Ionic Covalent Organic Frameworks: Design of a Charged Interface Aligned on 1D Channel Walls and Its Unusual Electrostatic Functions

Article abstract of DOI:10.1002/anie.201611542

Covalent organic frameworks (COFs) have emerged as a tailor-made platform for designing layered two-dimensional polymers. However, most of them are obtained as neutral porous materials. Here, we report the construction of ionic crystalline porous COFs wit

Full text of DOI:10.1002/anie.201611542

Angewandte
Communications
Chemie
International Edition: DOI: 10.1002/anie.201611542
German Edition: DOI: 10.1002/ange.201611542
Carbon Capture
Ionic Covalent Organic Frameworks: Design of a Charged Interface
Aligned on 1D Channel Walls and Its Unusual Electrostatic Functions
+
+
Ning Huang , Ping Wang , Matthew A. Addicoat, Thomas Heine, and Donglin Jiang*
Abstract: Covalent organic frameworks (COFs) have emerged
as a tailor-made platform for designing layered two-dimen-
sional polymers. However, most of them are obtained as
neutral porous materials. Here, we report the construction of
ionic crystalline porous COFs with positively charged walls
that enable the creation of well aligned yet spatially confined
ionic interface. The unconventional reversed AA-stacking
mode alternately orientates the cationic centers to both sides
of the walls; the ionic interface endows COFs with unusual
electrostatic functions. Because all of the walls are decorated
diction between the charged layers and the crystallinity and
porosity of COFs. Here, we report a general strategy for
designing ionic COFs with high crystallinity and porosity,
through the combination of ionic linkers and neutral knots for
the construction of ionic interfaces that are well aligned yet
spatially confined on the pore walls. The COFs assume an
unconventional reverse AA-stacking mode in which the
cationic benzimidazolium linkers are alternately orientated
and aligned on both sides of the pore walls. We highlight that
such an alternate alignment exerts profound effects on the
ionic interface and triggers unusual electrostatic functions of
COFs. By virtue of reduced charge repulsion between layers,
the ionic COFs possess high crystallinity and porosity. With
electric dipoles on both sides of the walls, the COF enhances
the CO2 adsorption by even three fold. The alternately
aligned layers offer sufficient open space around cationic
centers and the ionic interfaces exhibit exceptional accessi-
bility, efficiency, and selectivity in trapping and removing
anionic pollutants.
[
4d]
with electric dipoles, the uptake of CO is enhanced by three
2
fold compared to the neutral analog. By virtue of sufficient
open space between cations, the ionic interface exhibits excep-
tional accessibility, efficiency, and selectivity in ion exchange to
trap anionic pollutants. These findings suggest that construc-
tion of the ionic interface of COFs offers a new way to
structural and functional designs.
C
tures.
ovalent organic frameworks (COFs) are crystalline porous
polymers with designable primary- and high-order struc-
We synthesized 4,4’,4’’,4’’’-(pyrene-1,3,6,8-tetrayl) tetraa-
niline (PyTTA) as neutral knot and 5,6-bis(4-formylbenzyl)-
1,3-dimethyl-benzimidazolium bromide (BFBIm, see the
Supporting Information) as cationic linker for the construc-
tion of imine-linked positively charged COFs in which the
benzimidazolium cationic sites were exposed to the wall
surface (Figure 1a, PyTTA-BFBIm-iCOF). The reaction was
carried out in a mixture of o-dichlorobenzene and n-butanol
in the presence of acetic acid catalyst under solvothermal
conditions at 1208C for 3 days (see the Supporting Informa-
tion). PyTTA-BFBIm-iCOF was obtained as yellow powder
at an isolated yield of 82%. A variety of methods were
employed for structural characterizations. The infrared spec-
[
1,2]
Recent progress in the chemistry of COFs had
significant effect on enhancing their structural diversity and
[3]
complexity. However, most of COFs still rely on neutral
skeletons. Integration of ionic modules into the frameworks
has a high probability of generating ionic interfaces to control
the interactions with molecules and ions that would induce
[
1,4]
novel functions distinct from those of neutral skeletons.
In
this sense, the wall surface of the one-dimensional (1D)
channels of COFs is of great interest because it constitutes the
interface between molecules and COFs.
To implant ionic interface on the pore walls requires the
use of ionic building blocks, which however, prevent p–p
stacks owing to strong charge repulsion and usually result in
À1
trum revealed a stretching vibration band at 1624 cm that
[
4]
low crystallinity and porosity. Therefore, there is a contra-
was assigned to the C=N bonds (see Figure S1 in the
Supporting Information). Elemental analysis corroborates
well with the theoretical values of infinite 2D sheet
(Table S1). Field emission scanning electronic microscopy
revealed that PyTTA-BFBIm-iCOF adopts micrometer-scale
belt morphology (Figure S2). High-resolution transmission
electron microscopy enables the direct visualization of pores
[
+]
[+]
[
*] Dr. N. Huang, P. Wang, Prof. Dr. D. Jiang
Field of Energy and Environment, School of Materials Science
Japan Advanced Institute of Science and Technology
1-1 Asahidai, Nomi 923-1292 (Japan)
E-mail: djiang@jaist.ac.jp
Dr. M. A. Addicoat, Prof. Dr. T. Heine
Wilhelm-Ostwald-Institut fꢀr Physikalische und Theoretische Chemie
Universitꢁt Leipzig, Linnꢂstrasse 2, 04103 Leipzig (Germany)
(Figure S3). PyTTA-BFBIm-iCOF is thermally stable up to
4
508C under nitrogen (Figure S4).
PyTTA-BFBIm-iCOF is a highly crystalline polymer with
strong signals in powder X-ray diffraction (PXRD). PyTTA-
BFBIm-iCOF exhibited diffraction peaks at 3.488, 5.148,
[
+]
P. Wang
Department of Structural Molecular Science
School of Physical Science, SOKENDAI
Hayama 240-0193, Kanagawa (Japan)
7
.068, 10.608, 14.358, and 23.888, which were assignable to the
(110), (020), (220), (040), (060), and (001) facets, respectively
Figure 1 f, red curve). The presence of (001) facets indicates
+
[
] These authors contributed equally to this work.
(
Supporting information and the ORCID identification number(s) for
the author(s) of this article can be found under:
http://dx.doi.org/10.1002/anie.201611542.
that PyTTA-BFBIm-iCOF has periodic orders in all three
dimensions. The Pawley-refined pattern (black curve) with Rw
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Figure 1. a) Schematic representation of the synthesis of PyTTA-BFBIm-iCOF. b) Top and c) side views of the reversed slipped AA-stacking mode
À
of PyTTA-BFBIm-iCOF (gray: C, orange: Br , blue: N, white: H); d) Top and e) side views of slipped AA-stacking mode. f) PXRD patterns of
PyTTA-BFBIm-iCOF of experimentally observed (red), Pawley refined (black), their difference (green), simulated curves for reversed slipped AA-
stacking mode (blue), slipped AA-stacking mode (purple), and staggered AB-stacking mode (orange). Units cells of g) reversed slipped AA,
h) slipped AA, and i) staggered AB-stacking modes.
and RWP values of 5.57% and 7.23%, respectively, confirmed
the correctness of peak assignments as evident by negligible
deviation from the observed PXRD patterns (green curve).
Structural simulations were conducted by using the self-
consistent charge density functional tight binding (SCC-
DFTB) method with starting structures created by AuTo-
GraFS and pre-optimized using a topology-preserving force
field (see the Supporting Information). We optimized the
monolayer and then various layered framework structures
with different stacking modes. In PyTTA-BFBIm-iCOF, the
reversed slipped AA-stacking mode is the most stable
structure in the total energy among the various stacking
modes, including slipped AA- and staggered AB-stacking
modes (Figures S5 and S6, Tables S2 and S3). The reversed
slipped AA-stacking mode avoids the direct overlap of
benzimidazolium cationic centers on each other between
neighboring layers and reduces the repulsion between layers
mode distributes the benzimidazolium cationic centers on
both sides of the pore walls (Figure 1b,c).
The high crystallinity of PyTTA-BFBIm-iCOF intrigues
us to evaluate its porosity. PyTTA-BFBIm-iCOF exhibited
reversible type IV sorption curves (Figure 2a), which are
Figure 2. a) Nitrogen sorption curves of PyTTA-BFBIm-iCOF at 77 K
(filled circles for adsorption, open circles for desorption). b) The pore
(
Figure 1b,c). The reversed slipped AA-stacking mode
size distribution and pore volume of PyTTA-BFBIm-iCOF.
yielded a PXRD pattern (Figure 1 f, blue curve) that was in
good agreement with the experimentally observed PXRD
profile. PyTTA-BFBIm-iCOF assumes the space group of
Pmm2 with a = 24.46 ꢀ, b = 28.61 ꢀ, c = 7.44 ꢀ, and a = b =
g = 908 (for atomic coordinates see Table S4). On the other
hand, the staggered AB-stacking mode could not reproduce
the PXRD pattern (Figure 1 f, orange curve). In contrast to
the slipped AA-stacking mode that gives rise to an orientation
of the benzimidazolium cationic centers to only one side of
the pore walls (Figure 1d,e), the reverse slipped AA-stacking
characteristics of mesoporous materials. The Brunauer—
Emmett–Teller (BET) surface area was calculated to be as
2
À1
high as 1532 m g . To the best of our knowledge, this surface
[4]
area is the highest among ionic COFs reported to date. We
evaluated the pore size and its distribution by using the
nonlocal density functional theory method (Figure 2b).
PyTTA-BFBIm-iCOF exhibited only one type of pore at
2.3 nm, which is close to its theoretical value. The total pore
3
À1
volume was estimated to be 0.7 cm g .
2
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[
6a]
Chemical stability is important for ionic materials. With
273 K and 1 bar, the same at below),
COF-102
ILCOF-
TpPa-
[
6a]
[6a]
the high crystallinity and porosity in mind, we treated the
PyTTA-BFBIm-iCOF samples in different solvents, including
N,N-dimethylformamide (DMF), boiling water, and aqueous
HCl (3m) and NaOH (3m) solutions at 258C for 24 h. The
COF samples were collected, washed with water and THF,
dried under vacuum at 1208C for 12 h, and subjected to
(1.21 wt%),
COF-103
(7.6 wt%),
[
6b]
[6c]
1
(6.0 wt%),
TDCOF-5
(9.2 wt%),
and even carboxylic acid functionalized
-H P-COF (17.4 wt%). As a control, we syn-
2
[
6d]
1 (15.6 wt%),
[
5b]
[HO C]
2
100%
thesized PyTTA-TPhA-COF that is a neutral analog to
PyTTA-BFBIm-iCOF without ionic interface on the pore
walls (Figures S7 and S8). PyTTA-TPhA-COF exhibits a high
PXRD (Figure 3a) and N sorption isotherm measurements
2
2
À1
BET surface area of 1754 m g
(Figure S9). However,
PyTTA-TPhA-COF uptakes CO with capacities of only
2
À1
À1
6
5 mgg at 273 K and 36 mgg at 298 K and 1 bar (Fig-
ure S10). Therefore, the ionic interface in the COFs enhances
the CO adsorption by almost three fold. The Q value was
2
st
À1
calculated from the isotherms to be 30.2 kJmol , which is
moderate in COFs (Figure 4b).
The alternate orientation of cationic centers to both sides
of the walls leaves enough space between cationic sites. Such
a spatial alignment greatly enhances the accessibility of the
cationic sites by guest molecules. Herein, we developed the
ionic interface to trap ionic pollutants through ion exchange,
by dispersing insoluble PyTTA-BFBIm-iCOF powder (5 mg)
to the ethanol/water solution (1/1 by vol., 15 mL) of anionic
Figure 3. a) PXRD patterns and b) N sorption curves of PyTTA-BFBIm-
iCOF upon 24-hour treatment in different solvents (color in b is the
same as that in a).
2
À1
methyl orange (MO, 200 mgL ) at room temperature. The
trapping process is easily monitored by electronic absorption
spectroscopy (Figure 5a). Time-dependent spectral change
shows that the absorption band of MO at 465 nm decreased
with time. The PyTTA-BFBIm-iCOF can rapidly capture
MO; after 10 h the residual MO concentration in the solution
(
Figure 3b). Surprisingly, all these samples exhibited intense
PXRD patterns without changes in the peak position and
intensity, indicating that the high crystallinity is retained
under these harsh conditions (Figure 3a). Moreover, the BET
surface areas were also retained under these conditions
À1
was smaller than 0.1 mgL . This result suggests that over
99.9% of MO was removed by PyTTA-BFBIm-iCOF. The ion
exchange between the anionic MO and the bromide anions
occur on the wall surfaces of PyTTA-BFBIm-iCOF, leading to
the trap of MO.
(
Figure 3b).
To date, a number of porous materials have been
[
5]
developed for CO capture and separation. These inves-
2
tigations revealed that the nature of chemical functionality
along with the textural properties of polymers is an important
We investigated the removal capacity by keeping the
amount COF and changing the initial concentration (Ci) of
the MO solutions. As a result, the adsorption capacity versus
concentration plot reveals a sharp increase at low concen-
parameter to tailor CO affinity of these materials. In the case
2
of COFs, introduction of polar groups such as amine and
À1
À1
carboxylic acid units has shown positive effects on CO
tration (0–30 mgL ) and saturated after 50 mgL (Fig-
ure 5b). Surprisingly, the maximum removal capacity of
2
[5]
adsorption. Although ionic surface is promising to enhance
the CO2 affinity through dipole–quadruple interactions,
however, to what extent an ionic interface of COFs will
À1
PyTTA-BFBIm-iCOF was as high as 553 mgg (see the
Supporting Information). This maximum capacity is equiv-
alent to 0.81 MO anion per benzimidazolium cation, suggest-
ing the high accessibility of benzimidazolium cationic sites to
the MO anions. To the best of our knowledge, the capacity of
PyTTA-BFBIm-iCOF is the highest among adsorbent mate-
rials reported to date and is much higher than those of
affect the CO adsorption remains unprecedented.
2
PyTTA-BFBIm-iCOF uptakes CO with capacities of
2
À1
À1
9
3 mgg at 298 K and 177 mgg at 273 K and 1 bar (Fig-
ure 4a). The ionic COF is superior to COF-5 (5.9 wt%, at
benchmark porous materials, for example, nanosize SiO -
2
À1 [7a]
Al O mixed oxides (381 mgg ), nanostructured proton-
2
3
À1 [7b]
containing H-d-MnO nanoparticles (427 mgg ),
alkali-
2
activated
multi-walled
carbon
nanotube
CNTs-A
À1 [7c]
À1 [7d]
(149 mgg ),
and NH -MIL-101(Al) (199 mgg ).
The
2
equilibrium adsorption isotherm can be perfectly fitted with
2
Langmuir model to yield a high correlation coefficient (R >
0
.999) (Figure 5c, see the Supporting Information). This
linear curve reflects that trapping MO by PyTTA-BFBIm-
iCOF is based on Langmuir adsorption model.
To investigate the kinetics of the trapping process by
dispersing PyTTA-BFBIm-iCOF (5 mg) in the ethanol/water
solution of MO (1/1 by volume, 30 mgL , 50 mL), we
Figure 4. a) CO (circles) and N (triangles) adsorptions at 273 K (red)
2
2
À1
and 298 K (blue). b) Qst value for CO adsorption at low coverage.
2
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By virtue of skeleton stability in acidic and basic solutions,
we further investigated the removal of MO under different
pH conditions. PyTTA-BFBIm-iCOF exhibited the removal
efficiency of 99% at the pH values of 1 and 4 (Figure 5 f). To
our surprise, the efficiencies were as high as 95% and 91% at
pH values of 10 and 13, respectively. The slight decrement
À
under basic condition originates from the enhanced OH
anions that compete with the MO anions. High performance
over a wide pH range is important for applications. In this
sense, PyTTA-BFBIm-iCOF is much superior to porous
silicas that deteriorate under harsh conditions.
Interestingly, the ionic surface can also trap dianions
efficiently. For example, when the dianionic indigo carmine
acid blue 74 (IC-74) was used, PyTTA-BFBIm-iCOF can
remove IC-74 with a high efficiency of 98.5% (Figure 5d and
Figure S11). By contrast, PyTTA-TPhA-COF cannot trap
neutral and cationic molecules (Figure 5d). Indeed, neutral
nile red (NR) or coumarin 6 (C6), and cationic rhodamine B
(RB) exhibited very low trapping levels of only 1.6%, 4.3%
and 2.4%, respectively (Figure 5g, Figures S12–S14). These
contrastive results indicate that the ionic interfaces recognize
the opposite charges and the electrostatic interactions on the
wall surfaces enable a distinct discrimination between anions,
cations, and neutral species.
After trapping anionic pollutants, the ionic interface can
be simply regenerated by treating the COF samples with
aqueous NaBr solution (1.0m) at room temperature for 48 h.
The MO anions can be desorbed nearly quantitatively. This
high regeneration yield of COFs makes the repetitive use
possible. It is worthy to mention that PyTTA-BFBIm-iCOF
retained 92% of the original capacity even after six cycles
(Figure 5h). All the above results indicate that the ionic COF
sets a new benchmark that combines capacity, efficiency,
durability, selectivity, and reusability in removing anionic
pollutants.
In summary, we have shown that COFs offer a wonderful
extended scaffold for creating ionic interfaces that are well
aligned and spatially confined on the pore walls of one-
dimensional channels. We elucidated two fundamental
aspects of ionic interface, that is, electric dipole and electro-
static interactions through the findings of their unusual
Figure 5. a) Time-dependant electronic absorption spectral change
from top: 0 min, 1 min, 2 min, 3 min, 5 min, 10 min, 12 min, 15 min,
(
2
0 min, 30 min, 1 h, 2 h, 3 h, 5 h, 10 h) of an ethanol/water solution
À1
(
1/1 by volume, 15 mL) of MO at initial concentration of 200 mgL
functions in CO adsorption and ion exchange to remove
2
upon addition of PyTTA-BFBIm-iCOF (5 mg). b) Adsorption isotherm
of MO. c) Linear regression using Langmuir adsorption model.
d) Effect of contact time on the MO adsorption at initial concentration
of 30 mgL . e) Pseudo-second-order kinetics of MO adsorption.
f) Capture efficiency of MO at different pH values. g) Capture efficiency
of different dyes. h) Cycle performance.
anionic pollutants. It becomes clear that ionic interfaces can
induce new functions or boost physiochemical properties.
With the availability of various types of charged species as
well as the possibility to design COFs, the creation of ionic
interfaces provides a new chemical platform for structural and
functional designs.
À1
evaluated the contact time-dependent adsorption profiles. As Acknowledgements
shown in Figure 5d, the adsorption was quick and completed
within 100 min. By using the pseudo-second-order kinetics
Figure 5e, correlation coefficient R = 0.998), the kinetic
constant (k) was evaluated to be 5.32 ꢁ 10 gmg min .
This work was supported by ENEOS Hydrogen Trust Fund.
(
À2
À1
À1
Notably, this k value is larger than those of other porous Conflict of interest
materials,
including
activated
carbon
(2.17 ꢁ
À4
À1
À1 [7e]
À4
À1
À1 [7f]
1
0
gmg min ),
MOF-235 (7.67 ꢁ 10 gmg min ),
The authors declare no conflict of interest.
À3
À1
À1 [7e]
and PED-MIL-101 (2.75 ꢁ 10 gmg min ).
4
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Keywords: anionic pollutants · carbon dioxide ·
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Manuscript received: November 25, 2016
Revised: March 13, 2017
Final Article published: && &&, &&&&
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Communications
Carbon Capture
A scaffold for ionic interfaces: Covalent
organic frameworks were synthesized.
They bear ionic interfaces that are well
aligned and spatially confined on the one-
dimensional channel walls. The ionic
interfaces exert profound effects on the
frameworks and trigger unusual electro-
static functions, such as the adsorption
N. Huang, P. Wang, M. A. Addicoat,
T. Heine, D. Jiang*
&&&& — &&&&
Ionic Covalent Organic Frameworks:
Design of a Charged Interface Aligned on
1
D Channel Walls and Its Unusual
Electrostatic Functions
of CO and the selective removal of
2
anionic pollutants.
6
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