An isoreticular series of metal-organic frameworks with dendritic hexacarboxylate ligands and exceptionally high gas-uptake capacity

Article abstract of DOI:10.1002/anie.201001009

(Figure Presented) Holding gas: One of the isoreticular metal-organic frameworks (MOFs) that have been synthesized and characterized structurally, PCN-68 (see structure), has a Langmuir surface area of as high as 6033 m ² g^-1. The MOFs also display excellent gas (H₂, CH₄, and CO₂) adsorption capacity.

Full text of DOI:10.1002/anie.201001009

Angewandte
Chemie
DOI: 10.1002/anie.201001009
Metal–Organic Frameworks
An Isoreticular Series of Metal–Organic Frameworks with Dendritic
Hexacarboxylate Ligands and Exceptionally High Gas-Uptake
Capacity**
Daqiang Yuan, Dan Zhao, Daofeng Sun, and Hong-Cai Zhou*
Metal–organic frameworks (MOFs) are newly emerging
porous materials.[1] Owing to their large surface area and
tunable pore size and geometry, they have been studied for
applications in gas storage and separation, especially in
hydrogen and methane storage and carbon dioxide capture.[2]
It has been well established that the high-pressure gravimetric
hydrogen-adsorption capacity of an MOF is directly propor-
tional to its surface area.[3] However, MOFs of high surface
areas tend to decompose upon activation. In our previous
work, we described an approach toward stable MOFs with
high surface areas by incorporating mesocavities with micro-
windows.[4] To extend this work, we now present an isoretic-
ular[5] series of (3,24)-connected MOFs made from dendritic
hexacarboxylate ligands, one of which has a Langmuir surface
area as high as 6033 m2 gÀ1. In addition, the gas-adsorption
properties of this new isoreticular MOF series have been
studied.
To construct the (3,24)-connected isoreticular MOF
series, the ligands should have C3 symmetry with three
coplanar isophthalate moieties.[4] Bearing this in mind, we
designed and synthesized two dendritic hexacarboxylic acids:
H6ptei and H6ttei (Figure 1a). The ensuing solvothermal
reactions between these carboxylic acids and copper salts led
to two isostructural MOFs with the same (3,24)-connected
network (Figure 1b), designated PCN-68 (Cu3(H2O)3-
(ptei)·13H2O·33dmf)
and
PCN-610
(Cu3(H2O)3-
(ttei)·19H2O·22dmf) (PCN stands for porous coordination
[*] Dr. D. Yuan,[+] D. Zhao,[+] Prof. Dr. H.-C. Zhou
Department of Chemistry, Texas A&M University
College Station, TX 77843 (USA)
Figure 1. a) Nanoscopic ligands btei (PCN-61), ntei (PCN-66), ptei
(PCN-68), and ttei (PCN-610); b) (3,24)-connected network in PCN-68;
c) 3D polyhedra packing in PCN-68.
Fax: (+1)979-845-1595
E-mail: zhou@mail.chem.tamu.edu
Homepage: http://www.chem.tamu.edu/rgroup/zhou/
Prof. Dr. D. Sun
Key Lab for Colloid and Interface Chemistry
Shandong University, Jinan (P.R. China)
network). Together with PCN-61 and PCN-66,[4] four MOFs
form a new isoreticular MOF series. As reported previously,
the structure of these MOFs can be described as the packing
of three types of polyhedra: cuboctahedra (cubOh, red),
truncated tetrahedra (T-Td, green), and truncated octahedra
(T-Oh, blue; Figure 1c). The diameters of spheres represent-
ing the void inside these polyhedra are listed in Table 1. As
expected, the ligand extension has enlarged the size of
T-Oh, which is accompanied by a mild increase in the size of
T-Td, and no change in the size of cubOh. It is evident that the
pore size of T-Oh has reached the meso range in PCN-66,
PCN-68, and PCN-610.
[+] These authors contributed equally to this work.
[**] This work was supported by the US Department of Energy (DE-
FC36-07GO17033) and the Welch Foundation (A-1725). The
microcrystal diffractions of PCN-68 and PCN-610 were carried out
with the assistance of Yu-Sheng Chen at the Advanced Photon
Source on beam line 15ID-B at ChemMatCARS Sector 15, which is
principally supported by the National Science Foundation/Depart-
ment of Energy under grant number CHE-0535644. Use of the
Advanced Photon Source was supported by the US Department of
Energy, Office of Science, Office of Basic Energy Sciences, under
Contract No. DE-AC02-06CH11357.
Calculations and experimental evidence support the
assessment that given fixed framework topology, the surface
Supporting information for this article is available on the WWW
under http://dx.doi.org/10.1002/anie.201001009.
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ꢀ
Table 1: Unit cell length (Fm3m), ligand size (L size), and polyhedron
Table 2: Surface areas, pore volumes, and porosities of the isoreticular
size of the isoreticular PCN-6X MOF series.
PCN-6X MOFs.
Material
Unit cell
length [ꢀ]
L
CubOh
size [ꢀ]
T-Td
size [ꢀ]
T-Oh
size [ꢀ]
Material
Surface area [m2 gÀ1
]
Pore volume [cm3 gÀ1
]
Porosity[a]
size [ꢀ][a]
(Langmuir/BET/calcd[a]) (exptl/calcd[a])
PCN-61
PCN-66
PCN-68
PCN-610
42.796
49.112
52.738
59.153
6.906
9.758
11.243
13.815
12.0
12.0
12.0
12.0
11.8
12.0
14.8
18.6
18.8
20.6
23.2
26.0
PCN-61
PCN-66
PCN-68
3500/3000/3455
4600/4000/3746
6033/5109/3871
1.36/1.37
1.63/1.75
2.13/2.17
NA/3.00
77.0%
80.0%
82.9%
86.8%
PCN-610[b] NA/NA/4160
[a] The ligand size is defined as the distance between the center of the
ligand and the center of a terminal benzene ring.
[a] Calculated using Material Studio 4.4. [b] NA=not available.
area of a framework increases with ligand extension in all
currently explored systems.[6] In reality, however, frameworks
built with long spacers tend to collapse after the removal of
guest molecules.[7] In addition, longer ligands may cause
framework interpenetration, resulting in a reduced surface
area or even a nonporous structure.[8] In the (3,24)-connected
network, the commonly encountered framework instability
accompanying ligand extension can be alleviated by using
dendritic ligands.[4] The isophthalate moiety of the ligand
produces cubOh with a fixed size, limiting the open window
sizes of the T-Td and T-Oh, although the sizes of the T-Td and
T-Oh will expand with the ligand extension. Thus, by using
ligands longer than those in PCN-61 and PCN-66, stable
MOFs with surface areas higher than those found in PCN-61
and PCN-66 can be made. This hypothesis will be examined in
PCN-68 and PCN-610.
sorption behavior, which is typical for materials with hier-
archical pore size distribution.[4] However, with PCN-610, in
which an even larger ligand was used, there is barely any
nitrogen sorption observed, implying a complete collapse of
the framework. The same conclusion is also drawn from the
powder X-ray diffraction (PXRD) data, which reveal that
PCN-610 lost its crystallinity completely upon activation
(Figure S2 in the Supporting Information).
From the above discussion, it is evident that by using the
dendritic hexacarboxylate ligands, isoreticular MOFs with
higher surface areas can be obtained by ligand extension.
However, this approach, which is based on the formation of
cuboctahedra and a (3,24)-connected framework, has its
limitations. The ligand size that may lead to a stable MOF
with the highest surface areas in this series falls between ptei
(11.2 ꢀ) in PCN-68 and ttei (13.8 ꢀ) in PCN-610. In addition,
the (3,24)-connected network can incorporate ligands as large
as 11.2 ꢀ without framework decomposition, whereas in the
twisted boracite network, which is composed of tricarboxylate
ligands (less dendritic) and dimetal paddlewheels,[10] even a
ligand as small as 4.179 ꢀ (tatb, 4,4’,4’’-s-triazine-2,4,6-triyl-
tribenzoate) would lead to the disintegration of the PCN-6’
framework.[10c] It is our belief that dendritic ligands with more
branches will lead to stable MOFs that can tolerate more
extended ligands, leading to even higher surface areas.[11]
The high surface areas of the isoreticular PCN-6X series
of PCN-61, PCN-66, and PCN-68 prompted us to study their
gas-uptake capacity, especially that for hydrogen, methane,
and carbon dioxide.[2] Hydrogen is an ideal energy carrier.
However, the lack of an effective storage method hinders its
application. The US Department of Energy (DOE) recently
reset the gravimetric and volumetric storage targets for on-
To test the framework stability, nitrogen sorption meas-
urements were carried out in fully activated PCN-68 and
PCN-610. In PCN-68, a dramatic increase of nitrogen sorption
was observed (Figure 2). The BET surface area calculated on
board hydrogen storage for the year 2010 (4.5 wt%, 28 glÀ1
)
and 2015 (5.5 wt%, 40 glÀ1).[12] MOF-based hydrogen storage
has attracted remarkable attention recently because of its fast
kinetics and favorable thermodynamics in hydrogen adsorp-
tion and release.[3,9b,13] The hydrogen-uptake capacities of
PCN-6X series are shown in Figure 3. In the low-pressure
region (< 1 bar), the hydrogen-uptake capacity is mainly
controlled by the hydrogen affinity towards the framework,
which can be quantified by the isosteric heat of adsorption
(Figure S3 in the Supporting Information). PCN-61, which
has the smallest pore size, also has the highest heat of
adsorption and highest capacity (2.25 wt% at 77 K, 1 bar).
PCN-66 and PCN-68 have heats of adsorption and adsorption
capacities similar to each other (1.79 wt% in PCN-66 vs.
1.87 wt% in PCN-68). This trend is consistent with the nature
Figure 2. N2 sorption isotherms of PCN-61, PCN-66, and PCN-68 at
77 K.
the basis of the low-pressure region data can reach as high as
5109 m2 gÀ1, and the Langmuir surface area as high as
6033 m2 gÀ1. To the best of our knowledge, PCN-68 possesses
the highest surface area reported to date for MOFs based on
paddlewheel clusters, and it is also among the highest
reported (Table 2).[6a,9] The pore size data calculated on the
basis of nitrogen sorption isotherms are consistent with the
crystal data (Figure S1 in the Supporting Information). Care-
ful examination of the low-pressure region reveals stepwise
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130 mggÀ1 (100 bar) (Figure S4 in the Supporting Informa-
tion), which makes it one of the best adsorbents with the
highest gravimetric hydrogen-uptake capacity.[2] It is worth
noting that the maximum adsorption pressure increases from
PCN-61 (33 bar) to PCN-66 (45 bar) and PCN-68 (50 bar),
indicating higher pressure is needed to reach maximum
adsorption in sorbents with higher pore volumes.
Using the crystal-density data, the volumetric hydrogen-
uptake capacities were also calculated (Figure 3b). Unlike the
trend in gravimetric capacity, in which the material with the
highest surface area has the highest capacity, the volumetric
capacity follows the opposite trend, which is dominated by the
densities of the sorbents. The gravimetric capacity has been
emphasized in past hydrogen-storage research, and rightfully
so. However, the volumetric capacity is particularly relevant
in volume-limited fuel-cell applications.[17] Both of these
criteria should be emphasized equally in the search for ideal
hydrogen-storage materials.
Natural gas (methane being the main component) is
another alternative on-board fuel that has aroused much
interest. Like hydrogen, however, it also lacks an effective
storage method. The DOE target for on-board methane
storage is based on volumetric capacity (180 v(STP)/v(STP)
under 35 bar and near ambient temperature; STP = standard
temperature and pressure; T= 273.15 K, P = 101.325 kPa),
which requires the adsorbents to have not only high porosity,
but also high packing density and good thermal conductiv-
ity.[18] PCN-6X series MOFs have been tested for their
methane-uptake capacities at 298 K. As can be seen from
Figure 4a, the gravimetric methane-uptake capacities in these
Figure 3. a) Gravimetric and b) volumetric H2-uptake in PCN-6X series
at 77 K. The inset in (a) shows the low-pressure region enlarged.
of physisorption, in which narrower pores would have
stronger interactions with the guest gas molecules because
of the increased interaction between the guests and the
opposite potential walls within small pores.[14]
Unlike the low-pressure hydrogen sorption capacity,
which is dominated by the hydrogen affinity, the maximum
excess hydrogen-uptake capacity in MOFs, which typically
can only be reached in the high-pressure range, is controlled
mainly by the surface area and pore volume.[3,15] This behavior
is consistent with what has been observed in the PCN-6X
series. As can be seen from Figure 3a, PCN-68, which has the
highest surface area, also has the highest maximum excess
hydrogen-uptake capacity (73.2 mggÀ1, Table 3). Its hydro-
gen-uptake capacity is comparable with that of the current
record holder, MOF-177 (75 mggÀ1).[16] Taking into consider-
ation the gaseous hydrogen compressed within the framework
void, its total hydrogen-uptake capacity would reach
Table 3: Hydrogen-uptake capacities and isosteric heats of adsorption in
the PCN-6X series.
Material H2 uptake at 77 K,
Maximum excess H2
QST [kJmolÀ1
]
[a]
[a]
1 atm [wt%] (glÀ1
)
uptake [mggÀ1] (glÀ1
)
PCN-61 2.25 (12.6)
PCN-66 1.79 (7.98)
PCN-68 1.87 (7.20)
62.4 (35.0) 33 bar 77 K 6.36
6.67 (3.74) 90 bar 298 K
66.5 (29.6) 45 bar 77 K 6.22
7.85 (3.50) 90 bar 298 K
73.2 (28.0) 50 bar 77 K 6.09
10.1 (4.10) 90 bar 298 K
Figure 4. a) Gravimetric and b) volumetric capacities of CH4 adsorp-
tion in the PCN-6X series at 298 K. The inset in (a) shows the
medium-pressure region enlarged.
[a] The values in parentheses represent the volumetric hydrogen-uptake
capacities.
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MOFs are also proportional to their surface areas. In the
medium-pressure range (< 20 bar), PCN-61 has the highest
capacity, possibly because of the stronger methane affinity of
the framework, which can be ascribed to the small pore size.
When the pressure goes to high range (> 60 bar), the effect of
surface area and pore volume starts to dominate, making
PCN-68 the one with the highest uptake. By assuming the
crystal density as the packing density, the volumetric meth-
ane-uptake capacities were also calculated (Figure 4b). PCN-
61 has the highest capacity at 35 bar (145 v/v), followed by
PCN-66 (110 v/v), and PCN-68 (99 v/v) (Table 4). This trend
can be ascribed to the difference in crystal density among the
Table 4: CH4 and CO2 excess uptake capacities in the PCN-6X series at
35 bar and 298 K.
Material
CH4 [mmolgÀ1
]
CH4 [vvÀ1
]
CO2 [mmolgÀ1
]
PCN-61
PCN-66
PCN-68
11.6
11.1
11.6
145
110
99
23.5
26.3
30.4
three structures (0.56 gcmÀ3 in PCN-61 vs. 0.45 gcmÀ3 in
PCN-66 and 0.38 gcmÀ3 in PCN-68). From this study, it can be
concluded that high surface area should not be the sole
emphasis if the aim is to achieve high volumetric methane-
uptake capacity. Instead, a balance should be maintained
among porosity, density, pore size, and other factors.
Figure 5. Gravimetric CO2 uptake (a) and density (b) in the PCN-6X
series at 298 K.
Aggravated global warming, which is partially attributed
to the increasing carbon dioxide concentration in the air, has
aroused worldwide concerns. Carbon capture and sequestra-
tion (CCS), a process involving the capture of carbon dioxide
from the air and sequestering it underground, has been
proposed as a feasible way to control the atmospheric carbon
dioxide concentration.[19] Using porous materials to capture
carbon dioxide based on the sorption mechanism will be an
energy-conserving alternative approach. The study of MOF-
based carbon dioxide capture is growing dramatically.[2] The
high-pressure gravimetric carbon dioxide adsorption capaci-
ties of the PCN-6X series at 298 K are shown in Figure 5a.
Once again, their storage capacities follow a trend similar to
those found in the aforementioned hydrogen- and methane-
adsorption studies. PCN-68 has the highest gravimetric
carbon dioxide storage capacity among the three frameworks,
and is also among the highest reported (Table 4). The density
of the carbon dioxide captured can be calculated on the basis
of the amount of gas adsorbed and the pore volume of the
frameworks (Figure 5b). The density of adsorbed carbon
dioxide is the highest in PCN-61. Based on the total capacity,
at 35 bar and room temperature, a container filled with PCN-
61 can store 8.2 times the amount of CO2 in an empty
container, and this volumetric capacity is 7.3 for PCN-66 and
7.4 for PCN-68, which make PCN-6X series compounds good
adsorbents for carbon dioxide capture.
late moieties throughout the framework. The mesocavities,
which are connected by the microwindows, however, are
sustained by these nanoscopic ligands and responsible for the
porosity improvement with ligand extension. In addition, the
formation of isophthalate-sustained cuboctahedra in the
(3,24)-connected network prohibits framework interpenetra-
tion, leading to MOFs with close to record-high surface areas.
Hydrogen, methane, and carbon dioxide adsorption studies of
MOFs in this series also revealed close to record-high gas-
adsorption capacities. However, this approach has its limi-
tations. The ligand size that may lead to a stable MOF with
the highest surface areas in this isoreticular series falls
between 11.2 and 13.8 ꢀ. We propose that dendritic ligands
with even more branches should lead to stable MOFs that can
tolerate more extended ligands leading to even higher surface
areas. Work along those lines is currently underway in our
laboratory.
Experimental Section
Crystal data for PCN-68: C54H30Cu3O15, M = 1109.40, green prism,
3
ꢀ
0.03 ꢁ 0.02 ꢁ 0.02 mm , cubic, space group Fm3m, a = 52.738(5), V=
146679(24) ꢀ3, Z = 32, 1calcd = 0.402 gcmÀ3, F000 = 17952, synchrotron
radiation, l = 0.41328 ꢀ, T= 173(2) K, 2qmax = 23.98, 389054 reflec-
tions collected, 3753 unique (Rint = 0.2923). Final GooF = 1.429, R1 =
0.1556, wR2 = 0.3923, R indices based on 2340 reflections with I >
In summary, an isoreticular MOF series with the (3,24)-
connected network topology has been synthesized by using a
series of dendritic hexacarboxylate ligands. The framework is
stabilized by incorporating microwindows, whose size is fixed
by the formation of cuboctahedra supported by the isophtha-
2s(I), m = 0.193 mmÀ1
.
Crystal data for PCN-610: C60H30Cu3O15, M = 1181.46, green
3
ꢀ
prism, 0.03 ꢁ 0.02 ꢁ 0.02 mm , cubic, space group Fm3m, a = 59.153(6),
V= 206977(39) ꢀ3, Z = 32, 1calcd = 0.303 gcmÀ3, F000 = 19104, syn-
chrotron radiation, l = 0.41328 ꢀ, T= 150(2) K, 2qmax = 15.88,
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189298 reflections collected, 1650 unique (Rint = 0.2187). Final
GooF = 1.210, R1 = 0.1227, wR2 = 0.3300, R indices based on 1395
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.
CCDC 764972 (PCN-68) and 764973 (PCN-610) contain the
supplementary crystallographic data for this paper. These data can be
obtained free of charge from The Cambridge Crystallographic Data
Centre via www.ccdc.cam.ac.uk/data_request/cif.
Full experimental details are presented in the Supporting
Information.
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Keywords: carbon storage · clean energy · hydrogen ·
metal–organic frameworks · methane
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