A microporous metal-organic framework constructed from a new tetracarboxylic acid for selective gas separation

Article abstract of DOI:10.1021/cg500235j

A new organic ligand of pyrene-containing tetracarboxylic acid and its first metal-organic framework UTSA-72 was designed and synthesized. The MOF has the two-dimensional (4,4) framework topology. The activated UTSA-72a exhibits permanent porosity and moderately high selectivities for CO₂/N ₂, C₂H₂/CH₄, and CO ₂/CH₄ gas separations at room temperature because of the small pores within the framework.

Full text of DOI:10.1021/cg500235j

Article
pubs.acs.org/crystal
A Microporous Metal−Organic Framework Constructed from a New
Tetracarboxylic Acid for Selective Gas Separation
Hussah Alawisi,† Bin Li,† Yabing He,† Hadi D. Arman,† Abdullah M. Asiri,‡ Hailong Wang,*,†
and Banglin Chen*,†,‡
†Department of Chemistry, University of Texas at San Antonio, San Antonio, Texas 78249-0698, United States
‡Department of Chemistry, Faculty of Science, King Abdulaziz University, Jeddah 22254, Saudi Arabia
S
* Supporting Information
ABSTRACT: A new organic ligand of pyrene-containing tetracarboxylic acid
and its first metal−organic framework UTSA-72 was designed and synthesized.
The MOF has the two-dimensional (4,4) framework topology. The activated
UTSA-72a exhibits permanent porosity and moderately high selectivities for
CO2/N2, C2H2/CH4, and CO2/CH4 gas separations at room temperature
because of the small pores within the framework.
Scheme 1. Schematic Molecular Structure of H4PTTB
Ligand
INTRODUCTION
■
Microporous metal−organic frameworks (MOFs) are very
promising porous materials for gas separation.1,2 Such materials
can be readily constructed from self-assembly of the suitable
metal ions/clusters and organic linkers.3,4 Because the
chemistry of metal ions/clusters and organic linkers is very
rich, an almost infinite amount of porous MOFs can be
theoretically synthesized in which their pores can be system-
atically varied based on the different combinations of metal
ions/clusters and organic linkers, and diverse framework
topologies.5,6 Indeed, a very wide range of porous MOFs
from those ultramicroporous (pore sizes smaller than 3.0 Å) to
those mesoporous (pore sizes larger than 25 Å) have been
realized with the highest BET surface area up to 7000 m2/g and
pore volume of 4.40 cm3/g.7 In terms of MOFs for their gas
separation, high porosities are not the prerequisite, whereas
suitable pore sizes/windows for their size-exclusive effects and
functional sites for their differential interactions with gas
molecules are even much more important.8−10 There have been
extensive research endeavors on the construction of micro-
porous MOFs for gas separation.11 Over the past several years,
we have been particularly interested in those porous MOFs
with small pores for gas separation and realized a series of such
porous MOF materials for such a purpose.12 On the one hand,
detailed studies on some reported MOFs will be still necessary
to rediscover their values for gas separation;13 on the other
hand, it will be certainly important to target some new organic
linkers and their constructed MOFs for their diverse functions
as well. With this in mind, we developed a new organic linker,
3,3′,3″,3‴-(pyrene-1,3,6,8-tetrayl)tetrabenzoic acid (H4PTTB)
(Scheme 1). This linker can be straightforwardly synthesized by
the coupling and hydrolysis reaction from its bromo precursor.
Solvothermal reaction of this organic linker with Zn(NO3)2 led
to the formation of a new microporous MOF [Zn2(PTTB)-
(DMF)2]n·(DMF)n (UTSA-72) in which the well-known
paddle-wheel Zn2(COO)4 cluters are bridged by PTTB
tetracarboxylates to form a two-dimensional MOF. The
single-crystal X-ray structure of UTSA-72 was characterized.
With two kinds of small micropores of about 2.9 × 2.9 and 2.4
× 4.6 Å2, the activated UTSA-72a exhibits moderately high
selective gas separation for C2H2/CH4, CO2/CH4, and CO2/N2
at room temperature.
EXPERIMENTAL SECTION
■
All reagents and solvents were used as received from commercial
suppliers without further purification. 1,3,6,8-Tetrabromopyrene was
prepared according to the reported literature.14 The multidentate O-
donor ligand of 3,3′,3″,3‴-(pyrene-1,3,6,8-tetrayl)tetrabenzoic acid
(H4PTTB) was prepared referring to the published procedure with
slight modification.14 The powder X-ray diffraction (PXRD) pattern
was recorded by a Rigaku Ultima IV diffractometer with Cu Kα
radiation operated at 40 kV and 44 mA with a scan rate of 2.0° min−1.
The FTIR spectrum was performed at a Bruke Vector 22 infrared
1
spectrometer at room temperature. H NMR and 13C NMR spectra
Received: February 14, 2014
Revised: March 29, 2014
© XXXX American Chemical Society
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were obtained using a Varian INOVA 500 MHz spectrometer at room
temperature. Tetramethylsilane (TMS) and deuterated solvents
(DMSO-d6, δ = 39.5 ppm) were used as internal standards in H
paper. These data can be obtained free of charge from the Cambridge
Crystallographic Data Centre via www.ccdc.cam.ac.uk/data_request/
cif.
1
NMR and 13C NMR experiments, respectively. The elemental analyses
were performed with PerkinElmer 240 CHN analyzers from Galbraith
Laboratories, Knoxville, TN. Thermal gravimetric analysis (TGA) was
performed under a nitrogen atmosphere with a heating rate of 3 °C/
min using a Shimadzu TGA-50 thermogravimetric analyzer. A
Micromeritics ASAP 2020 surface area analyzer was used to measure
gas adsorption isotherms. The methanol-exchanged UTSA-72 was
activated under high vacuum at room temperature for 24 h to generate
the activated UTSA-72a. A sample of activated UTSA-72a was used
for the sorption measurement and was maintained at 196 K with a dry
ice−acetone slurry, at 273 K with an ice−water bath. As the center-
controlled air condition was set up at 23 °C, a water bath was used for
adsorption isotherms at 296 K.
RESULTS AND DISCUSSION
■
UTSA-72 was synthesized by the solvothermal reaction
between zinc nitrate and H4PTTB in the presence of DMF
solvent at 80 °C. UTSA-72 crystallizes in the monoclinic
system and P2/c space group.19 As quite frequently observed in
MOFs, the framework contains paddle-wheel binuclear Zn2-
(COO)4 secondary building units (Figure 1a), which are
Synthesis of H4PTTB Ligand. A mixture of (3-(methoxy-
carbonyl)phenyl)boronic acid (2.5 g, 16.5 mmol), 1,3,6,8-tetrabromo-
pyrene (1.42 g, 2.75 mmol), potassium carbonate (3.0 g, 22 mmol),
and dry dioxane (40 mL) was stirred under nitrogen for 30 min at
room temperature, and then palladium tetrakis(triphenylphosphine)
(0.05 g, 0.045 mmol) was added. The temperature of the reaction
mixture was refluxed for 3 days. After it cooled to room temperature,
the reaction mixture was poured into a solution of 150 mL of ice
containing concentrated hydrochloric acid (3:1). The solution with a
yellow suspension was extracted with chloroform (100 mL × 3), and
the organic phases were combined and dried over anhydrous sodium
sulfate. The solvent was removed on a rotatory evaporator under
vacuum, giving 1,3,6,8-tetrakis(3-(methoxycarbonyl)phenyl)pyrene
with a yield of 1.54 g, 76%. The product was directly used to give
the H4PPTB ligand in the detailed procedure as below.
A mixture of 1,3,6,8-tetrakis(3-(methoxycarbonyl)phenyl)pyrene
(0.5 g), an excess amount of NaOH (1.5 g), and 150 mL of THF/
dioxane/H2O (1:1:1) was stirred and refluxed for 24 h. The organic
solvent was removed under vacuum, and the mixture was filtrated. The
pH value of the filtrate was adjusted to 2−4 by using concentrated
HCl. The resulting yellow solid was collected by filtration, washed with
water and methanol, and then dried under vacuum to construct the
Figure 1. X-ray crystal structure of UTSA-72 indicating (a) the
coordination geometry for Zn(II) atoms (the hydrogen atoms and
solvent molecules omitted for clarity), (b) 2D square grid, and the 3D
framework packing of UTSA-72 along (c) a and (d) c axes,
respectively.
1
metal−organic framework. Yield: 0.44 g, 95%. H NMR (DMSO-d6):
δ 13.12 (s, 4H), 8.21 (s, 4H), 8.12 (s, 4H), 8.08 (d, J = 5 Hz, 4H), 8.04
(s, 2H), 7.95 (d, J = 5 Hz, 4H), 7.72 (t, J = 5 Hz, 4H) (Figure S1,
Supporting Information). 13C NMR (DMSO-d6): δ 167.18, 140.09,
136.25, 134.85, 131.23, 131.04, 129.04, 127.58, 125.23 (Figure S2,
Supporting Information). Anal. Calcd for C44O8H26·2H2O: C, 75.42;
H, 4.03. Found: C, 75.42; H, 4.00.
bridged by organic PTTB tetracarboxylates to form a slightly
distorted two-dimensional (2D) square grid {Zn2(PTTB)2}
(Figure 1b). The fifth coordination sites of paddle-wheel
Zn2(COO)4 units were occupied by the DMF molecules. The
topology of UTSA-72 can be best described as a simple 4,4-
connected net (Figure 1c,d). The structure is quite similar to
those well-established ones, such as MOF-2 Zn(BDC)-
(DMF),20 Cu(BDC-OH),21 and Zn2(TBAPy).22 The adjacent
2D square grids are packed parallelly, leading to the final
porous-containing frameworks with the two kinds of cavities of
2.9 × 2.9 Å2 for i and 2.4 × 4.6 Å2 for ii.
[Zn2(PTTB)(DMF)2]n·(DMF)n (UTSA-72). The starting materials of
Zn(NO3)2·6H2O (0.2 g), H4PTTB (0.11 g), and DMF (2 mL) were
sealed in a 23 mL vial and heated at 80 °C for 48 h. After being cooled
to room temperature, the oven was cut off, leading to the separation of
perfect yellowish orange crystals suitable for X-ray diffraction by
filtration with a yield of 0.13 g, 81% (based on H4PTTB ligand). Anal.
Calcd for C53H43O11N3Zn2: C, 61.88; H, 4.21; N, 4.08. Found: C,
61.91; H, 4.23; N, 4.07. IR/cm−1 (KBr): 2927 (m), 1624 (s), 1394 (s),
1086 (s), 772 (s), 734(m), 696 (m).
Single-Crystal X-ray Diffraction Determination. A crystal
suitable for X-ray diffraction was mounted in Paratone oil onto a
glass fiber and frozen under a nitrogen cold stream. The data were
collected at 98(2) K using a Rigaku AFC12/Saturn 724 CCD fitted
with Mo Kα radiation (λ = 0.71073 Å). Data collection and unit cell
refinement were performed using CrystalClear software.15 Data
processing and absorption correction, giving minimum and maximum
transmission factors, were accomplished with Crystal Clear and
ABSCOR,16 respectively. All structures were solved by direct methods
and refined on F2 using full-matrix, least-squares techniques with
SHELXL-97.17,18 All non-hydrogen atoms were refined with
anisotropic displacement parameters. All carbon bound hydrogen
atom positions were determined by geometry and refined by a riding
model. “DFIX”, “ISOR”, “EADP”, and “PART” commands were used
to deal with the disorder of solvent DMF molecules. CCDC 986601
for UTSA-72 contains the supplementary crystallographic data for this
The phase purity of the material in bulk amount was
confirmed by elemental analysis and powder X-ray diffraction
(PXRD) (Figure S3, Supporting Information). As shown in
Figure S4 (Supporting Information), the thermogravimetric
analysis (TGA) studies reveal that UTSA-72 gradually loses the
free and coordinated DMF molecules (obsd. 21.2%, calcd.
21.4%) in the temperature range from 25 to 385 °C to form the
desolvated framework. The activated UTSA-72a still exhibits a
highly crystalline nature whose PXRD pattern is slightly right-
shifted, indicating a certain degree of framework flexibility and
shrinkage of the framework.
The structurally porous nature of UTSA-72 and its similar
structure with MOF-2 Zn(BDC)(DMF),20 Cu(BDC-OH),21
and Zn2(TBAPy)22 have encouraged us to examine permanent
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porosity and thus for gas separation. The methanol-exchanged
UTSA-72 was activated under high vacuum at room temper-
ature for 24 h to generate the activated UTSA-72a. The CO2
gas sorption isotherm at 196 K (Figure 2) clearly indicates its
Figure 2. CO2 sorption isotherm of UTSA-72a at 196 K (solid
symbols: adsorption; open symbols: desorption).
microporous nature. UTSA-72a has a Brunauer−Emmett−
Teller (BET) surface area of 173 m2 g−1 (Figure S5, Supporting
Information), which is smaller than 270 m2/g in MOF-2
Zn(BDC)(DMF),20 584 m2/g in Cu(BDC-OH),21 and 523
m2/g in Zn2(TBAPy).22 As revealed in MOF-220 and
Zn2(TBAPy),22 the release of the terminal DMF molecules
might lead to the formation of a three-dimensional framework
Zn2(PTTB)2 (UTSA-72a). Because the new organic linker
PTTB is spatially smaller than the organic linker in Zn2-
(TBAPy),22 it is understandable that UTSA-72a exhibits
smaller permanent porosity as well.
The small pore spaces and the establishment of its
permanent porosity within UTSA-72a motivated us to examine
its C2H2, CO2, CH4, and N2 gas sorption isotherms and
potential for these gas separations. As shown in Figure 3,
UTSA-72a takes up moderate amounts of acetylene (27.8 cm3
g−1) and carbon dioxide (21.7 cm3 g−1),23 while much lower
amounts of methane (4.4 cm3 g−1) and nitrogen (1.1 cm3 g−1)
at 296 K and 1 atm.23 Their sorption isotherms at 273 K further
confirm the different gas uptakes of UTSA-72a for these
examined gas molecules, underlying the potential of this new
MOF for the selective gas separation of CO2/N2, C2H2/CH4,
and CO2/CH4.
The coverage-dependent adsorption enthalpies of UTSA-72a
to these four gas molecules were calculated based on the virial
method,24 a well-established and reliable methodology from fits
of their adsorption isotherms at 273 and 296 K (Figures S6 and
S7, Supporting Information). The enthalpies at zero coverage
of gas were calculated to give the values of 20.2, 34.6, 11.4, and
10.2 kJ/mol for C2H2, CO2, CH4, and N2, respectively. The
adsorption enthalpies for C2H2 and CO2 in UTSA-72a are
moderately high,24 whereas those for CH4 and N2 are slightly
lower than those reported values. The relatively high Qst of this
compound may be due to the small pore size and open metal
sites in the activated framework, which favors the selective gas
separation for these small gas molecules. Accordingly, the
Henry’s law selectivities for CO2/N2 calculated based on the
equation Si/N2 = KH(i)/KH(N2) are 61.6 at 273 K and 33.4 at
296 K. Such Henry’s law selectivities for CO2/N2 are quite
high. The selectivity of 61.6 at 273 K is much higher than 6.4 in
a much more porous MOF. The selectivities for C2H2/CH4 and
CO2/CH4 calculated based on the equation Sii/CH4 = KH(i)/
Figure 3. C2H2 (black), CO2 (red), CH4 (blue), and N2 (green)
sorption isotherms of UTSA-72a at (a) 273 and (b) 296 K (solid
symbols: adsorption; open symbols: desorption).
KH(CH4) are also shown in Table 1, which are moderately
high. In fact, the CO2/CH4 selectivity of 7.2 at 296 K is higher
than 4.4 in Zn2(BDC)2(DABCO), 6.7 in Cu(BDC-OH), 7.0 in
UTSA-50a, and 6.2 in M’MOF-20a.21,24 The smaller pores
within UTSA-72a apparently play a role in the moderately high
selectivities for gas separations.
To further confirm the moderately high gas separation
selectivities of UTSA-72a, we applied the well-known ideal
adsorbed solution theory (IAST) calculation25 to evaluate the
IAST CO2/N2, C2H2/CH4, and CO2/CH4 adsorption
selectivities. Mixture adsorption isotherms and the selectivities
at different temperatures and pressures calculated by IAST for
mixed CO2/N2 (CO2/N2 = 15:85), C2H2/CH4 (C2H2/CH4 =
50:50), and CO2/CH4 (CO2/CH4 = 50:50) in this activated
MOF as a function of total bulk pressure are shown in Figure 4
and Figures S8 and S9 (Supporting Information), respectively.
As shown in Table S1 (Supporting Information), the IAST
selectivities for CO2/N2, C2H2/CH4, and CO2/CH4 are 48.3,
68.9, and 40.7, respectively, at 273 K and are 35.6, 26.5, and 9.3,
respectively, at 296 K. The moderately high IAST selectivities
once again established the good performance of UTSA-72a for
the above-mentioned gas separations. The CO2/N2 selectivities
with 0.15 bar of CO2 and 0.85 bar of N2 (modeling the typical
composition of flue gas mixture from power plants) at 273 K
are in the range of 48.3−47.6 (Figure 4), which are higher than
those for Ni-MOF-74 (∼30)25a and a py-CF3 modified MOF
(25−45)25b in similar conditions. The IAST CO2/CH4
separation selectivity of 40.7 at 273 K in UTSA-72a is
moderately high as well, and comparable to those found in a
microporous Ni MOF (∼65),26c a Co(II) carborane-based
MOF (∼47),27a and a mixed-ligand MOF (30).27b
CONCLUSION
In summary, we realized a new organic linker of pyrene-
containing tetracarboxylic acid and its first metal−organic
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Table 1. Virial Graph Analyses Data for UTSA-72a and Its C2H2/N2, CO2/N4, C2H2/CH4, and CO2/CH4 and Separation
Selectivity
a
adsorbate
C2H2
T (K)
KH (mol g−1 Pa−1
)
A0 (ln(mol g−1 Pa−1))
A1 (g mol−1
)
Si/N2
Sii/CH4
Qst (kJ mol−1
)
296
273
296
273
296
273
296
273
6.54 × 10−7
1.55 × 10−6
2.22 × 10−7
6.61 × 10−7
3.10 × 10−8
3.36 × 10−8
6.64× 10−9
1.07 × 10−8
−14.24
−13.38
−15.32
−14.23
−17.29
−17.21
−18.83
−18.35
−1181.0
−1342.7
−198.8
−957.3
−868.6
−208.7
−7659.3
−2544.5
98.5
144.0
33.4
61.6
4.7
21.1
46.1
7.2
20.2
CO2
CH4
N2
34.6
11.4
10.2
19.7
3.1
a
The Henry’s law selectivity for gas component i over N2 and CH4 at the speculated temperature is calculated based on the equations Si/N2 = KH(i)/
KH(N2) and Sii/CH4 = KH(i)/KH(CH4).
AUTHOR INFORMATION
■
Corresponding Authors
*E-mail: hailong.wang@utsa.edu (H.W.).
*E-mail: banglin.chen@utsa.edu (B.C.).
Notes
The authors declare no competing financial interest.
ACKNOWLEDGMENTS
■
This work was supported by the grant AX-1730 from the Welch
Foundation (B.C.). We would like to thank Prof. Dr. Daqiang
Yuan for his valuable input and providing the software to
calculate IAST gas separation selectivities.
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ASSOCIATED CONTENT
■
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* Supporting Information
X-ray crystallographic file (CIF), virial graphs for adsorption of
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charge via the Internet at http://pubs.acs.org.
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