A Robust 3D Cage-like Ultramicroporous Network Structure with High Gas-Uptake Capacity

Article abstract of DOI:10.1002/anie.201800218

A three-dimensional (3D) cage-like organic network (3D-CON) structure synthesized by the straightforward condensation of building blocks designed with gas adsorption properties is presented. The 3D-CON can be prepared using an easy but powerful route, whi

Full text of DOI:10.1002/anie.201800218

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Accepted Article
Title: Robust 3D cage-like ultramicroporous network structure with high
gas uptake capacities
Authors: Javeed Mahmood, Seok-Jin Kim, Hyuk-Jun Noh, Sun-Min
Jung, Feng Li, Jeong-Min Seo, and Jong-Beom Baek
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COMMUNICATION
Robust 3D cage-like ultramicroporous network structure with high gas uptake capacities
Javeed Mahmood,‡ Seok-Jin Kim, Hyuk-Jun Noh, Sun-Min Jung, Ishfaq Ahmad, Feng Li, Jeong-Min Seo and
‡
Jong-Beom Baek*
[
5a]
Abstract: We report a three-dimensional (3D) cage-like organic
network (3D-CON) structure synthesized via the straightforward
condensation of building blocks designed with gas adsorption
properties. The 3D-CON can be prepared using an easy but powerful
route, which is essential for commercial scale-up. The resulting fused
aromatic 3D-CON exhibited a high Brunauer-Emmett-Teller (BET)
strategies . To fabricate stable OPMs, it is typically necessary to
apply rigid building blocks (repeating units) that prevent the collapse
of the framework and fill the volume space in a more periodic manner.
OPM rigidity is usually created by fusing repeating aromatic units.
However, while significant progress has been made in developing
robust OPMs , a better understanding of methods for fabricating
rigid structures with permanent pores using light elements is still
highly desired.
[
11]
2
1
specific surface area of up to 2247 m g . More importantly, the 3D-
CON displayed outstanding low pressure hydrogen (H , 2.64 wt%, 1.0
bar and 77 K), methane (CH , 2.4 wt%, 1.0 bar and 273 K) and carbon
dioxide (CO ,26.7 wt%, 1.0 bar and 273 K) uptake with a high isosteric
heat of adsorption (H
2
In the pursuit of high performance OPMs, we employed a strategy
4
[
12]
2
based on insights about the C N structure , to realize a uniformly
2
1
1
, 8.10 kJ mol ; CH
4
, 18.72 kJ mol ; CO
2
, 31.87
microporous robust three-dimensional (3D) cage-like organic network
(CON) structure by the condensation of triptycene-based hexamine
2
1
kJ mol ). These values are among the best reported for organic
networks with high thermal stability (~600 °C).
[
13]
(
THA) and hexaketocyclohexane (HKH) octahydrate (Figure 1; S1,
S2;). The resulting 3D-CON has a high Brunauer-Emmett-Teller
BET) specific surface area as well as good thermal and
With the growing consumption of fossil fuels and demand for clean
energy, worldwide environmental problems and gas storage needs
(
physiochemical stability. In addition to its exceptional surface area,
the as-produced 3D-CON outperformed highly porous MOFs in
thermal and hydrothermal stability, and demonstrated great potential
[
1]
have become increasingly important . Organic porous materials
(
OPMs) are considered fundamentally valuable for capturing carbon
[
2]
[1b]
dioxide (CO
2
)
and the safe storage of clean energy resources as
2 4 2
for H and CH storage as well as CO capture.
[
3]
well as explosive industrial gases (e.g., methane, CH
4
) . Among
The condensation reaction between THA and HKH spontaneously
results in the irreversible formation of fused aromatic pyrazine rings
without the use of an expensive catalyst. The structure of resulting
material is highly stable in a practical range of thermal and
physiochemical conditions.
Since 3D network structures result in a higher surface area
compared to two-dimensional (2D) framework structures, a potential
multifunctional candidate (monomer) with 3D topology was
deliberately selected to synthesize the 3D-CON in this study. This
clean energy sources, hydrogen (H ) has long been regarded as one
2
of the best alternatives to replace fossil fuels. It outperforms the others,
because it possesses the highest heat of combustion, and water is
[
4]
the only by-product after combustion .
Recent efforts have been undertaken to improve the design of
porous materials and develop processes which result in intrinsic
2 4 2
porosities, with the goal of enhancing H and CH storage, and CO
[
5]
capture . A notable area of progress in porous materials research
has been the evolution of porous high crystallinity metal-organic
frameworks (MOFs), which are constructed from metal ions and
[
3+3] condensation with THA used to form the pyrazine rings has
never been previously exploited. Triptycene is considered a promising
unit for the synthesis of 3D-CONs with good gas storage performance,
[
6]
organic linkers using reticular chemistry . Many of these interesting
materials have been reported to have the highest surface area and
[
14]
because it has a special ‘internal free volume’ feature . Moreover,
the presence of periodic nitrogen atoms, aromatic phenyl and
pyrazine rings in the 3D-CON are very useful for the adsorption and
desorption of gases and other metals in the structure.
[
6b, 7]
gas uptake capacity among all porous materials
. However,
despite their huge flexibility in design and diversity of structure, MOFs
inevitably contain a considerable amount of metal centers and
relatively weak coordination bonds, which can badly hamper their
After completing the condensation reaction between the THA and
HKH, a monolithic solid gel-like material was formed, and the reaction
solvent (ethylene glycol) around the material was almost clean
[
8]
applications . The poor stability problems might be resolved by
substituting susceptible chemical coordination bonds with stronger
covalent bonds, as has been demonstrated using covalent organic
(Figure 2a, b), suggesting the complete digestion of the starting
[
5a, 9]
frameworks (COFs) and porous polymeric materials (PPMs)
.
monomers. The subsequent Soxhlet extraction with water and
methanol also confirmed the clean reaction (no monomer residues),
with no color removal during the Soxhlet extraction process (Figure
OPMs (COFs and PPMs) are constructed from lightweight building
blocks with strong covalent bonding, and have attracted a great
amount of scientific and technological curiosity, while achieving critical
importance in many applications such as gas storage, catalysis and
2c). In the ethylene glycol and acetic acid mixture, the material looked
black (Figure 2a, b). After the removal of ethylene glycol and acetic
acid by washing with water, the material turned bright brown (Figure
[
5a, 9a]
gas separation
. These OPMs generally possess stable and
perpetual porosity, synthetic diversity, low mass densities and
physiochemical stability, which makes them immensely competitive in
2c) and the color remained after freeze drying, with an almost
quantitative yield (Figure 2d).
[
10]
gas storage applications . Further vigorous and intensive efforts are
The bright brown color is due to the breaking of aromaticity by a
barrelene-like moiety. It is this barrelene-like core in the THA that is
responsible for the formation of the stable and high surface area
material. Once the condensation between ortho-diamines in the THA
and diketones in HKH occurs, a fused aromatic pyrazine ring forms a
stable and rigid linker between the THA and HKH units. The resulting
underway to produce OPMs with higher surface areas via different
[*]
Dr. J. Mahmood, S.-J. Kim, H.-J. Noh, Dr. S-M. Jung, Dr. F. Li, J.-
M. Seo, Prof. J.-B Baek
School of Energy and Chemical Engineering/Center for Dimension
Controllable Organic Frameworks, Ulsan National Institute of
Science and Technology (UNIST), Ulsan 44919 (Korea)
E-mail: jbbaek@unist.ac.kr, Homepage: http://jbbaek.unist.ac.kr
‡
These authors contributed equally.
Supporting information for this article is given via a link at the end
of the document.
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Angewandte Chemie International Edition
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COMMUNICATION
CON. The survey scan spectrum from the 3D-CON
indicated the presence of C 1s, N 1s and O 1s
without any other elements in the structure (Figure
S5a). The peak, which appeared at 398.7 eV, was
2
attributed to the characteristic sp -hybridized
nitrogen atoms in the 3D-CON structure. In the high
resolution XPS spectrum, C 1s can be deconvoluted
into 284.3, 285.2 and 288.7 eV, which are
2
2
assignable to sp C-C and sp C-N in the aromatic
ring, and the minor peak at 288.7 eV is attributed to
2
2
2
the C-heteroatoms, e.g., sp C=O and sp C-NH at
the edges (Figure S5b). The N 1s peak shows one
major peak at 398.7 eV for the pyrazine-like nitrogen
in the structure (Figure S5c). The presence of the O
1s peak in the 3D-CON can be assigned to trapped
moisture and/or oxygen in the pores and residual
carbonyl (C=O) groups at the edges (Figure S5d).
The porous properties and surface area of the 3D-
CON was investigated by subjecting the framework
to nitrogen adsorption-desorption experiments at 77
Figure 1. Schematic illustration of robust 3D-CON structure. Triptycene-based hexamine
(THA) and hexaketocyclohexane (HKH) in ethylene glycol and acetic acid (3 M) mixture used
to form the 3D-CON. The three structures on the right side are from the different view angle.
structure is highly rigid and retains a diamond-like structural stability,
K. Before the sorption isotherm measurements, the sample was
preheated at 150 °C for 12 h under dynamic vacuum. As the sorption
isotherm displayed in Figure 3f, the 3D-CON isotherm was fully
reversible with an extremely steep nitrogen uptake in the low pressure
range (0-0.01). This result reflects the permanent microporous nature
of the material according to the IUPAC of relative pressure suggests
and also creates sufficient periodic micropores with greatly increased
13
internal surface areas. In addition, solid-state C cross-polarization
magic angle spinning (CP-MAS) nuclear magnetic resonance (NMR)
spectroscopy also revealed that condensation of the starting
monomers resulted in the complete transformation to pyrazine-linked
13
fused aromatic rings (Figure 1). The solid-state C CP-MAS NMR
[
15]
that the pore surface has relatively classification . The small
hysteresis observed over the whole range strong gas binding force.
spectrum revealed seven carbon peaks with chemical shifts of 53.5,
1
13, 124.1, 133.63, 143, 184 and 203 ppm, which can be assigned to
3
2
The sharp uptake at very low p/p
adsorptive interactions in the ultramicropores, resulting in micropore
filling at very low p/p . The Brunauer-Emmett-Teller (BET) model was
used on the isotherms at a relative p/p
o
is due to enhanced adsorbent-
the sp bridge carbon (e), aromatic (sp ) carbons (a, b, c, d, h) and the
edge carbonyl (C=O) groups (f, g), respectively (Figure 2e). In order
to investigate the long-range structure of the 3D-CON, powder X-ray
diffraction (PXRD) and transmission electron microscopy (TEM) were
performed. Although the peaks are broad due to the massive
molecular size (~∞), the PXRD pattern still revealed some order in the
structure (Figure 3a). The 3D-CON material does not exhibit long
range crystallographic ordering, but the locally
o
o
range (0.005-0.05) to generate
2
the BET surface area. The specific surface area found to be 2247 m
–1
3
–1
g
with a total pore volume of 1.06 cm
g and an average pore
diameter of 1.8 nm.
ordered structure is expected to support a high
surface area (vide infra).
Thermogravimetric analysis (TGA) revealed that
the 3D-CON was thermally stable. When the
temperature was raised from 50 to 600 °C, less than
4% weight loss occurred (Figure 3b). The 3D-CON
is insoluble in common organic solvents such as
DMF, alcohols, acetone and organic acids, even
after stirring at ambient condition for a long time (~
month), indicating that the 3D-CON framework
possesses high chemical stability. Transmission
electron microscopy (TEM) images obtained from
the dispersed sample revealed that the texture is
sheet-like (Figure S3a), but at high resolution it
exhibited uniform micropores (Figure S3b, c). The
Figure 2. Digital images and NMR spectrum of 3D-CON. (a) Tilted Pyrex glass ampule
bulk morphologies of the 3D-CON were visualized showing the clean reaction solvent after completion of the reaction. (b) After draining the
reaction solvent from the Pyrex glass ampule. (c) During Soxhlet extraction with water and
with field-emission scanning electron microscopy
FE-SEM). The 3D-CON showed uniform
micropores and a clean morphology. Its grain size
methanol. (d) After freeze drying at 120 °C for four days under dynamic vacuum. (e) Solid-
(
13
state C CP-MAS NMR spectrum.
varied from tens to hundreds of micrometers, suggesting a fine
microporous structure (Figure 3c, d). SEM coupled energy-dispersive
spectroscopy (SEM-EDS) (Figure 3e) and SEM elemental mapping
were used to corroborate the elemental composition of the 3D-CON.
The presence of carbon (C), nitrogen (N) and oxygen (O) was
confirmed by elemental mappings of the SEM-EDS analysis (Figure
S4). Using different elemental analyses techniques, the chemical
composition of the 3D-CON was determined, and the results are
summarized in Table S1. The X-ray photoelectron spectroscopy
Pore size distribution obtained using the nonlocal density functional
theory (NLDFT), which gives a more closely matching adsorption
isotherm, was centered at around 0.55 nm (inset, Figure 3f). The
BET measurements suggest that the 3D-CON possesses a uniform
pore size (narrow pore size distribution), which is well related to the
dimensions of the structure. Thus, it is clear that this material has an
ordered structure. Given the high specific surface area, microporous
nature and narrow pore size distribution of 3D-CON material, the
potential gas uptake capacities of small target molecules (H
CO ) were investigated.
2 4
, CH and
(
XPS) technique was used to probe the bonding nature of the 3D-
2
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COMMUNICATION
3
–1
(
137 cm g ) at 273 K (Figure 4c; S6c) and 17.15
3
–1
wt% (88 cm g ) at 298 K for CO
Adsorption and desorption isotherms showed no
hysteresis, indicating the CO uptake in 3D-CON
was a reversible process; the interactions between
the 3D-CON and CO are weak, and the framework
can be regenerated without the application of heat
Again, the adsorption capacity values for 3D-CON
2
(Figure S8b).
2
2
[
16]
.
were found to be among the highest compared to
most of the OPMs previously reported, and were
even competitive with the best reported MOFs under
[
17]
the same conditions (Table S2)
. To further
understand the interactions and adsorption
properties of gases with the 3D-CON, the isosteric
heat of adsorption (Qst) for H , CH and CO was
2 4 2
calculated from the gas adsorption isotherms at two
different temperatures by fitting the values into the
[
18]
Clausius-Clapeyron equation
hydrogen was examined by using the H
experiments at 77 and 87 K (inset in Figure 4a; S9).
One of the reasons for a lower uptake of H is the
with the adsorbent, due to a
magnifications. (e) Energy dispersive X-ray spectroscopy (EDS) spectrum with corresponding lack of binding sites. The 3D-CON displayed a Qst
SEM image, showing elemental contents. (f) Nitrogen adsorption and desorption isotherm at
7 K. The inset is the corresponding pore size distribution from the NLDFT approximation.
.
The
Qst for
2
adsorption
Figure 3. Structural characterization of the robust 3D-CON structure. (a) Powder X-ray
diffraction (PXRD) pattern. (b) TGA curve of the as-prepared sample under nitrogen
atmosphere after in situ activation at 150 °C in a TGA instrument, to remove any adsorbed
2
guest molecules, at a ramping rate of 10 ℃ min . (c, d) SEM images at different weak interaction of H

1
2
–1
2 2
value of 8.10 kJ mol for H adsorption at low H
uptake. Then, the Qst value decreased slowly as the
7
hydrogen uptake increased, and reached a value of
It has been reported that nitrogen containing microporous frameworks
generally perform well as material for storing small gas
uptake capacity of the 3D-CON was then
explored. The physiosorption storage of H for energy applications is
a promising approach to replace conventional fossil energy sources.
The standard for on-board H storage systems set by the US
Department of Energy (DOE) by the year 2020 is 5.5 wt% and 40 g of
–1
7
.25 kJ mol (inset, Figure 4a). This value is at the higher end
a
[
5a]
[
14b]
compared to the reported literature . At the same time, the higher
st value in the low pressure region is indicative of the higher affinity
molecules
.
The H
2
Q
2
toward 3D-CON, due to the narrow ultramicroporous pore size
distribution and robust fused-aromatic framework. The Qst values of
2
4 2
the 3D-CON toward CH and CO were estimated from the adsorption
–1
data collected at 273 and 298 K (inset, Figure 4b, c). In the low CH
4
H
2
2
L . The H adsorption-desorption isotherm of the 3D-CON was
–1
uptake zone, the Qst value (18.72 kJ mol ) implied a highly reversible
(absence of hysteresis) CH attraction toward 3D-CON. A strong
binding energy is preferred for storing a large amount of CH at low
pressure (inset, Figure 4b). The magnitude of Qst was among the
optimum heat of adsorption values reported for CH adsorption,
allowing both adsorption and desorption to occur at a fast rate, which
collected at 77 K with pressures up to 1.0 bar (Figure 4a; S6a). The
3
–1
4
highest H
higher than most OPMs reported recently (Figure 4f; Table S2). This
high H uptake capacity can be attributed to the large surface area,
2
uptake was 2.64 wt% (296.30 cm g ). This value was
4
2
4
which results from the combined effect of the ‘internal free volume’ of
the triptycene-based 3D framework. The absence of hysteresis
confirms the reversible physiosorption of H . In addition to exhibiting
2
high surface area and stability, the 3D-CON met the DOE 2020
[
19]
2
is desirable for a fuel storage system . In the low CO uptake zone,
–1
the 3D-CON exhibited a large Qst value (31.87 kJ mol ) implying high
CO affinity toward the 3D-CON. The reason for the high Qst value
observed in the low pressure region may be the strong interactions
between CO and the 3D-CON, as well as the narrow
2
storage target at 77 K and 59 bar (Figure 4d; S7).
As the basic constituent of natural gas, methane (CH
alternative fuel that is cleaner than petroleum oils due to its lower
carbon emissions. CH furnishes more energy because of its higher
hydrogen to carbon ratio. Although CH is more abundant and
4
) is an
2
ultramicroporosity (inset, Figure 4c). Furthermore, the 3D-CON
showed a gradual decrease in Qst as a function of the quantity
4
4
adsorbed. All of the Qst values (H
reported values for OPMs, and comparable to MOFs as well
2 4 2
, CH , CO ) were among the highest
economical than gasoline, for use in automobiles an efficient and
secured storage is required. The storage capacity should allow the
vehicle to drive more than several hundred kilometers before refueling.
[
3a, 20]
. The
low pressure gas sorption studies showed that the 3D-CON was far
from saturation at 1 bar pressure. Thus, to evaluate the high pressure
To further explore the different aspects that affect the CH
the 3D-CON, CH adsorption assessments were performed at 273 K
and 298 K in the low pressure range (Figure 4b; S6b). As shown in
4
uptake in
gas uptake capacity, high pressure gas sorption analyses for H
and CO were also performed (Figure 4d). The H uptake by the 3D-
CON at 77 K revealed a gradual increase with pressure, and the H
2
2 4
, CH
4
2
2
3
–1
Figure 4b, the CH
4
uptake at 1 bar is 2.4 wt% (33.5 cm g ) at 273 K
–1
3
–1
storage at 59 bar reached 5.5 wt% (27.24 mmol g ) (Figure 4d; S7a)
with saturation being reached at 70 bar (5.8 wt%). This exceeds the
hydrogen uptake capacities of most OPMs having a similar surface
and 1.55 wt% (21.6 cm g ) at 298 K (Figure S8a). This CH
4
uptake
of 3D-CON is among the best reported values in the literature (Table
S2).
The discharge of CO due to the combustion of fossil fuels is now
2
considered responsible for abnormal climate change, rising sea levels
and an irreversible increase in the acidity of the oceans, resulting in
adverse impacts on the sea ecology and environment. These issues
area (Table S2). The high pressure uptake capacity of H
was investigated (Fig. S10) and found to be 0.23 wt% at 38 bar
Verified high pressure gas adsorption certificate has been appended
in the Supplementary Information). The high pressure CH uptake
2
at 298 K
(
4
capacity of the 3D-CON at 298 K and 84 bar was found to be 24.5
have inspired the pursuit of state-of-the-art CO
and materials. The 3D-CON material, with its well-defined
microporous structure, holds great potential for CO capture. Testing
2
capture technology
which is fairly comparable to the best reported values (Table S2). The
–1
CO
2
storage was quite significant, reaching 70 wt% (15.90 mmol g )
2
at 298 K and 35 bar (Figure 4d; S7c). This value exceeds those of
of the low pressure CO
exhibited excellent CO
2
uptake of the 3D-CON was performed, and it
uptake at 1.0 bar, with a value of 26.7 wt%
2
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Angewandte Chemie International Edition
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COMMUNICATION
most reported OPMs (Table S2). The
microporosity of the 3D-CON was
further confirmed by measuring the
argon (Ar) gas adsorption isotherm.
Moreover, measuring Ar adsorption at
87 K has some advantages for
micropore analysis, because Ar does
not have a quadrupole interaction.
Figure 4e shows the Ar isotherm
measured for 3D-CON, which exhibits
a rapid Ar uptake at a very low relative
pressure, indicating the typical
behavior of permanent microporosity,
followed by
increase in Ar uptake (P/P
.9). The steep uptake at very low
a
very small gradual
o
= 0.05
̶
0
pressure is due to enhanced
interactions in the narrow micropores,
a typical type I isotherm, resulting in
micropore filling at very low pressure.
The pore size distributions were
estimated by using NLDFT from the
adsorption of the Ar isotherm (inset,
Figure 4e), showing that the 3D-CON
has only one major peak centered at
Figure 4. Gas storage properties of 3D-CON and literature comparison. (a) Hydrogen adsorption-
desorption isotherm at 77 K. Inset: isosteric heat of adsorption (Qst) as a function of gas loading calculated
from low pressure isotherms at 77 and 87 K. (b) Methane adsorption-desorption isotherm at 273 K. Inset: Qst
as a function of gas storage obtained from low pressure isotherms at 77 and 87 K. (c) Carbon dioxide
2
.82 Å. This ultrahigh microporosity adsorption-desorption isotherms at 273 K. Inset: Qst for the CO
2
as a function of gas uptake estimated from
low pressure isotherms at 273 and 298 K. (d) High pressure gas (H , CH and CO ) uptakes. (e) Argon
could be the reason of its exceptional
H
should be associated with the robust
fused-aromatic ring-based 3D-CON
structure, suggesting a promising potential for clean energy and
environmental applications.
2
4
2
adsorption-desorption isotherm measured at 87 K. Inset: pore size distribution calculated from NLDFT. (f)
Comparison of hydrogen uptakes for organic porous materials (OPMs) at 1 bar and 77 K (data taken from
Table S2).
2
uptake at low pressure, which
[
[
4]
5]
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persistent cage-like organic network structure using a rigid shape
persistent building block derived from triptycene hexamine. This
robust structure is thermally stable, ultramicroporous and display
outstanding gas adsorption property. The cage-like organic network
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adsorption capacity. Owing to the small pore size distribution and
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excellent H
2
uptake of up to 2.64 wt % at 77K and 1.0 bar. Uptake for
is 2.4 wt % at 273 K and 1.0 bar. This
CO is 26.7 wt % and CH
2
4
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strategy of exploiting the effective condensation reaction to synthesize
organic frameworks with high uptake capacity and high
physiochemical stabilities hold huge promise for practical applications.
CON demonstrates huge advance in the preparation of cage-like
porous aromatic frameworks for high gas storage capacity.
Acknowledgements
This work was supported by the Creative Research Initiative (CRI),
the BK21 Plus, Science Research Center (SRC) and Climate Change
programs through the National Research Foundation (NRF) of Korea
and by UNIST.
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This article is protected by copyright. All rights reserved.

Angewandte Chemie International Edition
10.1002/anie.201800218
COMMUNICATION
Table of Contents
COMMUNICATION
Design and synthesis of shape
persistent cage-like organic network
structure using a rigid shape persistent
building block derived from triptycene
hexamine. This robust structure is
thermally stable, ultramicroporous and
display outstanding gas adsorption
property. The cage-like organic
Javeed Mahmood, Seok-Jin Kim, Hyuk-
Jun Noh, Sun-Min Jung, Feng Li, Jeong-
Min Seo and Jong-Beom Baek*
Page 1. – Page 5.
Robust 3D cage-like ultramicroporous
network structure with high gas
uptake capacities
network structure exhibits
surface area up to 2247 m
a
g
BET
and
2
−1
high gas adsorption capacity.
.
This article is protected by copyright. All rights reserved.