Selective Sorption of Light Hydrocarbons on a Family of Metal-Organic Frameworks with Different Imidazolate Pillars

Article abstract of DOI:10.1021/acs.inorgchem.6b00136

Four isostructural pillared-layer metal-organic frameworks (as 1-ims series) are successfully synthesized via the charge-balance approach, where trigonal [Zn₂(CO₂)₃] cluster-based cationic layers [Zn₂(NH₂-BTB)]⁺ (NH₂-H₃BTB = 1,3,5-(3-benzoic acid) aniline) are connected by a series of 2-substituted imidazolates. The 1-ims supply a systematic platform to explore the adsorption of light hydrocarbons. Especially, 1-ims shows good adsorption selectivity of C₃/C₁ and C₂/C₁, and the selectivities of C₃H₈/CH₄ are all over 100 at room temperature. These results demonstrate that introduction of functional group plays a key role on tuning the channel and pore size as well as improving the adsorption selectivity.

Full text of DOI:10.1021/acs.inorgchem.6b00136

Article
pubs.acs.org/IC
Selective Sorption of Light Hydrocarbons on a Family of Metal−
Organic Frameworks with Different Imidazolate Pillars
Hong-Ru Fu and Jian Zhang*
State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences,
Fuzhou, Fujian 35002, China
*
S Supporting Information
ABSTRACT: Four isostructural pillared-layer metal−organic frameworks (as
-ims series) are successfully synthesized via the charge-balance approach,
1
+
where trigonal [Zn (CO ) ] cluster-based cationic layers [Zn (NH −BTB)]
2
2 3
2
2
(
2
NH −H BTB = 1,3,5-(3-benzoic acid) aniline) are connected by a series of
2
3
-substituted imidazolates. The 1-ims supply a systematic platform to explore
the adsorption of light hydrocarbons. Especially, 1-ims shows good adsorption
selectivity of C /C and C /C , and the selectivities of C H /CH are all over
3
1
2
1
3
8
4
1
00 at room temperature. These results demonstrate that introduction of
functional group plays a key role on tuning the channel and pore size as well
as improving the adsorption selectivity.
INTRODUCTION
also illustrate structure−property relationship via a combination
■
of functionalized linkers.
In recent years, porous metal−organic frameworks (MOFs)
have been emerging as a class of crystalline materials that is
extensively attractive for potential applications in gas storage/
EXPERIMENTAL SECTION
■
1
separation. Compared to the conventional porous materials,
Materials and Instruments. The 1,3,5-(tribenzoic acid)aniline
ligand was synthesized via Suzuki reaction. Powder X-ray diffraction
6
such as zeolites, the great advantages of MOFs lie in the pore
dimension and tunable features (such as tunable pore
geometries and adjustable surface functionality). An increas-
(PXRD) patterns were measured on a MiniFlex-II diffractometer using
Cu (λ = 1.541 78 Å) radiation. Thermogravimetric (TG) analysis was
performed on Netzsch STA449C. Gas sorption experiments were
performed with ASAP 2020 system. The materials maintain the
crystallinity after the removal of solvent molecules. Elemental analyses
were characterized by a Vario EL III elemental analyzer.
2
ingly inviting area in which MOFs have shown excellent
potential is adsorption and selective capture of light hydro-
3
carbons. Nevertheless, to date, a systematic investigation into
the effect of functional groups of isoreticular MOFs on the
adsorption and separation of light hydrocarbons is still seldom.
For the synthesis of functional materials with tailored
properties, structure predictability has been proved to be an
Synthesis of 1-mim. A mixture of 2-methylimidazole (2-mim,
0
.0155 g, 0.19 mmol), NH −H BTB (0.0245 g, 0.057 mmol),
2
3
Zn(NO ) ·6H O (0.0560 g, 0.2 mmol), tetramethylammonium
3
2
2
4
bromide (0.0153 g, 0.10 mmol), and dimethylformamide (DMF)/
efficient strategy for the design of MOFs. Among the methods
H O (v/v = 3:0.5, 3.5 mL) was heated in a 20 mL scintillation vial at
2
to construct porous MOFs, the concordance of functionaliza-
tion of the organic linker and the pillar−layer architecture is an
attractive approach to tune the properties of these materials,
because the functionalization of the pillared linkers not only
enhances the modification of the physicochemical properties of
the framework without a network rearrangement but also
generates the important effect on shape/size/enantioselective
1
00 °C for 24 h, followed by cooling to room temperature. The
resulting colorless crystals were washed with DMF and water and dried
in air. Anal. Calcd for [Zn (NH −BTB)][2-mim]·3DMF·7H O: Calcd
2
2
2
C, 47.43; H, 4.74; N, 8.30; found C, 47.98; H, 4.78; N, 8.81%.
Synthesis of 1-eim. A mixture of 2-ethylimidazole (2-eim, 0.0120
g, 0.13 mmol), NH −H BTB (0.0195 g, 0.044 mmol), Zn(NO ) ·
2
3
3 2
6H O (0.053g, 0.19 mmol), tetramethylammonium bromide (0.020g,
2
5
catalysis and the selective adsorption of guests.
0.13 mmol), and DMF/EtOH/H O (v/v/v = 4:4:1, 9 mL) was heated
2
Here we report a systematic approach toward fine-tuning the
pore and small hydrocarbons sorption behavior of the pillar-
type MOFs. The isostructural porous materials of [Zn (NH −
in a 20 mL scintillation vial at 100 °C for 24 h, followed by cooling to
room temperature. The resulting colorless crystals were washed with
DMF and water and dried in air. Anal. Calcd for [Zn (NH −BTB)][2-
2
2
2
2
eim]·3DMF·5H O: Calcd C, 49.70; H, 4.65; N, 8.48; found C, 49.54;
BTB)(2R-im)] (denoted as 1-ims, NH −H BTB = 1,3,5-(3-
2
2
3
H, 4.60; N, 8.17%.
benzoic acid) aniline, 2R-im = 2-substituted imidazolate)
exhibit high porosity. Moreover, the series of 1-ims show
light hydrocarbon storage capacity as well as good C H /CH ,
Received: January 22, 2016
3
8
4
C H /CH , C H /CH , and C H /CH selective separation,
2
6
4
2
4
4
2
2
4
©
XXXX American Chemical Society
A
DOI: 10.1021/acs.inorgchem.6b00136
Inorg. Chem. XXXX, XXX, XXX−XXX

Inorganic Chemistry
Article
Synthesis of 1-pim. A mixture of 2-propylimidazole (2-pim,
0
.0150 g, 0.14 mmol), NH −H BTB (0.0150 g, 0.035 mmol),
2
3
Zn(NO ) ·6H O (0.0400 g, 0.14 mmol), tetramethylammonium
3
2
2
bromide (0.0200 g, 0.13 mmol), and DMF/H O (v/v = 3:0.5, 3.5
2
mL) was heated in a 20 mL scintillation vial at 100 °C for 24 h,
followed by cooling to room temperature. The resulting colorless
block crystals were washed with DMF and water and dried in air. Anal.
Calcd for [Zn (NH −BTB)][2-pim]·3DMF·6H O: Calcd C, 49.31;
2
2
2
H, 4.89; N, 8.22; found C, 48.9; H, 4.73; N, 8.11%.
Synthesis of 1-buim. A mixture of 2-buthylimidazole (2-buim,
0
.0150 g, 0.12 mmol), NH −H BTB (0.0180 g, 0.042 mmol),
2
3
Zn(NO ) ·6H O (0.0560 g, 0.2 mmol), tetramethylammonium
3
2
2
bromide (0.0085 g, 0.055 mmol), and DMF/EtOH/H O (v/v/v =
2
4:2:1, 7 mL) was heated in a 20 mL scintillation vial at 100 °C for 24
h, followed by cooling to room temperature. The resulting crystals
were washed with DMF and water and dried in air. Anal. Calcd for
[
Zn (NH −BTB)][2-buim]·3DMF·5H O: Calcd C, 50.69; H, 4.91;
2
2
2
N, 8.25; found C, 48.79; H, 4.68; N, 7.73%.
X-ray Diffraction Analysis. Single-crystal X-ray structural
measurement analyses were performed on a Agilent SuperNova X-
ray diffractometer with Cu Kα radiation (λCu−Kα = 1.541 78 Å) at 100
K. The structures were solved and refined by using the SHELX-97
7
program package. Part solvent molecules in the structure were
disordered. The SQUEEZE program of PLATON was used to
eliminate the contribution of these disordered guest molecules.
Crystallographic data for four compounds were listed in Tables S1
and S2.
RESULTS AND DISCUSSION
■
[
Four pillared−layer MOFs were of the isostructural family
Zn (NH −BTB)(2R-im)], where R signifies the substituted
2
2
Figure 2. (a) The pillared-layer framework of 1-mim along the b-axis
group on the imidazole ligand. Figure 1 shows the related
(
green polyhedra: [Zn (CO ) ] units); (b) The framework of 1-buim
2 2 3
along the c-axis.
Figure 1. Basic structure in 1-ims and four kinds of imidazolate linkers.
building units and the structures of all ligands. Here, we
describe two representative structures, namely, 1-mim and 1-
buim, in detail. As shown in Figure 1, the asymmetric unit of 1-
mim contains a dinuclear zinc unit, one NH −BTB, and one 2-
2
mim ligand. The dinuclear Zn unit is surrounded by six
3
−
carboxylate groups from three NH −BTB ligands, forming a
2
tritopic paddle-wheel building unit. A triangle-planar
+
Zn (NH −BTB) layer is formed by [Zn (COO) ] paddle-
2
2
2
3
8
3−
wheel units and NH −BTB ligands. The μ -mim acts as a
2
2
Figure 3. (a, b) View of the interpenetrated framework along a- or b-
axis; (c) view of the interpenetrated framework along c-axis, showing
two kinds of windows.
pillar interconnecting the Zn ((NH −BTB) layers in [100]
2
2
direction, forming a three-dimensional neutral framework
[
Zn (NH −BTB)(2-mim)] (Figure 2). Because of the large
2
2
size of NH −BTB ligand, the pores are large enough for a
2
second net, which interpenetrates the first one (Figure 3).
Although the blockage of long side chain of the 2-butyl
imidazole linker, the interpenetration also occurred in 1-buim
unit cell volume of the isolated structure becomes gradually
smaller (36.3% in 1-mim and 20.2% in 1-buim), estimated by
9
using the PLATON program. The alkane groups of the
(Figure S2). Therefore, the free solvent-accessible volume per
imidazolate ligands are limited on the wall of the channels,
B
DOI: 10.1021/acs.inorgchem.6b00136
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Inorganic Chemistry
Article
having no effect on the distribution of channels (Figure 3a,b).
Thus, the size and shape of pores in these MOFs are very close
to each other. The sizes of two kinds of windows along the c-
axis are 6.7 × 9.2 and 12.3 × 10.7 Å , respectively (Figure 3c).
The TG analyses of these compounds were investigated
The slight differences of the microporous environment may
drastically affect adsorption behaviors. That prompted us to
further explore their adsorptive properties of light hydro-
carbons. 1-ims exhibit different adsorption capacities upon
response to C H , C H , C H , C H , and CH at 273 and 297
2
3
8
2
6
2
4
2
2
4
(Figure S12), and they exhibit similar weight loss steps. The
K (Table 1 and Figure 5). In general, 1-ims have an adsorption
first weight loss between 40 to ∼190 °C can be assigned to the
loss of the solvent water and DMF molecules. The second
weight loss is corresponding to the decomposition of the
frameworks. There are obvious plateaus between two weight
loss steps, and the frameworks do not collapse until near 500
°C, indicating these materials own excellent thermal stability.
The TG analyses of activated frameworks were performed, the
plateaus range from 40 to 500 °C show well that the initial
guest molecules can be fully exchanged by methanol, and
methanol molecules can be completely removed by the
thermal/vacuum activation at 333 K. The results of the
effective activation laid the foundation for gas sorption.
To investigate the pore characterization and adsorption
behavior of these materials, N physisorption measurements
2
were performed at 77 K. Because of the microporosity feature
of these MOFs, all of the compounds displayed typical type-I
gas sorption isotherms (Figure 4). Their surface areas
Figure 5. (a) C H sorption isotherms of 1-ims at 273 K; (b) C H
8
sorption isotherms of 1-ims at 273 K.
Figure 4. N sorption isotherms of 1-ims at 77 K.
2
2
3
2
(
Brunauer−Emmett−Teller model) are listed as follows: 1-
2
capacity with the following trend: C > C > C . Moreover, the
3 2 1
2
−1
2
−1
mim, 940.26 m g ; 1-eim, 877.41 m g ; 1-pim, 839.04 m
gas uptake capacities basically obey the order: 1-mim > 1-eim >
1-pim > 1-buim, in line with the order of surface areas and
porous volumes of these frameworks (Table 1 and Figures S5−
S9). The combination of pillared−layer frameworks and the
substituents offers the advantage for a fine-tuning of such
properties.
−1
2
−1
g ; 1-buim, 769.67 m g . Obviously, the steric bulk of the -R
group reduced the pore space, decreasing the surface areas. The
pore size of each compound is ∼10.2 Å calculated from
Horvath−Kawazoe equation (Figure S4). Moreover, the
adsorption of CO was also performed at 273 K and room
2
temperature (Table 1). The results exhibit that the series of
To further understand the gas adsorption behaviors, isosteric
heats of adsorption were calculated from the 273 and 297 K
functionalized ligands do not affect CO adsorption signifi-
2
cantly.
data, using the virial equation. A summary of Q for different
st
Table 1. Uptake Values of Small Hydrocarbons for Four Compounds at 273 and 297 K and 1 bar
V (cm g −1) (273 K/297 K)
3
a
CH4
C H
C H
C H
C H
8
CO2
2
2
2
4
2
6
3
1
1
1
1
-mim
-eim
14.65
19.32
16.24
14.08
10.64
11.48
9.70
119.42
117.84
102.42
93.54
76.26
73.70
65.00
56.14
92.37
87.30
84.54
73.16
64.95
61.29
53.72
48.70
101.03
79.91
75.38
71.65
63.00
102.92
97.36
97.31
83.46
96.87
86.60
83.29
75.22
66.84
70.25
62.24
54.38
37.82
37.50
42.30
29.40
99.348
93.78
81.77
-pim
-buim
8.86
C
DOI: 10.1021/acs.inorgchem.6b00136
Inorg. Chem. XXXX, XXX, XXX−XXX

Inorganic Chemistry
Article
gases were listed in Table 2. Among these frameworks, the
isosteric heat values of isolated MOF basically follow the trend:
adsorption capacity is commonly CH < C H < C H < C H
2
4
2
4
2
6
2
<
C H , making the feasibility of these MOFs for the separation
3 8
of light hydrocarbons. Four compounds all display great
separation ratio of C H /CH and C H /CH at 297 K. The
−
1
Table 2. Summary of the Enthalpies (Qst,n=0, kJ mol ) of
Gas Adsorption on Four Compounds
2
4
4
2
6
4
separation ratio value of 1-mim or 1-pim is ∼12, higher than
1-mim
1-eim
1-pim
1-buim
13
14
15
that of ZJU-48a (6), ZIF-8 (10), and Mg-MOF-74 (7) but
CH4
16.15
16.13
15.5
16.58
18.13
19.78
21.12
27.89
19.51
14.62
15.15
19.00
22.76
28.41
22.04
14.99
17.55
20.94
22.95
27.97
21.17
15
lower than that of Fe-MOF-74 (18). Noteworthily, the
C H
2
2
4
6
8
selectivity of C H /CH for each compound reported here is
C H
2
3
8
4
C H
2
19.51
21.39
18.08
over 100 at room temperature, much higher than those of
1
6
17
C H
3
UTSA-35a (80) and JLU-Liu18 (108.2). Such high
selectivities reveal that these compounds have the great
potential on separation of light hydrocarbons.
CO2
C H > C H > C H > C H > CH . The increasing isosteric
3
8
2
6
2
4
2
2
4
10
heats are proportional to the polarity of gas molecules.
CONCLUSION
■
Moreover, it also can be attributed to the confined pore space
In summary, we designed a family of pillared−layer frameworks
generated by the substituded alkyl groups of the pore, which
11
enhance the gas affinity of porous materials. However, no
linear relationship of isosteric heats can be found among these
compounds.
with Zn (NH −BTB) layers and different imidazole pillars. 1-
2 2
ims exhibit exceptionally high hydrocarbon uptake and show
good adsorption selectivity of C /C and C /C . Especially, the
3
2
2
1
The adsorption selectivities of C /C and C /C (equimolar
3
1
2
1
selectivities of C H /CH for 1-ims are over 100 at room
3
8
4
binary mixtures) were calculated by the ideal adsorption
12
temperature. These results reveal a fine-tuning approach for the
precise design and application of porous MOFs.
solution theory (IAST) at 273 and 297 K (Figure 6 and
Figure S12). The IAST calculations show that the hierarchy of
Figure 6. IAST-predicted adsorption selectivity of C /C , C /C , and CO /CH on 1-ims at 297 K (C /C and C /C equimolar binary mixtures).
3
1
2
1
2
4
3
1
2
1
(
a) 1-mim; (b) 1-eim; (c) 1-pim; (d) 1-buim.
D
DOI: 10.1021/acs.inorgchem.6b00136
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Inorganic Chemistry
Article
M.; van der Voort, P. J. Phys. Chem. C 2013, 117, 22784−22796.
ASSOCIATED CONTENT
Supporting Information
The Supporting Information is available free of charge on the
ACS Publications website at DOI: 10.1021/acs.inorg-
chem.6b00136.
■
(d) Devic, T.; Horcajada, P.; Serre, C.; Salles, F.; Maurin, G.; Moulin,
*
S
B.; Heurtaux, D.; Clet, G.; Vimont, A.; Grenec
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Daturi, M.; Ferey, G. J. Am. Chem. Soc. 2010, 132, 1127−1136.
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8) Wang, X. S.; Chrzanowski, M.; Gao, W. Y.; Wojtas, L.; Chen, Y.
̀
he, J. M.; Ouay, B. L.;
́
(
Additional figures, TGA, powder X-ray diffraction
patterns, adsorption isotherms. (PDF)
X-ray crystallographic information (CCDC Nos.
(
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1440818−1440821). (CIF)
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AUTHOR INFORMATION
Corresponding Author
E-mail: zhj@fjirsm.ac.cn.
■
*
1
2
(
630−1635. (b) Li, J. R.; Kuppler, R. J.; Zhou, H. C. Chem. Soc. Rev.
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The authors declare no competing financial interest.
2
(
ACKNOWLEDGMENTS
This work is supported by 973 program (2012CB821705), and
NSFC (21425102, 21521061).
■
1209−1212.
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DOI: 10.1021/acs.inorgchem.6b00136
Inorg. Chem. XXXX, XXX, XXX−XXX