Two Functional Porous Metal-Organic Frameworks Constructed from Expanded Tetracarboxylates for Gas Adsorption and Organosulfurs Removal

Article abstract of DOI:10.1021/acs.cgd.6b01539

Two fof-type porous metal-organic frameworks (MOFs), [Cu₂(bdfdpa)(H₂O)₂]·8DMF·2H₂O (JLU-Liu29) and [Cu₂(btadpa)(H₂O)₂]·7DMF·8H₂O (JLU-Liu30) (H₄bdfdpa = 5,5

Full text of DOI:10.1021/acs.cgd.6b01539

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Article
Two Functional Porous Metal-Organic Frameworks Constructed from
Expanded Tetracarboxylates for Gas Adsorption and Organosulfurs Removal
Xiaolong Luo, Liang Kan, Xiang Li, Libo Sun, Guanghua Li,
Jun Zhao, Dong-Sheng Li, Qisheng Huo, and Yunling Liu
Cryst. Growth Des., Just Accepted Manuscript • DOI: 10.1021/acs.cgd.6b01539 • Publication Date (Web): 14 Nov 2016
Downloaded from http://pubs.acs.org on November 18, 2016
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Two Functional Porous Metal-Organic Frameworks Constructed
from Expanded Tetracarboxylates for Gas Adsorption and
Organosulfurs Removal
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Xiaolong Luo,a Liang Kan,a Xiang Li,a Libo Sun,a Guanghua Li,a Jun Zhao,b Dong-Sheng Li,*,b
Qisheng Huoa and Yunling Liu*,a
aState Key Laboratory of Inorganic Synthesis and Preparative Chemistry, College of Chemistry,
Jilin University, Changchun 130012, P. R. China
bCollege of Mechanical & Material Engineering, Hubei Provincial Collaborative Innovation
Center for New Energy Microgrid, Key Laboratory of Inorganic Nonmetallic Crystalline and
Energy Conversion Materials, China Three Gorges University, Yichang 443002, P. R. China
*To whom correspondence should be addressed.
Professor Yunling Liu
College of Chemistry
Jilin University
Changchun 130012, P. R. China
Fax: +86-431-85168624
E-mail: yunling@jlu.edu.cn (Y.L.).
Professor Dong-Sheng Li
College of Mechanical & Material Engineering
China Three Gorges University
Yichang 443002, P. R. China
E-mail: lidongsheng1@126.com (D.-S.L.).
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ABSTRACT
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Two fof type porous metal-organic frameworks (MOFs), [Cu2(bdfdpa)(H2O)2]·8DMF·2H2O
(JLU-Liu29) and [Cu2(btadpa)(H2O)2]·7DMF·8H2O (JLU-Liu30), (H4bdfdpa = (5,5’-
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(benzo[1,2-b:4,5-b’]difuran-2,6-diyl)diisophthalic
acid
and
H4btadpa
acid)
=
5,5’-
been
(benzo[c][1,2,5]thiadiazole-4,7-diylbis(ethyne-2,1-diyl))diisophthalic
have
successfully synthesized by using different expanded tetracarboxylates ligands. Both of them
exhibit good permanent porosity and high surface areas of 2205 m2 g-1 and 1791 m2 g-1,
respectively. Due to open metal sites, different functional groups and suitable pore spaces, the
two porous MOFs exhibit high adsorption performance for small molecule gases (CO2, CH4,
C2H6 and C3H8) and removal of refractory organosulfur compounds.
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INTRODUCTION
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Recently, great energy consumption accompanied with the high level discharge of carbon
dioxide far beyond the standard line has aroused the global concern. It is necessary to reduce the
growth of the carbon dioxide concentration in the atmosphere. Several methods can be
considered helpful to dispose carbon dioxide. One is to use clean energy instead of fossil energy,
another can be the separation of carbon dioxide from emission sources, also the improvement of
the energy conversion efficiency can be an effective method.1-4 In recent years, the storage of the
small hydrocarbon (CH4, C2H6, C3H8) are also highly in demand as promising new energy
alternatives. CH4 as the predominant ingredient of Natural gas (NG), and small amounts of CO2
and hydrocarbon as the impurities, it is necessary for separation and purification of CH4.5
Especially CH4 is a considerable cleaner energy source for our daily life as the primary
component of natural gas and future vehicles.6 The organosulfur content in fuels is another
environmental concern because the combustion organosulfur is changed into SOx, which not
only contributes to acid rain, but also has a negative effect on human health. Many studies have
been undertaken to develop adsorbents for the desulfurization of transportation fuels using
zeolites, mesoporous materials and activated carbons. Apart from the several methods
investigated (geological storage, terrestrial ecosystems storage, biological storage, ocean storage
and mineral storage etc.), the porous materials are also investigated for their possibility to storage
of carbon dioxide, small hydrocarbon (CH4, C2H6, C3H8), and removal of organosulfurs.7-9
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Porous metal-organic frameworks (MOFs), which offer large surface areas, high void
volumes, suitable pore size and chemical stability, have proven their potential application as a
series of promising materials in the gas storage areas these years.10-13 A large amount of MOFs
have been applied to gas absorption and natural gas purification，such as Al-soc-MOF-1,
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UTSA-35a and FIR-7a-ht,14-16 because of the open metal sites and suitable pore cage for their
interactions with the gas molecules. However, only a few MOFs materials are known to possess
significant organosulfur adsorption properties, such as benzothiophene (BT), dibenzothiophene
(DBT) and 4,6- dimethyldibenzothiophene (DMDBT), which are undesirable to refiners (Scheme
1).17-20
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Among diverse investigated MOFs, those constructed with isophthalate included
carboxylate acid ligands have drawn great attentions. For instance, since first report by Chen and
Schröder in their pioneer works,21-22 those MOFs assembled from inorganic copper paddle wheel
Cu2(CO2)4 secondary building units (SBUs) and organic tetracarboxylate acid ligands are greatly
developed.23-29 Such kind of MOFs can provide available open Cu2+ sites, variable and suitable
pore spaces through the selection of different size ligands, which can provide the efficient gas
storage and sulfur adsorption. Furthermore, the frameworks can be easily decorated with
functional groups embedded in the ligands, which is believed to be beneficial for special of gases
by enhancing their interactions with the pores. Here in this work, two functional groups,
dibenzofuran and benzothiadiazole, have been incorporated between two isophthalate acid
moieties to form two new tetracarboxylates ligands, (5,5’-(benzo[1,2-b:4,5-b’]difuran-2,6-
diyl)diisophthalic acid (H4bdfdpa) and 5,5’-(benzo[c][1,2,5]thiadiazole-4,7-diylbis(ethyne-2,1-
diyl))diisophthalic acid (H4btadpa). Thus, two MOFs, JLU-Liu29 and JLU-Liu30 with fof
topology have been successfully synthesized, they exhibit high performance for adsorption of
small molecule gases (CO2, CH4, C2H6 and C3H8) and removal of refractory organosulfur
compounds.
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EXPERIMENTAL SECTION
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Materials and physical characterizations
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The related chemicals and reagents were purchased from commercial sources and used without
further purification. Infrared spectra were recorded on a Bruker IFS-66v/S FTIR spectrometer in
the range of 400-4000 cm-1 using the KBr pallet. Powder X-ray diffraction (PXRD) data were
collected on a Rigaku D-Max 2550 diffractometer with Cu-Kα radiation (λ = 1.5418 Å) over the
2θ range of 3-40° at room temperature. Thermogravimetric analyses (TGA) were carried out
o
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with the TA Q500 thermogravimetric analyzer under a heating rate of 10 C min-1 to 800 C in
air. Elemental analyses (C, H, N and S) were carried out with a vario MICRO elemental
analyzer.
Synthesis and Characterization of Organic Ligands (Scheme 2)
Synthesis of dimethyl 5-ethynylisophthalate (1) and 2,5-diiodo-1,4-phenylene diacetate (2).
Compounds 1 and 2 were synthesized according to the literature procedures.30-32
Synthesis
of
tetramethyl
5,5'-((2,5-diacetoxy-1,4-phenylene)bis(ethyne-2,1-
diyl))diisophthalate (3) and 5,5'-(benzo[1,2-b:4,5-b']difuran-2,6-diyl)diisophthalic acid (4).
The reaction of compound 1 (5.17 g, 21 mmol), compound 2 (4.46 g, 10 mmol), PdCl2(PPh3)2
(50 mg, 0.07 mmol), CuI (27 mg, 0.14 mmol), and Et3N (7.5 mL) in DMF (7.5 mL) afforded the
coupling product (4.33 g, 83.7%) as a yellow solid after being stirred at 70 oC for 24 h under N2.
Then NaOH (5 g, 125 mmol) was added to a solution of compound 3 (4.33 g, 6.9 mmol)
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dissolved in a mixture of tetrahydrofuran (THF, 20mL), methanol (30 mL) and water (30 mL).
The mixture was stirred under reflux for 5 h, and the resulting solution was acidified to pH 1-2
with concentrated aqueous HCl (12 M). The precipitated solid was separated by filtration and
washed successively with water to give compound 4 (3.5 g, 7.1 mmol, 81%) as a yellow solid.
1H NMR (300 MHz, DMSO-d6, 25 °C) δ (ppm): 13.54 (s, 4H), 8.63 (d, J = 1.5 Hz, 4H), 8.44 (t,
J = 3 Hz, 2H), 7.91 (s, 2H), 7.79 (s, 2H). Anal. Calcd for C26H14O10 (486.38): C 64.2, H 2.9.
Found: C 61.2, H 3.2%.
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Synthesis
diyl))diisophthalate
diyl))diisophthalic acid (6).
of
tetramethyl
5,5'-(benzo[c][1,2,5]thiadiazole-4,7-diylbis(ethyne-2,1-
5,5'-(benzo[c][1,2,5]thiadiazole-4,7-diylbis(ethyne-2,1-
(5) and
The reaction of compound 1 (5.64 g, 23 mmol), 4,7-dibromobenzo[c][1,2,5]thiadiazole (3.2 g,
11 mmol), PdCl2(PPh3)2 (30 mg, 0.042 mmol), CuI (15 mg, 0.084 mmol), and Et3N (10 mL) in
DMF (10 mL) afforded the coupling product (4.5 g, 80%) as a brown solid after being stirred at
o
70 C for 24 h under N2. Then NaOH (5 g, 125 mmol) was added to a solution of compound 5
(4.5 g, 7.9 mmol) dissolved in a mixture of methanol (30 mL) and water (30 mL). The mixture
was stirred under reflux for 5 h, and the resulting solution was acidified to pH = 1-2 with
concentrated aqueous HCl (12 M). The precipitated solid was separated by filtration and washed
1
successively with water to give compound 6 (3.6 g, 7.0 mmol, 80%) as a brown solid. H NMR
(300 MHz, DMSO-d6, 25 °C) δ (ppm): 13.61 (s, 4H), 8.49 (t, J = 3.1 Hz, 2H), 8.32 (d, J = 1.8 Hz,
4H), 8.07 (s, 2H). Anal. Calcd for C26H12N2O8S (512.45): C 60.94, H 2.36, N 5.46, S 6.26.
Found: C 59.43, H 2.9, N 5.26, S 6.06%.
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Synthesis of [Cu2(bdfdpa)(H2O)2]·8DMF·2H2O (JLU-Liu29). A mixture of H4bdfdpa (0.0024
g, 0.005 mmol), CuI (0.010 g, 0.05 mmol), HBF4 (100 ꢀL) and DMF (1 mL) was sealed in a 20
mL vial, and ultrasonic treated for 3 minutes at room temperature until it changed to clear
solution, then kept in an oven at 85 °C for 24 h, and cooled to room temperature. The green
block crystals were collected, washed with DMF, and air-dried (76% yield based on CuI). Anal.
Calcd for Cu2C50H66O19N8: C 48.79; H 4.67; N 0.46%; found: C 46.73; H 3.33; N 0.50%.
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Synthesis of [Cu2(btadpa)(H2O)2]·7DMF·8H2O (JLU-Liu30). A mixture of H4btadpa (0.0025
g, 0.005 mmol), CuI (0.002 g, 0.001 mmol), HBF4 (100 ꢀL) and DMF (1 mL) was sealed in a 20
mL vial and ultrasonic treated for 3 minutes at room temperature until it changed to clear
solution, then kept in an oven at 85 °C for 24 h, and cooled to room temperature. The green
block crystals were collected, washed with DMF, and air-dried (65% yield based on CuI). Anal.
Calcd for Cu2C47H75N9O27S: C 41.60; H 5.53; N 9.28, S 2.36%; found: C 42.70; H 5.18; N 10.67,
S 1.87%.
The phase purity of as-synthesized samples was confirmed by the evident similarities
between the calculated and the experimental PXRD patterns (Fig. S2). The IR spectra for
compounds are shown in the Supporting Information (Fig. S4).
X-ray crystallography
Single-crystal X-ray diffraction measurements were carried out on a Bruker Apex II CCD
diffractometer for JLU-Liu29 and JLU-Liu30 with graphite monochromated Mo Kα (λ =
0.71073 Å) radiation at 293 K. Data processing was accomplished with the SAINT processing
program.33 The structures of these compounds were solved by direct method and refined on F2 by
full-matrix least-squares with the SHELEX-2014/7 program.34 All the non-hydrogen atoms were
refined with anisotropic displacement parameters. The hydrogen atoms on the aromatic rings
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were located geometrically with isotropic thermal parameters of 1.2 times those of the attached
carbon atoms. The void volume of these compounds can be obtained by the
PLATON/SQUEEZE program,35-36 and the related topology analysis is obtained from the
TOPOS software.37 Formulas of these two compounds were designated from the crystallographic
data combined with experimental ones (element analyses, TGA). Crystallographic data for JLU-
Liu29, JLU-Liu30 (1479873-1479874) have been deposited with Cambridge Crystallographic
Data Centre. Data can be obtained free of charge upon request at
www.ccdc.cam.ac.uk/data_request/cif. The summary of the crystallographic data and related
parameters can be seen in Table 1, while the selective bond lengths and angles of these
compounds are given in Tables S1 and S2 (Supporting Information).
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Gas Adsorption Measurements
The N2, CO2, CH4, C2H6 and C3H8 gas adsorption measurements were performed on a
Micromeritics ASAP 2420, Micromeritics ASAP 2020 and Micromeritics 3-Flex instruments.
Before gas adsorption measurements, JLU-Liu29 and JLU-Liu30 were exchanged with fresh
acetone for 3 days to fully removal the guest DMF and water molecules, which can be proved by
TGA analysis (Fig. S3). The samples were activated by drying under a dynamic vacuum at room
temperature for 1 hour. Before the measurement, the sample was dried again by using the ‘outgas’
function of the surface area analyzer for 10 h at 100 °C.
GC-MS Measurements
A GC-MS system (GCMS-QP 2010 plus, Shimadzu, Kyoto, Japan) was used.
Chromatographic separation was conducted with a DB-5MS capillary column (30 m × 0.25 mm
i.d., film thickness of 0.25 ꢀm, J & W Scientific, Folsom, CA, USA). Helium (purity ≥ 99.999%)
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was used as carrier gas at a constant flow of 1.0 mL min-1. The temperature program was set
140 °C for benzothiophene (BT), 250 °C for dibenzothiophene (DBT) and 4,6-
dimethyldibenzothiophene (DMDBT). Injector temperature was maintained at 250 °C, and the
injection volume was 1.0 ꢀL in the splitless mode. The ion source and interface temperatures
were 200 °C and 250 °C, respectively, and electron impact ionization energy was 70 eV. The
mass spectrometer was operated in the selective ion monitoring (SIM) mode. Full-scan MS data
were acquired in the range of m/z 50-900 to obtain the fragmentation spectra of the analytes.
And the sample of acetone exchanged JLU-Liu29 and JLU-Liu30 were degassed at room
temperature for 10 h to activate the sample on a degassing station.
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RESULTS AND DISCUSSION
Crystal Structure Descriptions.
Single crystal X-ray diffraction and TOPOS analyses suggest that both of the compounds are
fof-type MOFs. JLU-Liu29 crystallizes in the trigonal R-3m space group. As expected, the 4-
connected copper paddle wheel Cu2(CO2)4 SBUs are further bridged by 3-connected organic
ligand to form a (3, 4)-connected structure, which belongs to fof topology with a Schläfli symbol
of (6.82)2(62.82.102.) (Fig. 1a-c).38 A further insight to this structure suggests that there are two
kinds of distinct cages alternatively packed with a ratio of 1:1 in this framework. As shown in
Fig. 1d, the spherical-like cages are composed of six Cu2(CO2)4 SBUs and twelve bdfdpa4-
ligands, and the cage can be regarded as edge decorated by bdfdpa4- ligands with the diameter is
ca. 12 Å. The shuttle-like cages are composed of six bdfdpa4- ligands and twelve Cu2(CO2)4 units,
while the cage can also be regarded as face-decorated by the ligands, the diameter of such a cage
is about 6 Å when the Van der Waals radii of the atoms are not taken into account. The
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accessible void volume of JLU-Liu29 after removal of guest molecules is calculated to be 73.9%
when the single crystal structure is used with the PLATON/SQUEEZE program. JLU-Liu30 has
the same underlying net with JLU-Liu29, and the spherical-like cage is ca. 11Å, the shuttle-like
cage is ca. 6Å (Fig. 1e) and the calculated void volume is 70.9%.
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Gas Adsorption Behaviours
The permanent porosity of JLU-Liu29 and JLU-Liu30 were confirmed by nitrogen
adsorption-desorption isotherm at 77 K. All the samples were activated with acetone for about
three days and then degassed under high vacuum at 373 K for about 12 h to obtain the guest
molecule free frameworks. From the TGA curves, the guest-molecules are almost effectively
exchanged and the integrity of the samples was investigated with PXRD patterns, as can be seen
in Fig. S2. Both the samples exhibit the color change from green to purple, which suggests the
generation of open Cu2+ sites in the frameworks. The N2 adsorption isotherms of JLU-Liu29 and
JLU-Liu30 exhibit reversible typical type I adsorption behaviours with a large amount of N2 at
77 K (698 cm3 g−1 for JLU-Liu29 and 566 cm3 g−1 for JLU-Liu30, at 1 bar). Based on the
isotherms, the Brunauer-Emmett-Teller (BET) and Langmuir surface areas were estimated to be
2205 m2 g-1 and 2967 m2 g-1, respectively for JLU-Liu29, while 1791 m2 g-1 and 2409 m2 g-1 for
JLU-Liu30. The pore volumes calculated from the maximum amount of N2 absorbed were 1.07
cm3 g-1 and 0.81 cm3 g-1. The value of JLU-Liu29 are lower than NOTT-101,39 but slight higher
than ZJU-25,40 and comparable to ZJNU-40.41 Due to that benzothiadiazole moieties included in
the frameworks may block up the cages formed. The value of JLU-Liu30 are lower than JLU-
Liu29, and comparable to Cu2dbip42 (Table S3).
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The high surface area, large pore volume, open Cu2+ sites and functional groups moieties
of these two MOFs promoted us to investigate their capacities in the gas uptake. To investigate
the performance of these compounds for CO2 capture, low pressure CO2 adsorption-desorption
measurements were measured at 273 and 298 K, respectively. As illustrated in Figure 2, high
CO2 uptake of about 145 cm3 g−1 can be observed for JLU-Liu29 at 273 K and 1 bar, while
JLU-Liu30 reaches a value of 49 cm3 g−1. The uptakes of CO2 for these materials at 298 K also
reach to 72 cm3 g−1 and 26 cm3 g−1, respectively. Remarkably, though the CO2 uptake of JLU-
Liu29 and JLU-Liu30 is lower than that of NU-135,27 the relatively higher uptake value of
JLU-Liu29 is still significantly higher than NOTT-10139(Table S3).
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The potential of these compounds for small hydrocarbons adsorption are also explored. The
adsorption isotherms of CH4, C2H6 and C3H8 are measured at 273 and 298 K under 1 bar,
respectively. The maximum uptakes of JLU-Liu29 for CH4 is 25 and 15 cm3 g-1, for C2H6 is 201
and 127 cm3 g-1 and for C3H8 is 236 and 207 cm3 g-1, respectively. Another compound, JLU-
Liu30, also exhibits notable adsorption capacities to CH4, C2H6 and C3H8. Adsorption of CH4 is
29 and 17 cm3 g-1, C2H6 is 199 and 116 cm3 g-1 and C3H8 is 237 and 208 cm3 g-1 at 273 and 298
K under 1 bar, respectively, which overpass the values of JLU-Liu15,43 JLU-Liu22,44 and BIF-24
45 (Figure 3).
Organosulfurs Removal Experiments
Most MOF materials show a high affinity to water or hydrogen but only a few are known to
possess significant organosulfurs removal properties. In this study, we have investigated JLU-
Liu29 and JLU-Liu30’s performance for adsorption of benzothiophene (BT), dibenzothiophene
(DBT) and 4, 6-dimethyldibenzothiophene (DMDBT) molecules which were dissolved in n-
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hexane solvent. Measured 5 mg samples and added into 1 mL n-hexane solvent containing 0.01
mmol BT, 0.01 mmol DBT and 0.01 mmol DMDBT. Make a series of the same mixture while
increasing the sample weight by 5 mg each time until the sample weight reaches 60 mg. The
mixture was standing for 12 h at room temperature. The amount of BT, DBT or DMDBT in the
n-hexane phase was determined by GC-MS analysis. The results clearly show the decrease of BT,
DBT and DMDBT in the n-hexane solvent with increasing the amount of the samples. The
concentration of the BT treated by JLU-Liu29 was reduced from 10 mmol L-1 to 2.14 mmol L-1.
The DBT and the DMDBT were reduced to 0.59 mmol L-1 and 0.8 mmol L-1, respectively. As
for the other compound, JLU-Liu30, the final concentration of BT, DBT and DMDBT were 3.09
mmol L-1, 2.17 mmol L-1, and 1.58 mmol L-1 (Figure 4). These results are better than HKUST-
146 and comparable to the reported porous MOFs, such as [In3(bpdc)3(HCOO)(H2O)3/2]·xDMF.17
Both the compounds exhibiting great adsorption for organosulfurs can be attributed to the π-
complexation between the organosulfur compounds and the functional groups, dibenzofuran and
benzothiadiazole.17-19
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CONCLUSION
In summary, by utilizing two tetracarboxylate acid ligands including functional moieties such
as dibenzofuran and benzothiadiazole, two fof type MOFs, JLU-Liu29 and JLU-Liu30, have
been obtained. Both of these compounds exhibit high permanent porosity with the pore volume
about 1.07 and 0.81 cm3 g-1. Combined with high surface areas, open Cu2+ sites, and functional
groups, these compounds show high capacity of CO2 and evaluate their abilities for sulfur-
removal of different benzothiophene, dibenzothiophene and 4,6- dimethyldibenzothiophene. This
work can further demonstrate the potential application of the fof type MOF families in the gas
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storage and organosulfur purification areas. Thus the further development of fof type MOFs is
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worth to be done in the future.
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ASSOCIATED CONTENT
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Supporting Information.
Crystallographic data in CIF format, table for selected bonds and distances for JLU-Liu29-30,
PXRD patterns, IR spectra, Thermogravimetric analysis, Elemental analyses (C, H, N and S) for
1
JLU-Liu29-30, and H NMR for (5,5’-(benzo[1,2-b:4,5-b’]difuran-2,6-diyl)diisophthalic acid
(H4bdfdpa) and 5,5’-(benzo[c][1,2,5]thiadiazole-4,7-diylbis(ethyne-2,1-diyl))diisophthalic acid
(H4btadpa). This material is available free of charge via the Internet at http://pubs.acs.org.
AUTHOR INFORMATION
*(Y.L.) Fax: +86-431-85168624. E-mail: yunling@jlu.edu.cn.
*(D.-S.L.) E-mail: lidongsheng1@126.com.
Notes
The authors declare no competing financial interests.
ACKNOWLEDGMENT
This work was supported by the National Natural Science Foundation of China (Nos. 21373095
21371067, 21373122 and 21621001).
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Figure Captions
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Scheme 1 The structures of benzothiophene (BT), dibenzothiophene (DBT) and 4,6-
dimethyldibenzothiophene (DMDBT).
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Scheme 2 Synthesis of the organic ligands of 5,5'-(benzo[1,2-b:4,5-b']difuran-2,6-
diyl)diisophthalic acid (H4bdfdpa) and 5,5'-(benzo[c][1,2,5]thiadiazole-4,7-diylbis(ethyne-2,1-
diyl))diisophthalic acid (H4btadpa).
Figure 1 Description of the structures of JLU-Liu29 and JLU-Liu30: (a) Cu paddlewheel SBUs,
and organic bdfdpa4- and btadpa4- ligands viewed as a pair of 3-c node; (b) polyhedral view of
the fof topology; (c) the tiling illustration of fof net; (d) two types of cages in JLU-Liu29; (e) two
types of cages in JLU-Liu30; (f) ball and stick model of JLU-Liu29; (g) ball and stick model of
JLU-Liu30; Color scheme: carbon = gray, oxygen = red, nitrogen = blue, sulfur = yellow,
copper = green. Guest molecules and H atoms have been omitted for clarity.
Figure 2 CO2 adsorption isotherms for JLU-Liu29 (a) and JLU-Liu30 (b) at 273 and 298 K
under 1 bar, respectively. Qst of CO2 for JLU-Liu29 (c) and JLU-Liu30 (d)
Figure 3 (a) CH4, (c) C2H6, (e) C3H8 gas sorption isotherms for JLU-Liu29 and (b) CH4, (d)
C2H6, (f) C3H8 gas sorption isotherms for JLU-Liu30 at 273 and 298 K under 1 bar.
Figure 4 The adsorption performance of JLU-Liu29 and JLU-Liu30 for BT, DBT, and
DMDBT dissolved in n-hexane.
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Scheme 1
Scheme 2
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Figure 1
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Figure 2
Figure 3
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Figure 4
Table 1 Crystallographic data for JLU-Liu29-30.
Compound
Formula
Formula weight
Temperature (K)
Wavelength (Å)
Crystal system
Space group
a (Å)
JLU-Liu29
Cu2C50H66O19N8
1210.18
JLU-Liu30
Cu2C47H75N9O27S
1357.30
296(2)
296(2)
0.71073
0.71073
Trigonal
R-3m
Trigonal
R-3m
18.7967(9)
18.7967(9)
49.394(5)
90
18.8276(3)
18.8276(3)
54.1490(2)
90
b (Å)
c (Å)
α (o)
β (o)
γ (o)
90
90
120
120
Volume (Å3)
15114(2)
9
16623.1(8)
9
Z
F(000)
5688
6390
θ
range (deg)
1.237 to 24.999
32691 / 3263
0.1499
1.128 to 25.045
36018 / 3611
0.0419
reflns collected/unique
Rint
data/restraints/params
Goodness-of-fit on F2
3263 / 128 / 99
1.032
3611 / 133 / 133
1.175
R1, wR2 [I>2
σ
(I)]
0.0884, 0.2574
0.1735, 0.3311
0.0834, 0.2751
0.0939, 0.2868
R1, wR2 (all data)
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Two Functional Porous Metal-Organic Frameworks Constructed
from Expanded Tetracarboxylates for Gas Adsorption and
Organosulfurs Removal
Xiaolong Luo,a Liang Kan,a Xiang Li,a Libo Sun,a Guanghua Li,a Jun Zhao,b Dong-Sheng Li,*,b
Qisheng Huoa and Yunling Liu*,a
JLU-Liu29 and JLU-Liu30 have been constructed by using expanded tetracarboxylates
ligands and Cu2(CO2)4 paddle wheel building units. Both of the two compounds exhibit high
surface area, excellent adsorption for small molecule gases, and notable removal behavior of
refractory organosulfur compounds.
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