Expanded Porous Metal-Organic Frameworks by SCSC: Organic Building Units Modifying and Enhanced Gas-Adsorption Properties

Article abstract of DOI:10.1021/acs.inorgchem.6b00278

Two amino-functional copper metal-organic frameworks of formula [Cu₃(ATTCA)₂(H₂O)₃]·2DMF·11H₂O·12EtOH (1) (H₃ATTCA = 2-amino-[1,1:3,1-terphenyl]-4,4,5-tricarboxylic acid, pyz = pyrazine, DMF = dimethylformamide) and [Cu₃(ATTCA)₂(pyz)(H₂O)]·2DMF·12H₂O·8EtOH (2) were synthesized under solvothermal conditions and characterized by single-crystal X-ray diffraction, infrared spectroscopy, elemental analyses, thermogravimetric analyses, and powder X-ray diffraction. Single-crystal X-ray diffraction analysis revealed that both complexes 1 and 2 are built of the Cu₂(COO)₄ paddlewheel secondary building units with an fmj topology. Importantly, complex 1 can be transformed into complex 2 by the single-crystal to single-crystal transformation of which the coordinated water molecules are replaced with pyz molecules. However, the adsorption abilities of 2 are obviously lower than those of 1, as its pores are partially blocked by pyz molecules. Moreover, gas-adsorption analysis showed that the amino-functional 1 possesses higher gas-adsorption capacity than UMCM-151 for N₂, H₂, CH₄, and C₂H₂, especially for CO₂.

Full text of DOI:10.1021/acs.inorgchem.6b00278

Article
pubs.acs.org/IC
Expanded Porous Metal−Organic Frameworks by SCSC: Organic
Building Units Modifying and Enhanced Gas-Adsorption Properties
Weidong Fan, Huan Lin, Xue Yuan, Fangna Dai,* Zhenyu Xiao, Liangliang Zhang,* Liwen Luo,*
and Rongming Wang
State Key Laboratory of Heavy Oil Processing, College of Science, China University of Petroleum (East China), Qingdao, Shandong
266580, People’s Republic of China
S
* Supporting Information
ABSTRACT: Two amino-functional copper metal−organic frame-
works of formula [Cu3(ATTCA)2(H2O)3]·2DMF·11H2O·12EtOH
(1) (H3ATTCA = 2-amino-[1,1:3,1-terphenyl]-4,4,5-tricarboxylic
acid, pyz = pyrazine, DMF = dimethylformamide) and
[Cu3(ATTCA)2(pyz)(H2O)]·2DMF·12H2O·8EtOH (2) were syn-
thesized under solvothermal conditions and characterized by single-
crystal X-ray diffraction, infrared spectroscopy, elemental analyses,
thermogravimetric analyses, and powder X-ray diffraction. Single-
crystal X-ray diffraction analysis revealed that both complexes 1 and 2
are built of the Cu2(COO)4 paddlewheel secondary building units
with an fmj topology. Importantly, complex 1 can be transformed
into complex 2 by the single-crystal to single-crystal transformation of
which the coordinated water molecules are replaced with pyz
molecules. However, the adsorption abilities of 2 are obviously lower than those of 1, as its pores are partially blocked by pyz
molecules. Moreover, gas-adsorption analysis showed that the amino-functional 1 possesses higher gas-adsorption capacity than
UMCM-151 for N2, H2, CH4, and C2H2, especially for CO2.
carboxylate MOFs,30−33 where the axial locations are
dominated by organic ligands or solvent molecules. On the
basis of paddlewheel SBUs, the frameworks can be further
INTRODUCTION
■
As an emerging class of porous crystalline materials, metal−
organic frameworks (MOFs) have attracted broad interests due
expanded into complicated complexes by SCSC or adding the
to their various architectures,1,2 high porosity,3,4 and potential
organic bridging ligands.34,35 For example, the paddlewheel
utilization in gas adsorption/separation,5 catalysis,6,7 lumines-
SBUs were connected through 1,4-diazabicyclo[2.2.2]octane
cence,8,9 magnetism,10−13 and so on.14,15 For most of the
(DABCO) or 4,4′-bipyridine (BPY) in the reported works, as
reported studies, gas adsorption/separation played an impor-
the coordination ability of tertiary amine and pyridine are
tant role in MOF areas. Over the past decades, the frameworks
stronger than the coordinated solvent molecules.36−39 How-
with various pore size, shape, and chemical functionality have
ever, the breaking/forming of coordination bonds is still a
been developed by the extension or decoration of larger
challenge for those transformations.40 Susumu Kitagawa’s
bridging ligands,16−18 the utilization of highly connected
secondary building units (SBUs),19,20 and the modification of
group has made great contributions in this aspect, but some
of their reports are based on removing the coordinated solvent
the complexes, such as postsynthetic methods and single-crystal
molecules to form the vacant coordination sites.41
to single-crystal (SCSC) transformation.21−23
We are interested in the construction of new porous
The rational design or construction of functionalized MOFs
frameworks with multifunctional groups that possess better
can be conducted through the introduction of functional
gas-adsorption properties.42−44 Hence, the amino-functional
ligand is designed, and the relevant complexes [Cu3(ATTCA)2-
(H2O)3]·2DMF·11H2O·12EtOH (1) and [Cu3(ATTCA)2-
(pyz)(H2O)]·2DMF·12H2O·8EtOH (2) are synthesized
(H3ATTCA = 2-amino-[1,1:3,1-terphenyl]-4,4,5-tricarboxylic
acid, pyz = pyrazine, DMF = dimethylformamide). It is
interesting that complex 1 can be turned into 2 by the SCSC
transformation of replacing the coordinated water molecules
groups.24 Chemists have realized that the amino-functional
frameworks have better gas-adsorption abilities, especially for
CO2.25 For example, Bai and Zaworotko groups demonstrated
that the decorated MOFs with polar acylamide groups can
significantly enhance the CO2 binding ability and gas-
adsorption selectivity;26 Long and co-workers reported an
amino-functional MOF with an exceptionally high adsorption
capacity for CO2 at low pressures.27 Meanwhile, theoretical
calculations also confirmed this concept.28,29
The paddlewheel cluster [M2(COO)4] (M = Cu2+, Zn2+,
Ni2+) is the most well-known SBU among the reported metal-
Received: February 9, 2016
© XXXX American Chemical Society
A
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Non-hydrogen atoms were refined with anisotropic displacement
parameters during the final cycles. Hydrogen atoms were placed in
calculated positions with isotropic displacement parameters set to 1.2
× Ueq of the attached atom. The free solvent molecules in complexes
1 and 2 are highly disordered, and no satisfactory disorder model
could be achieved. The PLATON/SQUEEZE routine was used to
remove scattering from the disordered solvent molecules.48,49 Table 1
shows pertinent crystallographic data collection and refinement
parameters. Tables S1 and S2 shows selected bond angles and
distances. Crystallographic data of 1 and 2 have been deposited with
the Cambridge Crystallographic Data Center (CCDC: 1444849−
1444850).
with pyz molecules. Since the amino-functional ligand of
H3ATTCA is used, 1 shows better gas-adsorption abilities for
N2, H2, CO2, C2H2, and CH4 than the reported UMCM-151,
which is assembled by the nonamino-functional ligand of
[1,1:3,1-terphenyl]-4,4,5-tricarboxylic acid (H3TTCA).45 How-
ever, the gas-adsorption ability of 2 is lower than that of
UMCM-151, as its pores are partially blocked by pyz
molecules.
EXPERIMENTAL SECTION
■
Materials and General Methods. H3ATTCA ligand was
synthesized according to the route shown in Scheme 1, while Scheme
RESULTS AND DISCUSSION
■
Scheme 1. Synthetic Procedures of the H3ATTCA Ligand
Crystal Structures of Complexes 1−2. Single-crystal X-
ray structural analysis demonstrates that 1 crystallizes in the
orthorhombic space group of Immm and that its asymmetric
unit consists of one deprotonated ATTCA3− ligand, one and a
half copper ions, and one and a half coordinated water
molecules. Cu1 atom is connected by four carboxylate oxygen
atoms from four different ATTCA3− ligands and one oxygen
atom from coordinated water molecule to generate a
pentagonal pyramidal coordination geometry (Figure 1a).
Adjacent Cu1 atoms are connected by four carboxyls to
generate a [Cu2(COO)4] paddlewheel subunit with the Cu1···
Cu1 separation of 2.615 Å and Cu1−O bond length of 1.945 Å.
Two different coordinated water molecules occupy the axial
positions with the Cu1−Owater bond length of 2.179 Å (Table
S1). In the similar paddlewheel [Cu2(COO)4] subunits
constructed by two Cu2 or two Cu3 atoms, the separations
of Cu2···Cu2 and Cu3···Cu3 are 2.599 and 2.610 Å; the Cu2−
O and Cu3−O average bond lengths are 1.905 and 1.942 Å;
and the Cu2−Owater and Cu3−Owater bond distances are 2.123
and 2.205 Å, respectively. The three Cu2(COO)4 paddlewheel
SBUs connected by ATTCA3− ligands to generate a non-
interpenetrated three-dimensional (3D) network with large
cavities as shown in Figure 1c. A hexagonal-shaped channel
surrounded by six ATTCA3− ligands and four Cu2(COO)4
copper paddlewheel SBUs has the dimension of 31.1 Å × 7.4 Å
viewed along the a-axis (Figure 1b), and two pentagonal-
shaped channels surrounded by three ATTCA3− ligands and
three Cu2(COO)4 paddlewheel SBUs have the dimensions of
17.3 Å × 7.0 and 16.8 Å × 7.0 Å, respectively, viewed along the
c-axis (Figure 1d). PLATON50 program analysis of 1
demonstrates that there is ∼73.7% solvent-accessible volume
(23 183 Å3). If the Cu2(COO)4 paddlewheel SBUs as a four-
connected node, the ATTCA3− ligands as a three-connected
planar linker, and the acetic acid groups as a two-connected
node, obviously an fmj topology is employed by the 3D
framework of 1 (Figure 1e).51
Scheme 2. Synthetic Procedures of the Complexes 1, 2, and
UMCM-151
2 showed the synthetic procedures of the complexes 1, 2, and UMCM-
151. The detailed procedures for synthesis of the ligand and complexes
are listed in Supporting Information.46 All the solvents and materials
were purchased from chemical vendors and without further depuration
before used. The powder X-ray diffraction (XRD) diffractograms were
obtained on a Panalytical X-Pert pro diffractometer with Cu Kα
radiation. Elemental analyses (C, H, N) were performed using a CE
instruments EA 1110 elemental analyzer. Infrared (IR) spectroscopy
spectra were collected on a Nicolet 330 FTIR Spectrometer within the
4000−400 cm−1 region. Thermogravimetric analysis (TGA) measure-
ments were performed on a PerkinElmer TGA 7 instrument under a
static N2 atmosphere with a heating rate of 10 °C/min at the range of
40−900 °C. Gas-adsorption experiments were performed on the
surface area analyzer ASAP-2020.
In 1, the distance between the adjacent paddlewheel is 7.372
Å (Figure 1c), which is quite coincident with the length sum of
pyrazine molecule (∼2.85 Å) and two Cu−N bonds (∼4.32 Å).
Hence, the SCSC transformation from complex 1 to 2 was
easily realized by adding pyz into the solution of 1, and 2 keeps
the same fmj topology. 2 crystallizes in the orthorhombic space
group of Immm. One deprotonated ATTCA3− ligand, one and a
half copper ions, half of a coordinated pyz molecule, and two
coordinated water molecules can be observed in the
asymmetric unit. The Cu2 atom is connected by four
carboxylate oxygen atoms from four different ATTCA3− ligands
and one nitrogen atom from coordinated pyz molecule to
generate a pentagonal pyramidal coordination geometry
(Figure 2a). Adjacent Cu2 atoms are connected by four
X-ray Structural Studies. X-ray diffraction data were collected on
a Agilent Xcalibur Eos Gemini diffractometer with Mo Kα radiation (λ
= 0.710 00 Å) at 293 K. All structures were solved by direct methods
and refined by full-matrix least-squares on F2 using SHELXS-97.47
B
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Table 1. Crystal Data and Structure Refinements for Complexes 1, 2, and UMCM-151
identification code
empirical formula
formula weight
temperature/K
crystal system
space group
a/Å
1
2
UMCM-151
C42H26Cu3O15
930.96
C72H138Cu3N4O40
1890.33
C65H114Cu3N6O35
1768.35
293(2)
293(2)
293(2)
orthorhombic
Immm
orthorhombic
Immm
orthorhombic
Immm
34.1449(7)
34.1449(7)
19.8843(12)
90.00
34.1668(10)
34.1668(10)
19.3425(9)
90.00
33.8400(13)
33.8400(13)
21.699(4)
90.00
b/Å
c/Å
α/deg
β/deg
90.00
90.00
90.00
γ/deg
90.00
90.00
90.00
volume/Å3
23182.6(16)
8
22579.9(14)
8
24848(5)
8
Z
ρcalc, mg/mm3
m, mm−1
F(000)
0.569
0.609
0.498
0.570
0.586
0.536
4024.0
4184.0
3656.0
radiation
Mo Kα (λ = 0.710 00)
Mo Kα (λ = 0.710 00)
3.36 to 51.56°
22 252
Mo Kα (λ = 0.710 00)
3.28 to 51.44°
23 926
2Θ range for data collection 6.08 to 52.68°
reflections collected
74 379
independent reflections
data/restraints/parameters
goodness-of-fit on F2
12 610 [Rint = 0.1575, Rsigma = 0.1587] 9724 [Rint = 0.1347, Rsigma = 0.3225] 11 162 [Rint = 0.0663, Rsigma = 0.1081]
12 610/2/314
9724/7/308
11 162/0/292
0.902
0.652
0.803
final R indexes [I > 2σ(I)]
final R indexes [all data]
R1 = 0.1105, wR2 = 0.2785
R1 = 0.2214, wR2 = 0.3183
R1 = 0.0928, wR2 = 0.2145
R1 = 0.2042, wR2 = 0.2597
R1 = 0.1085, wR2 = 0.2816
R1 = 0.1650, wR2 = 0.3062
Figure 1. (a) Coordination situation of Cu2(COO)4 paddlewheel in 1
and the linkmode of H3ATTCA. (b) Projection view of 3D open
framework along the a axis, showing the rhombic channels. (c) The
single cavity of 1. (d) 3D porous non-interpenetrating framework
viewed along the c axis. (e) The fmj topological net.
Figure 2. (a, b) Coordination situation of Cu2(COO)4 paddlewheel in
2 and the linkmode of H3ATTCA and pyz. (c) The rhombic cavity of
2. (d) Cu2(COO)4 paddlewheel linked by pyz formed 1D chain
structure. (e−g) 3D porous non-interpenetrating network viewed from
the a, b, and c axes.
carboxyls to generate a [Cu2(COO)4] paddlewheel subunit
with a Cu2···Cu2 separation of 2.584 Å, and the average Cu2−
O bond length is 1.983 Å; the Cu2−N bond length is 2.159 Å.
The two axial sites of each paddlewheel SBU are occupied by
pyz molecules instead of coordinated water molecules in 1
(Figure 2a,b). In the paddlewheel SBUs formed by two Cu1 or
Cu3 atoms, the separations of Cu1−Cu1 and Cu3−Cu3 are
2.590 and 2.630 Å, respectively, and the average Cu1−O bond
length is 1.993 Å, the average Cu3−O bond length is 1.938 Å.
Two coordinated water molecules occupy the axial positions
with the Cu1−Owater and Cu3−Owater bond length of 2.254 and
2.23 Å, respectively. Along the c axis, pyz ligand connects two
adjacent Cu2 paddlewheel subunits to generate an infinite one-
dimensional (1D) chain (Figure 2d).
The Cu2(COO)4 paddlewheel SBUs are connected by
ATTCA3− ligands to generate a non-interpenetrated 3D
network with large cavities (Figure 2c). A hexagonal-shaped
C
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channel can be observed along the a axis, but it was separated
into two parts by coordinated pyz molecules: the bigger pore is
surrounded by two ATTCA3− ligands, two pyz molecules, and
four Cu2(COO)4 paddlewheel SBUs with a dimension of 16.8
Å × 7.1 Å, and the smaller pore can be observed along the b
axis with a dimension of 7.6 Å × 7.1 Å, which is formed through
the connection of two ATTCA3− groups, one pyz molecule,
and three Cu2(COO)4 paddlewheel SBUs (Figure 2e).
Moreover, along the c axis, two large pentagonal-shaped
channels surrounded by three ATTCA3− ligands and three
Cu2(COO)4 paddlewheel SBUs can be observed with the
dimensions of 17.3 Å × 8.26 and 16.8 Å × 9.25 Å, which are
slightly larger than those in 1 (Figure 2g). The PLATON50
program analysis of 2 demonstrates that there is ∼71.7% of the
solvent-accessible volume (22 580 Å3), which is smaller than
the value of 1, as coordinated pyz molecules are partially
stacked in the pores.
UMCM-151 [Cu2(C21H11O6)1.33] has been reported by
Matzger’s group using nonamino-functional ligand of
H3TTCA.45 Similar to 1 and 2, it keeps the same fmj topology
and possesses open porous network, which crystallizes in the
orthorhombic space group of Immm. Three crystallographically
independent copper atoms can be observed in the asymmetric
unit. The coordination situation of UMCM-151 is same as 1.
Along the a, b, and c axes, three pentagonal-shaped channels
were observed with the dimensions of 11.4 × 9.6 Å, 11.3 × 6.9
Å, and 28.4 × 11.0 Å, respectively (Figure S4). The PLATON50
program analysis of UMCM-151 demonstrates that there is
∼76.6% solvent-accessible volume (24 848 Å3), which is greater
than 1 and 2, as no amino groups stacked in the holes.
Gas-Adsorption of Complexes 1, 2, and UMCM-151.
Considering the existence of 3D channels, gas-uptake measure-
ments for desolvated 1, 2, and UMCM-151 were performed.
Before the measurement, the as-synthesized crystal samples of
1, 2, and UMCM-151 were immersed in methanol to exchange
the uncoordinated DMF, EtOH, and water moleculers. Then
drying was done at 60 °C under high vacuum for 3 h to get the
activated samples.
abilities of 213.62 cm3·g−1, indicating its permanent poros-
ity.52,53 The adsorption capacities for H2 are 131.38 and 91.08
cm3·g−1 at 77 and 87 K, respectively (Figure 3b and Table 2),
Table 2. Gas-Adsorption Data for Complexes 1, 2, and
UMCM-151
amount
[mmol·g−1
]
gas
N2
complex
T
V abs [cm3·g−1
]
[wt %]
1
2
77 K
77 K
213.62
138.24
195.67
131.38
91.08
83.75
60.73
106.67
63.59
85.92
49.63
53.30
30.80
55.97
22.28
87.50
68.50
49.91
22.79
17.18
10.47
9.54
6.17
8.74
5.86
4.07
3.74
2.71
4.76
2.84
3.83
2.21
2.38
1.37
2.50
0.99
3.91
3.06
2.23
1.02
0.77
0.47
26.71
17.27
24.47
1.17
0.81
0.75
0.54
0.95
0.57
16.85
9.72
10.47
6.03
11.00
4.36
10.17
7.96
5.80
1.63
1.23
0.75
UMCM-151
77 K
H2
1
77 K
1
87 K
2
77 K
2
87 K
UMCM-151
77 K
UMCM-151
87 K
CO2
1
273 K
298 K
273 K
298 K
273 K
298 K
273 K
273 K
273 K
273 K
273 K
273 K
1
2
2
UMCM-151
UMCM-151
C2H2
CH4
1
2
UMCM-151
1
2
UMCM-151
which is larger than UTSA-36 with a similar BET surface area54
of 806 m2·g−1 and a H2 adsorption capacity of 123.00 cm3·g−1
(1.1 wt %) at 77 K.55 The adsorption capacities for CO2, C2H2,
and CH4 are 85.92, 87.50, and 22.79 cm3·g−1 at 273 K, whereas
CO2 at 298 K is 49.63 cm3·g−1.
As shown in Figure 4, the maximum adsorption capacity of 2
is 138.24 cm3·g−1 for N2 at 77 K. The adsorption capacities for
H2 are 83.75 and 60.73 cm3·g−1 at 77 and 87 K, respectively
(Figure 4b and Table 2). The adsorption capacities for CO2,
As shown in Figure 3, complex 1 exhibits a typical type-I
isotherm for N2 at 77 K, with the Brunauer−Emmett−Teller
(BET) surface area of 746.19 m2·g−1 and the adsorption
Figure 3. Gas-adsorption isotherms for 1: (a) N2 at 77 K; (b) H2 at 77
Figure 4. Gas-adsorption isotherms for 2: (a) N2 at 77 K; (b) H2 at 77
and 87 K; (c) C2H2 and CH4 at 273 K; (d) CO2 at 273 and 298 K.
and 87 K; (c) C2H2 and CH4 at 273 K; (d) CO2 at 273 and 298 K.
D
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C2H2, and CH4 are 53.30, 68.50, and 17.18 cm3·g−1 at 273 K,
whereas CO2 at 298 K is 30.80 cm3·g−1. The adsorption abilities
for 2 are quite obviously lower than those of 1, which is
attributed to the introduced pyz having partially occupied the
pores of 2.
CONCLUSIONS
■
Two amino-functional MOFs based on Cu2(COO)4 paddle-
wheel SBUs were successfully synthesized. By replacing the
coordinated water molecule with pyz molecule, the SCSC
transformation of complex 1 to 2 was realized. Both complexes
1 and 2 show an fmj topology. The adsorption abilities of 2 are
lower than that of 1, as part of the pores is stacked by pyz in 2.
Compared with UMCM-151, the amino-functional 1 shows the
higher gas-adsorption capacity for N2, H2, CO2, CH4, and
C2H2, especially for CO2. This behavior further confirmed that
the amino-functional MOFs can significantly improve the CO2
adsorption capacity and selectivity, as the polar amino groups in
the tunnel walls can form the strong Lewis acid−base
interactions with the Lewis acid (CO2 and C2H2). Further
research work based on the amino-functional modification
ligand and potential application in gas storage or CO2 removal
from the natural gas are underway in our lab.
As shown in Figure 5, the maximum adsorption capacity of
UMCM-151 is 195.67 cm3·g−1 for N2 at 77 K. The adsorption
ASSOCIATED CONTENT
* Supporting Information
■
S
The Supporting Information is available free of charge on the
ACS Publications website at DOI: 10.1021/acs.inorg-
chem.6b00278.
Detailed synthetic procedures, selected bond angles and
lengths, 1H NMR spectrum, crystal structures of
UMCM-151, TGA curves, IR curves, PXRD patterns,
isosteric adsorption enthalpy (PDF)
X-ray crystallographic information (CIF)
X-ray crystallographic information (CIF)
Figure 5. Gas-adsorption isotherms for UMCM-151: (a) N2 at 77 K;
(b) H2 at 77 and 87 K; (c) C2H2 and CH4 at 273 K; (d) CO2 at 273
and 298 K.
AUTHOR INFORMATION
Corresponding Authors
*E-mail: fndai@upc.edu.cn. (F.D.)
*E-mail: liangliangzhang@upc.edu.cn. (L.Z.)
*E-mail: luolw@upc.edu.cn. (L.L.)
■
capacities for H2 are 106.67 and 63.59 cm3·g−1 at 77 and 87 K,
respectively (Figure 5b and Table 2). The adsorption capacities
for CO2, C2H2, and CH4 are 55.97, 49.91, and 10.47 cm3·g−1 at
273 K, whereas CO2 at 298 K is 22.28 cm3·g−1. Although the
pores of UMCM-151 are larger than those of 1, the lower gas
adsorption of UMCM-151 is easily attributed to the introduced
polar groups (NH2-) located at MOF channels, which can
significantly improve the CO2 adsorption capacity and gas-
adsorption selectivity. Amino groups play a role of Lewis base
to form the active sites on the tunnel walls, which have strong
interactions with Lewis acid (CO2 and C2H2). On the basis of
the above results, we can conclude that the introduction of
amino not only can occupy part of the channel structure but
also can improve the gas-adsorption ability, just like a “double-
edged sword”.
The virial-type expression was used to calculate H2 and CO2
gas isosteric heat of adsorption (Qst).56 By fitting the H2
adsorption isotherms at 77 and 87 K, the Qst for H2 was
obtained with the estimated value of 6.2 kJ mol−1 for 1 and 6.6
kJ mol−1 for 2, which are higher than that of UMCM-151 (4.9
kJ mol−1; Figures S12−S14). By fitting the CO2 adsorption
isotherms at 273 and 298 K, the Qst for CO2 was obtained with
the estimated value of 19.0 kJ mol−1 for 1 and 24.1 kJ mol−1 for
2 (Figures S12 and S13). The value is lower than that of
UMCM-151 (29.0 kJ mol−1; Figure S14), similar to those of
UMCM-150 (20.6 kJ mol−1), MIL-47 (20.8 kJ mol−1), and
HKUST-1 (25.1 kJ mol−1), but higher than those values for
MOF-177 (15.7 kJ mol−1), IRMOF-1 (15.8 kJ mol−1), and
UMCM-1 (15.5 kJ mol−1).57,58
Funding
This work was supported by the China Postdoctoral Science
Foundation (2012M510172), the NSFC (Grant Nos.
21371179 and 21201179), the Foundation of State Key
Laboratory of Structural Chemistry (20160006), and the
Fundamental Research Funds for the Central Universities
(14CX02213A and 16CX05015A).
Notes
The authors declare no competing financial interest.
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