial adsorbents and P(nDVB-IL)s
EVIMC12) and HP(DVB-EVIMC12). Additionally, no evident with common IL moieties. For example, the adsorption capacities of
differences in isosteric heats of adsorption were observed between tocopherols on P(DVB-EVIMC12) were up to 211.45 mg g-1 at 25 °C,
these two polymers (Fig. S13†), which indicated no apparent which is 3.35 and 2.17 times larger than that for commercial resin
change occurred in the interaction between the polymers and adsorbents, Amberlite XAD-4 (63.21 mg g-1) and Amberlite 717
targeted gas after hypercrosslinking treatment. The enhanced CO2 (97.49 mg g-1) as adsorbents, respectively. This was also significantly
uptake capacity of HP(DVB-EVIMC12) was attributed to its larger than the adsorption capacities of P(nDVB-IL)s with common
improved pore structure. The CO2 uptake capacity of HP(DVB- ILs, such as P(2DVB-EVIMTf2N) (96.67 mg g-1), P(2DVB-EVIMBr)
EVIMC12) (24.22 and 33.20 mg g-1 at 25 and 0 °C, respectively) was (106.81 mg g-1), P(2DVB-EVIMPF6) (119.34 mg g-1), and P(2DVB-
higher than that of imidazolium-type MPILs reported in the EVIMBF4) (148.61 mg g-1). Common MPILs, such as P(2DVB-
literature (approximately 27.42 mg g-1 at 0 °C and 1 bar).13
EVIMBF4), had a higher porosity (SBET, 374 m2 g-1; Vtotal, 0.446 cm3 g-1)
than that of P(DVB-EVIMC12). However, P(DVB-EVIMC12) still
demonstrated significantly higher adsorption capacities for
tocopherols (211.45 mg g-1 vs. 148.61 mg g-1). Similarly, P(2DVB-
Selective separation of tocopherol homologues and organic
phenolic compounds
The prepared MPILs exhibited selective separations for bioactive EVIMBr) (SBET, 371 m2 g-1; Vtotal, 0.271 cm3 g-1) showed relatively
compounds and organic compounds with similar structures. lower tocopherol uptake (106.81 mg g-1). LCC-ILs serve as stronger
Tocopherols are important fat-soluble vitamins in the biological hydrogen-bond acceptors than common ILs and own great affinity
system and act as effective antioxidants to scavenge free radicals. for tocopherols,36, 68 which are scarce in these commercial resin
However, highly biologically active α-tocopherol is always adsorbents. Therefore, the introduction of functional carboxylate
accompanied by three other tocopherol homologues (i.e., β-, γ-, anions into MPILs significantly enhanced its adsorption capacity for
This journal is © The Royal Society of Chemistry 20xx
J. Name., 2013, 00, 1-3 | 6
Please do not adjust margins

Please do not adjust margins
Journal of Materials Chemistry A
Page 7 of 11
ARTICLE
Journal Name
bioactive compounds. Moreover, the regeneration experiments In summary, we explored a facile methodology combining
View Article Online
DOI: 10.1039/C7TA01986F
showed that P(DVB-EVIMCm)s preserves its tocopherol adsorption microphase separation and hypercrosslinking to prepare anion-
capacity after four adsorption/desorption cycles (Fig. S15†).
functionalized MPILs. A new family of anion-functionalized MPILs
Anion-functionalized MPILs exhibited very high adsorption containing LCC-ILs were prepared. These MPILs possessed stable,
capacities for tocopherols, and demonstrated extraordinary well-developed mesopores and adequate functional IL contents.
selectivity for different homologues. As shown in Fig. 6C, the The hypercrosslinking treatment stabilized/rebuilt labile collapsed
selectivity of P(DVB-EVIMC12) for δ-tocopherol to α-tocopherol mesoporous network and produced new micropores, as shown by
(Sδ/α) and for β- and γ-tocopherol to α-tocopherol (Sβ&γ/α) were up improved surface area and enhanced gas adsorption capacity.
to 8.65 and 4.20, respectively. Striking differences in the selectivity Anion-functionalized MPILs demonstrated good CO2 capture
were observed among P(DVB-EVIMCm)s, commercial adsorbents, performance (P(DVB-EVIMC12): 28.18 mg g-1 at 0 °C and 1 bar) and
and common MPILs. The Sδ/α and Sβ&γ/α values of the two resins exhibited extraordinarily high adsorption capacities (i.e., 211.45 mg
were less than 1. P(nDVB-IL)s with common ILs also have poor g-1 for tocopherols) and excellent selectivities (i.e., Sδ/α, 8.65; Sβ&γ/α
,
separation selectivity. For example, the Sδ/α and Sβ&γ/α values of 4.20) over commercial adsorbents and common MPILs for bioactive
P(2DVB-EVIMBr) were low at 2.36 and 1.58, respectively, and for tocopherol homologues and organic phenolic compounds with high
P(2DVB-EVIMTf2N), these values were as low as 1.52 and 1.20, structural similarities. The prepared anion-functionalized MPILs had
respectively, which were distinctly inferior to those of all P(DVB- well-defined pore structure and possessed unique molecular
EVIMCm)s (Fig. 6C). To the best of our knowledge, P(DVB-EVIMC12) recognition abilities, which makes them competent candidates for
demonstrated the highest selectivity for tocopherol homologues advanced separations. Therefore, this study demonstrated the
among commercial adsorbents and reported porous materials. The potential of anion-functionalized MPILs as advanced adsorbents
excellent molecular selectivity of anion-functionalized MPILs for and facilitated a textural engineering approach to the development
tocopherol homologues was mainly attributed to the strong of novel porous ionic materials for other applications.
hydrogen-bond basicity of incorporated long chain carboxylate
anions in the polymers.36, 64, 68, 69
Experimental
Additionally, HP(DVB-EVIMC12) demonstrated
tocopherol adsorption performance (211.98 mg g-1 with Sδ/α and
β&γ/α values of 8.05 and 4.12, respectively) as that of the precursors
a
similar
Preparation of LCC-ILs
LCC-ILs were prepared as follows.35-37,
S
53
First, 1-ethyl-3-
of P(DVB-EVIMC12). This is because the adsorption of tocopherols
on MPILs primarily depends on the nature and composition of the
incorporated LCC-ILs, whereas the hypercrosslinking process gives
rise to more abundant porosity without significantly changing the
composition.
vinylimidazolium bromide ([EVIM][Br]) was synthesized as
described in the literature.70 A mixture of 1-vinylimidazole (9.41 g,
0.10 mol) and a slight excess of bromoethane (14.17 g, 0.13 mol)
were dissolved in 30 mL MeOH with stirring for 15 h at 55 °C. Crude
[EVIM][Br] was obtained by removing the solvent and then washing
with ethyl acetate three times. [EVIM][Br] white solid was obtained
after drying for 24 h at 50 °C. Afterward, [EVIM][Br] was dissolved in
deionized water and passed through a strongly basic anion-
exchange resin (Dowex Monosphere 550A UPW; OH type). The
eluted 1-ethyl-3-vinylimidazolium hydroxide ([EVIM][OH]) aqueous
solution was mixed with equimolar amounts of long-chain fatty
acids at room temperature for 24 h. Aqueous silver nitrate (AgNO3)
solution was used to confirm complete anion exchange and the
concentration of [EVIM][OH] was determined by acid-base titration.
After solvent removal by evaporation under reduced pressure at
50 °C, LCC-ILs were dried under high vacuum to remove trace water.
Seven IL monomers were prepared using different fatty acids,
including acetic acid, butyric acid, hexanoic acid, octanoic acid,
decanoic acid, laurate acid, myristic acid, and palmitic acid. The
Furthermore, P(DVB-EVIMCm)s also showed excellent
adsorption and separation performance for organic phenolic
compounds, such as phenol, p-cresol, and 2,6-dimethylphenol,
which have similar molecular structures shown in Fig. S16A.† As is
well-known, phenol, p-cresol and 2,6-dimethylphenol are important
feedstocks and intermediates in the chemical industry, and are
mostly derived from coal tar oil as a mixture. As shown in Figs. S16B
and C,† P(DVB-EVIMCm)s exhibited very high adsorption capacities
for the mixture of the above mentioned phenols with the values
ranging from 279.32 to 305.61 mg g-1 . These values were larger
than commercial adsorbents, such as Amberlite XAD-4 (107.76 mg
g-1) and P(nDVB-IL)s with common ILs, such as P(2DVB-EVIMTf2N)
(141.12 mg g-1), P(2DVB-EVIMPF6) (193.64 mg g-1), P(2DVB-EVIMBr)
(205.70 mg g-1), and P(2DVB-EVIMBF4) (240.13 mg g-1). Significantly,
for P(DVB-EVIMCm)s, the selectivity of phenol to 2,6-
dimethylphenol (Sphenol/2,6-dim) and the selectivity of p-cresol to 2,6-
dimethylphenol (Sp-cresol/2,6-dim) were both higher than those of
common MPILs. For instance, excellent selectivities were realized
even up to 9.49 (Sphenol/2,6-dim) and 6.12 (Sp-cresol/2,6-dim) with P(DVB-
EVIMC12) as the adsorbent, respectively. However, the Sphenol/2,6-dim
and Sp-cresol/2,6-dim values of P(2DVB-EVIMBr) were low at 5.32 and
3.59, respectively.
1
chemical structures of these obtained ILs were ascertained by H
NMR and 13C NMR spectra (in the ESI†).
Synthesis of P(nDVB-EVIMCm)s and P(nDVB-IL)s with common
anions
Typical copolymerizations of DVB and LCC-ILs were conducted as
follows. In a 50-mL Schlenk flask, 1.00 g of DVB crosslinker, 2.48 g of
[EVIM][C11COO] monomer, and 0.07
g
of 2,2’-azobis(2-
methylpropionitrile) (AIBN) initiator were added to 10 mL MeCN,
and the solution was stirred at room temperature for 2 h. Then, the
Conclusions
This journal is © The Royal Society of Chemistry 20xx
J. Name., 2013, 00, 1-3 | 7
Please do not adjust margins

Please do not adjust margins
Journal of Materials Chemistry A
Page 8 of 11
ARTICLE
Journal Name
where P (kPa) is the pressure of the bulk gas at the equilibrium;
mixture was deoxygenated for 20 min and backfilled with N2,
followed by vigorous stirring at 80 °C for 24 h. After cooling to
room temperature, the sample was washed with a large amount of
EtOH, and dried under vacuum at 65 °C for 24 h. Then, the resultant
yellow powder was ground for further applications.
N (mg g-1) is the adsorbed amount at the equilibriuVmie;wTA(rKtic)leisOntlhinee
DOI: 10.1039/C7TA01986F
corresponding temperature; Qst (KJ mol-1) is the isosteric heat; R is
the ideal gas constant, 8.314 J mol-1 K-1; and ai and bi are Virial
parameters.
P(nDVB-IL)s with common ILs ([EVIM][Br], 1-ethyl-3-
vinylimidazolium tetrafluoroborate ([EVIM][BF4]), 1-ethyl-3-
vinylimidazolium hexafluorophosphate ([EVIM][PF6]), and 1-ethyl-3-
vinylimidazolium bis(trifluoromethylsulfonyl)imide ([EVIM][Tf2N])
were obtained under similar methods, except the P(nDVB-IL)s
sample used a 2:1 DVB: ILs molar ratio. For [EVIM][Br], a mixture of
ethyl acetate, EtOH and H2O (volume ratio = 8:2:1) was used as the
porogenic solvent. And the textural parameters of, N2
adsorption/desorption isotherms and pore size distributions are
shown in Table S8 and Fig. S14. †
Batch adsorption experiments
The batch adsorption experiments were carried out as follows. For
tocopherol homologues, 40.00 mg adsorbent and 20 mL heptane
solution with a total tocopherol concentration of 3.54 mg mL-1 (the
concentration of δ-tocopherol at 0.50 mg mL-1, β- and γ-tocopherol
at 1.54 mg mL-1 in total, and α-tocopherol at 1.50 mg mL-1) were
added to the conical flask and shaken in a thermostatic rotary
shaker at 25 °C and 200 rpm for 24 h to achieve adsorption
equilibrium. Then, samples were taken from the solution, and the
concentrations of tocopherols were determined using high
performance liquid chromatography (HPLC).64 The adsorption
capacity Qi and selectivity of solute i versus j (Si/j) were calculated by
equations 5 and 6:
Synthesis of HP(DVB-EVIMCm)s
In a typical run for HP(DVB-EVIMCm)s, 0.40 g of the precursor
P(DVB-EVIMC12) was swollen using 20 mL of EtOH, followed by the
addition of 0.02 g of anhydrous FeCl3. Then, the mixture was
deoxygenated by pumping for 20 min, and backfilled with N2, and
stirred for 24 h at 80 °C. The produced sample was washed with
plenty of water and EtOH to remove the FeCl3 and was dried under
high vacuum at 65 °C for 24 h.
(Cei −Cfi)V
(5)
(6)
Qi =
W
Cei −Cfi
Cej −Cfj
Si/ j
=
Where Qi (mg g-1) is the uptake of solute i on the adsorbent; Cei
and Cfi (mg mL-1) are the concentrations of solute i in feed and
equilibrium solution, respectively; V (mL) is the volume of the
heptane solution and W (g) is the weight of the adsorbent. The
adsorption experiments were repeated at least three times. In the
adsorption experiments for organic phenolic compounds, the
heptane solution contained 1.00 mg mL-1 phenol, 1.15 mg mL-1 p-
cresol, and 1.30 mg mL-1 2,6-dimethylphenol.
The regeneration experiments were carried out as follows. After
achieving adsorption equilibrium each time, the adsorbent was
filtered, added to the conical flask with 25 mL EtOH, and shaken in a
thermostatic rotary shaker at 45 °C and 200 rpm for 8 h, this
procedure was performed for five times to regenerate the
adsorbent adequately. Then for next cycle, the adsorbent was dried
under high vacuum at 65 °C for 12 h.
Gas adsorption experiments
Adsorption isotherms of CO2 and N2 were measured on an ASAP
2050 (Micromeritics) at 25 and 0 °C and from 0 to 1 bar. All samples
were degassed at 100 °C for 12 h prior to the measurements.
Pure component isotherm data were fitted with the dual-
Langmuir-Freundlich isotherm (DSLF) model (equation 1) for the
calculation of the isosteric heat and adsorption selectivity：.
bA pν
1 + bA pν
bB pν
A
B
q = qA,sat
+ qB,sat
(1)
1 + bB pν
A
B
where P (kPa) is the pressure of the bulk gas at the equilibrium
with the adsorbed phase; q (mol kg-1) is the adsorbed amount at the
equilibrium; qA,sat and qB,sat (mol kg-1) are the saturation capacities
of site A and B; bA and bB (kPa-νi) are the affinity coefficients of site A
and B; and νA and νB are the Freundlich coefficients. The fitted
parameter values are presented in Table S6.†
The adsorption selectivity for CO2/N2 separation was estimated
using ideal adsorbed solution theory (IAST) (equation 2):71
xi / xj
Acknowledgements
The research was supported by the National Natural Science
Foundation of China (21222601, 21476192, and 21436010), the
Zhejiang Provincial Natural Science Foundation of China
(LR13B060001), and the Fundamental Research Funds for the
Central Universities (2014XZZX003-17).
Sads
=
(2)
yi / yj
where xi and xj are the adsorption capacity of component i and j,
and yi and yj are the gaseous molar fractions of i and j.
The isosteric heats of adsorption were calculated using Virial
equations (equation 3 and 4) based on isotherms at two different
temperatures (25 and 0 °C). The fitted curves and parameter values
are presented in Table S7 and Fig. S12: †
Notes and references
1. D. Wu, F. Xu, B. Sun, R. Fu, H. He and K. Matyjaszewski, Chem.
Rev., 2012, 112, 565-567.
2. P. Kuhn, M. Antonietti and A. Thomas, Angew. Chem. Int. Ed.,
2008, 47, 3450-3453.
m
m
1
T
lnp =lnN +
a Ni + b Ni
(3)
(4)
∑
∑
i
i
i=0
i=0
m
Qst = −R a Ni
∑
i
i=0
8 | J. Name., 2012, 00, 1-3
This journal is © The Royal Society of Chemistry 20xx
Please do not adjust margins

Please do not adjust margins
Journal of Materials Chemistry A
Page 9 of 11
ARTICLE
Journal Name
3. J. Byun, S.-H. Je, H. A. Patel, A. Coskun and C. T. Yavuz, J. Mater. 33. N. Li, M. Zheng, S. Feng, H. Lu, B. Zhao, J. Zheng, VSi.ewZhAratinclge,OGnl.inJei
Chem. A, 2014, 2, 12507-12512. and J. Cao, J. Phys. Chem. C, 2013, 117, 8784-8792.
4. F. Liu, L. Wang, Q. Sun, L. Zhu, X. Meng and F. S. Xiao, J. Am. 34. J. Zhang, Z. A. Qiao, S. M. Mahurin, X. Jiang, S. H. Chai, H. Lu, K.
Chem. Soc., 2012, 134, 16948-16950. Nelson and S. Dai, Angew. Chem. Int. Ed., 2015, 127, 4665-4669.
5. P. Zhang, Z. A. Qiao, X. Jiang, G. M. Veith and S. Dai, Nano Lett., 35. W. Jin, Q. Yang, Z. Zhang, Z. Bao, Q. Ren, Y. Yang and H. Xing,
DOI: 10.1039/C7TA01986F
2015, 15, 823-828.
Chem. Commun., 2015, 51, 13170-13173.
6. J. Yuan and M. Antonietti, Polymer, 2011, 52, 1469-1482.
7. J. Yuan, D. Mecerreyes and M. Antonietti, Prog. Polym. Sci., 2013,
38, 1009-1036.
8. S. Zhang, K. Dokko and M. Watanabe, Chem. Sci., 2015, 6, 3684-
3691.
9. S. Yuan, Q. Deng, G. Fang, M. Pan, X. Zhai and S. Wang, J. Mater.
Chem., 2012, 22, 3965-3972.
10. S. Zulfiqar, M. I. Sarwar and D. Mecerreyes, Polym. Chem., 2015,
6, 6435-6451.
11. D. Chandra and A. Bhaumik, J. Mater. Chem., 2009, 19, 1901-
1907.
12. A. Wilke, J. Yuan, M. Antonietti and J. Weber, ACS Macro Lett.,
2012, 1, 1028-1031.
13. S. Soll, Q. Zhao, J. Weber and J. Yuan, Chem. Mater., 2013, 25,
3003-3010.
14. K. Täuber, Q. Zhao, M. Antonietti and J. Yuan, ACS Macro Lett.,
2014, 4, 39-42.
36. X. Liu, Q. Yang, Z. Bao, B. Su, Z. Zhang, Q. Ren, Y. Yang and H.
Xing, Chem. Eur. J., 2015, 21, 9150-9156.
37. Y. Xie, H. Xing, Q. Yang, Z. Bao, B. Su and Q. Ren, ACS
Sustainable Chem. Eng., 2015, 3, 3365-3372.
38. X. Ni, H. Xing, Q. Yang, J. Wang, B. Su, Z. Bao, Y. Yang and Q.
Ren, Ind. Eng. Chem. Res., 2012, 51, 6480-6488.
39. M. Blahušiak, Š. Schlosser and J. Marták, Sep. Sci. Technol.,
2013, 119, 102-111.
40. L. Alonso, A. Arce, M. Francisco, O. Rodríguez and A. Soto, AIChE
J., 2007, 53, 3108-3115.
41. A. Arce, M. J. Earle, H. Rodríguez, K. R. Seddon and A. Soto,
Green Chem., 2008, 10, 1294-1300.
42. X. Cui, K. Chen, H. Xing, Q. Yang, R. Krishna, Z. Bao, H. Wu, W.
Zhou, X. Dong and Y. Han, Science, 2016, 353, 141-144.
43. A. Dani, E. Groppo, C. Barolo, J. G. Vitillo and S. Bordiga, J.
Mater. Chem. A, 2015, 3, 8508-8518.
44. Y. Luo, B. Li, W. Wang, K. Wu and B. Tan, Adv. Mater., 2012, 24,
5703-5707.
15. J. E. Bara, C. J. Gabriel, E. S. Hatakeyama, T. K. Carlisle, S.
Lessmann, R. D. Noble and D. L. Gin, J. Membr. Sci., 2008, 321, 45. L.-B. Sun, Y.-H. Kang, Y.-Q. Shi, Y. Jiang and X.-Q. Liu, ACS
3-7. Sustainable Chem. Eng., 2015, 3, 3077-3085.
16. X. Hu, J. Tang, A. Blasig, Y. Shen and M. Radosz, J. Membr. Sci., 46. L.-B. Sun, A.-G. Li, X.-D. Liu, X.-Q. Liu, D. Feng, W. Lu, D. Yuan
2006, 281, 130-138. and H.-C. Zhou, J. Mater. Chem. A, 2015, 3, 3252-3256.
17. Q. Zhao, P. Zhang, M. Antonietti and J. Yuan, J. Am. Chem. 47. G. Kyriakopoulos, D. Doulia and E. Anagnostopoulos, Chem. Eng.
Soc.,2012, 134, 11852-11855. Sci., 2005, 60, 1177-1186.
18. Y. Xie, Z. Zhang, J. Tao, J. He, B. Han, T. Wu and K. Ding, Angew. 48. X. Zeng, H. Yao, M. Ning, Y. Fan, C. Wang and R. Shi, J. Colloid
Chem. Int. Ed., 2007, 46, 7255-7258. Interface Sci., 2011, 354, 353-358.
19. X. Wang, Y. Zhou, Z. Guo, G. Chen, J. Li, Y. Shi, Y. Liu and J. Wang, 49.K. Aleksieva, X. Jing, M. W. Li, A. Sassi, Z. Pientka, Z. Zhang and K.
Chem. Sci., 2015, 6, 6916-6924. Jerabek, Polymer, 2006, 47, 6544-6550.
20. Q. Zhao, J. W. Dunlop, X. Qiu, F. Huang, Z. Zhang, J. Heyda, J. 50. S. Xu, Y. Luo and B. Tan, Macromol. Rapid Commun., 2013, 34,
Dzubiella, M. Antonietti and J. Yuan, Nat. Commun., 2014, 5,
4293-4293.
21. Y. Xiong, J. Liu, Y. Wang, H. Wang and R. Wang, Angew. Chem.
Int. Ed., 2012, 51, 9114-9118.
22. Y. Deguchi, Y. Kohno and H. Ohno, Chem. Commun., 2015, 51,
9287-9290.
23. C. Gao, G. Chen, X. Wang, J. Li, Y. Zhou and J. Wang, Chem.
Commun., 2015, 51, 4969-4972.
24. C. Liang and S. Dai, Chem. Mater., 2009, 21, 2115-2124.
25. M. Seo and M. A. Hillmyer, Science, 2012, 336, 1422-1425.
26. X. Feng, C. Gao, Z. Guo, Y. Zhou and J. Wang, RSC Adv., 2014, 4,
23389-23395.
27. D. Kuzmicz, P. Coupillaud, Y. Men, J. Vignolle, G. Vendraminetto,
M. Ambrogi, D. Taton and J. Yuan, Polymer, 2014, 55, 3423-
3430.
28. X. Wang, J. Li, G. Chen, Z. Guo, Y. Zhou and J. Wang,
ChemCatchem, 2015, 7, 993-1003.
29. F. Liu, W. Kong, C. Qi, L. Zhu and F. S. Xiao, ACS Catal., 2012, 2,
565-572.
471-484.
51. M. Seo, S. Kim, J. Oh, S. J. Kim and M. A. Hillmyer, J. Am. Chem.
Soc., 2015, 112, 297-311.
52. X. Zhao, Q. Yang, D. Xu, Z. Bao, Y. Zhang, B. Su, Q. Ren and H.
Xing, AIChE J. , 2015, 61, 2016-2027.
53. Q. Yang, D. Xu, J. Zhang, Y. Zhu, Z. Zhang, C. Qian, Q. Ren and H.
Xing, ACS Sustainable Chem. Eng., 2015, 3, 309-316.
54. Q. Zhao, S. Soll, M. Antonietti and J. Yuan, Polym. Chem., 2013,
4, 2432-2435.
55. M. P. Tsyurupa and V. A. Davankov, React. Funct. Polym., 2002,
53, 193-203.
56. C. D. Wood, B. Tan, A. Trewin, F. Su, M. J. Rosseinsky, D.
Bradshaw, Y. Sun, L. Zhou and A. I. Cooper, Adv. Mater., 2008,
20, 1916-1921.
57. Z. A. Qiao, S. H. Chai, K. Nelson, Z. Bi, J. Chen, S. M. Mahurin, X.
Zhu and S. Dai, Nat. Commun., 2014, 5, 643-648.
58. L. Hu, H. Ni, X. Chen, L. Wang, Y. Wei, T. Jiang, Y. Lü, X. Lu and P.
Ye, Polym. Eng. Sci., 2016, 56, 573-582.
59. J. Wang, Y. J. Wei, G. Yi and Y. Zhang, Chem. Commun., 2015, 51,
15708-15711.
30. Y. Yue, R. T. Mayes, J. Kim, P. F. Fulvio, X. G. Sun, C. Tsouris, J.
Chen, S. Brown and S. Dai, Angew. Chem. Int. Ed., 2013, 52, 60. A. Chinnappan and A. H. Tamboli, Chem. Eng. J., 2015, 285, 554-
13458-13462. 561.
31. Y. Zhang, S. Wei, F. Liu, Y. Du, S. Liu, Y. Ji, T. Yokoi, T. Tatsumi 61. J. Wang, W. Sng, G. Yi and Y. Zhang, Chem. Commun., 2015, 51,
and F. S. Xiao, Nano Today, 2009, 4, 135-142. 12076-12079.
32. S. Dutta, K. C. W. Wu and T. Kimura, Chem. Mater., 2015, 27, 62. X. Wu, Y. Liu, Y. Liu, D. Di, M. Guo and L. Zhao, RSC Adv., 2015,
6918-6928.
5, 72601-72609.
This journal is © The Royal Society of Chemistry 20xx
J. Name., 2013, 00, 1-3 | 9
Please do not adjust margins

Please do not adjust margins
Journal of Materials Chemistry A
Page 10 of 11
ARTICLE
Journal Name
63. J. Wang, L. Huang, R. Yang, Z. Zhang, J. Wu, Y. Gao, Q. Wang, D.
O'Hare and Z. Zhong, Energy Environ. Sci., 2014, 7, 3478-3518.
64. Q. Yang, H. Xing, Y. Cao, B. Su, Y. Yang and Q. Ren, Ind. Eng.
Chem. Res., 2009, 48, 6417-6422.
View Article Online
DOI: 10.1039/C7TA01986F
65. F. Bezold, M. E. Weinberger and M. Minceva, J. Chromatogr. A,
2017, 1491, 153-158.
66. L. Qin, J. Zhang, H. Cheng, L. Chen, Z. Qi and W. Yuan, ACS
Sustainable Chem. Eng., 2016, 4, 583-590.
67. H. Liu, G. Fang, C. Li, M. Pan, C. Liu, C. Fan and S. Wang, J.
Mater. Chem., 2012, 22, 19882-19887.
68. Q. Yang, H. Xing, B. Su, Z. Bao, J. Wang, Y. Yang and Q. Ren,
AIChE J., 2013, 59, 1657-1667.
69. J. Marták and Š. Schlosser, Sep. Sci. Technol., 2007, 57, 483-494.
70. J. Yuan and M. Antonietti, Macromolecules, 2011, 44, 744-750.
71. A. L. Myers and J. M. Prausnitz, AIChE J., 1965, 11, 121-127.
10 | J. Name., 2012, 00, 1-3
This journal is © The Royal Society of Chemistry 20xx
Please do not adjust margins

Page 11 of 11
Journal of Materials Chemistry A
View Article Online
DOI: 10.1039/C7TA01986F
Table of content
New anion-functionalized mesoporous poly(ionic liquid)s were synthesized via a microphase
separation-hypercrosslinking strategy, and were utilized as highly efficient adsorbents for
bioactive molecules.