A New Microporous Metal-Organic Framework for Highly Selective C2H2/CH4 and C2H2/CO2 Separation at Room Temperature

Article abstract of DOI:10.1002/cjoc.201700040

We have successfully designed and synthesized a new tetracarboxylic linker, which constructed its first three-dimensional microporous metal-organic framework (MOF), [Cu₂(DDPD)(H₂O)₂]?Gx (ZJU-13, H₄DDPD=5,5'-(2,6-dihydroxynaphthalene-1,5-diyl)diisophthalic acid, ZJU=Zhejiang University, G = guest molecules) via solvothermal reaction. Due to open Cu²⁺ sites and optimized pore size, the activated ZJU-13a displays high separation selectivity for C₂H₂/CH₄ of 74 and C₂H₂/CO₂ of 12.5 at low pressure by using Ideal Adsorbed Solution Theory (IAST) simulation at room temperature.

Full text of DOI:10.1002/cjoc.201700040

FULL PAPER
DOI: 10.1002/cjoc.201700040
A New Microporous Metal-Organic Framework for Highly
Selective C2H2/CH4 and C2H2/CO2 Separation
at Room Temperature
Xing Duan,*,a Tifeng Xia,b Zhenguo Ji,a Yuanjing Cui,b Yu Yang,b and Guodong Qian*,b
a College of Materials & Environmental Engineering, Hangzhou Dianzi University, Hangzhou,
Zhejiang 310027, China
b State Key Laboratory of Silicon Materials, Cyrus Tang Center for Sensor Materials and Applications,
School of Materials Science & Engineering, Zhejiang University, Hangzhou, Zhejiang 310027, China
We have successfully designed and synthesized a new tetracarboxylic linker, which constructed its first
three-dimensional microporous metal-organic framework (MOF), [Cu2(DDPD)(H2O)2]•Gx (ZJU-13, H4DDPD＝
5,5'-(2,6-dihydroxynaphthalene-1,5-diyl)diisophthalic acid, ZJU＝Zhejiang University, G＝guest molecules) via
＋
solvothermal reaction. Due to open Cu2 sites and optimized pore size, the activated ZJU-13a displays high sepa-
ration selectivity for C2H2/CH4 of 74 and C2H2/CO2 of 12.5 at low pressure by using Ideal Adsorbed Solution
Theory (IAST) simulation at room temperature.
Keywords metal-organic frameworks, micro-porous materials, selective separation, open metal sites, opti-
mizedpore size
Introduction
Metal organic frameworks (MOFs), as a novel fami-
ly of inorgainc-organic hybrid porous materials, have
exhibited excellent potential in the application of gas
storage and separation.[10-42] MOFs constituted from
metal ions/clusters and organic bridging linkers are a
kind of crystalline porous materials with periodic infi-
nite network structure. Due to their inherent characteris-
tics, MOFs have many advantages compared to conven-
tional porous materials: (1) the synthesis of MOFs is
mostly by a one-step method which is simple and facile;
(2) the shape and size of channel/pore/cage can be con-
trolled for the requirement of practical application by
choosing appropriate metal ions/secondary building
units (SBUs) or organic linkers, to achieve better effect
of gas screening and storage; (3) the surface of chan-
nel/pore/cage can be decorated by synthesis or post-
synthesis, such as immobilizing open metal sites (OMSs)
and/or organic-functional groups (NH2, OH, SO3H,
COOH), to reach the purpose of selective recognition
of different guest molecules.[25-48] Zaworotko and
co-workers[43,44] reported two MOFs materials with dif-
ferent pore size, SIFSIX-2-Cu (13.05×13.05 Å2) and
SIFSIX-2-Cu-I (5.15×5.15 Å2). IAST (Ideal Adsorbed
Solution Theory) simulation and breakthrough tests ex-
hibited the selectivity of SIFSIX-2-Cu-I for CO2/CH4
and CO2/N2 to be 7－10 times higher than that of
SIFSIX-2-Cu. Chen and co-workers[45] decorated OH
Acetylene is one of greatly important raw materials
in the field of petrochemical and industry, for example,
high-purity acetylene flame is often used for cutting and
welding of metal materials. Obtaining high purity of
acetylene is the precondition of making effective use of
this hydrocarbon. Therefore, the separation and purifi-
cation of acetylene are the extremely essential process
in the industry.[1-7] The traditional cryogenic distillation
method has been extensively applied to separate acety-
lene from other gas molecules, for example carbon di-
oxide and methane. Whereas due to the similarity of
molecule dimensional size, kinetic diameter and volatil-
ity for C2H2, CO2, and CH4, such separation process is
rather energy-consuming and ineffective. So, the design
and exploitation of economic efficient separation meth-
ods are the pursuing goal for numerous researchers.
Taking advantage of high surface area of the adsorbent
for cost- and energy-effective separation of acetylene is
considered to be one of the promising separation tech-
nology.[8,9] Some conventional porous carbon materials
and molecular sieve have been utilized in the separation
of acetylene, but their pore space cannot be effectively
controlled, the separation performance is not ideal. So,
it is necessary to seek the porous materials with high
separation selectivity for acetylene.
*
E-mail: star19871127@hdu.edu.cn
Received January 12, 2017; accepted March 30, 2017; published online XXXX, 2017.
Supporting information for this article is available on the WWW under http://dx.doi.org/10.1002/cjoc.201700040 or from the author.
Chin. J. Chem. 2017, XX, 1—5
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Duan et al.
FULL PAPER
groups on the pore surfaces of MOFs to obtain their
high separation selectivity of C2H2/CH4 and CO2/CH4 at
room temperature. It is an effective method to promote
gas separation selectivity by utilizing both the immobi-
lized functional sites within pore surface of MOFs and
size-exclusive effects. MOFs comprised of tetracarbox-
ylic acid linkers and Cu2+ paddle-wheel cluster
(Cu2(COO)4) with NbO-type topology are considered to
be one of the most competitive porous materials because
of their high gas storage and selective separation per-
formance. Herein, we introduced dihydroxynaphthalene
into ligand to develop a new tetracarboxylic organic
linker H4DDPD (H4DDPD＝5,5'-(2,6-dihydroxynaph-
thalene-1,5-diyl)diisophthalic acid, Scheme 1) and its
first 3D microporous MOF, [Cu2(DDPD)(H2O)2]•Gx
(ZJU-13, H4DDPD ＝ 5,5'-(2,6-dihydroxynaphthalene-
(65%, aq.) was added. The vial was capped and placed
in a precise oven at 80 ℃ for 3 d. The resulting blue
rhombic shaped crystals were washed with DMF to af-
ford ZJU-13. Elemental analysis: calcd for [Cu2-
(C26H12O10)(H2O)2]•(DMF)5•(H2O)2(C41H55Cu2N5O19,
%): C 46.9, H 5.30, N 6.68; found C 46.8, H 5.423, N
6.79.
Gas sorption measurements
A Micromeritics ASAP 2020 surface area analyzer
was used to measure the BET surface and gas sorption
isotherms of C2H2, CO2 and CH4. Prior to the measure-
ment, to have the guest-free framework, the fresh
as-synthesized sample was washed with DMF several
times, then guest-exchanged with anhydrous acetone at
least 10 times, then filtered. Afterwards, the sample was
vacuumed at 273 K for 24 h and at 298 K for 12 h and
then at 353 K until the outgas rate was 5 μmHg•min1.
An activated sample of ZJU-13 (100 mg) was used for
the gas adsorption measurements. The N2 adsorption
measurement was kept at 77 K with liquid nitrogen. The
C2H2, CO2 and CH4 adsorption measurements were
performed at 273 K with an ice-water bath and at 298 K
with a water bath.
1,5-diyl) diisophthalic acid, ZJU＝Zhejiang University,
＋
G＝guest molecules). With open Cu2 sites and opti-
mized pore size, ZJU-13a exhibited high separation
selectivity of 74 and 12.5 for C2H2/CH4 and C2H2/CO2
at room temperature, respectively.
Scheme 1 The organic linker H4DDPD for the construction of
ZJU-13
Results and Discussion
1,5-Dibromo-2,6-dimethoxynaphthalene was ob-
tained via Williamson etherification and addition reac-
tion. Dimethyl (5-pinacolboryl)isophthalate was synthe-
sized by substitution reaction using Pd(dppf)2Cl2 as cat-
alyst and KOAc as bases at 65 ℃. 1,5-Dibromo-2,6-di-
methoxynaphthalene and dimethyl (5-pinacolboryl) iso-
phthalate yielded tetramethyl 5,5'-(2,6-dimethoxynaph-
thalene-1,5-diyl)diisophthalate via Suzuki cross-cou-
pling reaction taking advantage of the Pd(PPh3)4-cata-
lysis, then demethylation, hydrolysis and acidification
reaction to give 5,5'-(2,6-dihydroxynaphthalene-1,5-diyl)
diisophthalic acid (H4DDPD) (Scheme S1). All chemi-
cal structures of above-mentioned reaction products
were confirmed by the 1H NMR spectra.
A single blue rhombic shaped crystal of ZJU-13 was
obtained by the solvothermal reaction of H4DDPD and
Cu(NO3)2•2.5H2O in a mixture solvent of DMF/EtOH/
H2O with the addition of a small amount of HNO3 at
80 ℃ for 72 h. The crystal structure was determined by
the single-crystal X-ray diffraction (SCXRD) analysis
which exhibited ZJU-13 crystallizes in the trigonal
space group R-3m. Crystallographic data, data collection
parameters, and refinement are summarized in Table S1.
As shown in the Figure 1a, ZJU-13 reveals two types of
cage along the c axis of about 7.2 Å and 6×20 Å2 in
diameter with －OH functional groups pointing to the
cages of the framework, taking into account the van der
Waals radii. The sizes of window openings are about 3
Å along c axis and 2 Å and 2.8×5.6 Å2 along a, b axis
(Figures 1b and 1c). Due to the introduction of the
naphthalene and －OH functional groups, the sizes of
Experimental
Materials and methods
All solvents and reagents were obtained from com-
mercial sources, and were used without further purifica-
1
tion. H NMR spectra were collected on a Bruker Ad-
vance DMX 500 MHz spectrometer in CDCl3 and
DMSO solution using tetramethylsilane (TMS, δ 0) as
an internal standard at room temperature. The X-ray
powder diffraction (PXRD) experiment was carried out
on a PANalyticalX’Pert Pro X-ray diffractometer with
Cu-Kα (λ＝1.542 Å) at room temperature and the data
were collected in the 2θ＝3°－50° range. Thermograv-
imetric analyses (TGA) were recorded on a Netszch
TGA 209 F3 thermogravimeter under N2 atmosphere
heated from room temperature to 900 ℃ at the heating
rate of 5 K•min1. Elemental analyses (C, H, and N)
were performed on an EA1112 micro elemental analyz-
er.
Synthesis of ZJU-13
In a 20 mL glass vial, the organic linker H4DDPD
(10 mg, 0.0204 mmol) was dissolved in 7.5 mL of
N,N-dimethyl formamide (DMF) and 2.5 mL of ethanol.
Then Cu(NO3)2•2.5H2O (20 mg, 0.086 mmol) and 5 mL
of H2O were added into the vial, then 250 µL of HNO3
2
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Chin. J. Chem. 2017, XX, 1—5

Metal-Organic Framework for C2H2/CH4 and C2H2/CO2 Separation
＋
open Cu2 sites encourage us to study its potential ap-
the cages and window openings are smaller than those
of NOTT-101. The phase purity of bulk crystal material
is confirmed by the good agreement with PXRD
(powder X-ray diffraction) of as-synthesized crystal
material and simulated one (Figure S1). TGA
(thermogravimetric analysis) exhibits a weight loss of
39.1% from room temperature to 250 ℃, corresponding
to the solvent molecules (five DMF and two H2O
molecules) and two coordinated water molecules
(Figure S2). The void volume of ZJU-13 is 64.7%
(7752 Å3 out of 11965 Å3) by the PLATON software.[49]
plication to selective gas separation. As shown in Figure
3, all of the adsorption isotherms are reversible.
ZJU-13a can take up C2H2 of 153 cm3•g1 at 273 K and
115 cm3•g1 at 298 K, which is further higher than that
of CO2 (122 cm3•g1 at 273 K and 70 cm3•g1 at 298 K)
and CH4 (31 cm3•g1 at 273 K and 20 cm3•g1 at 298 K).
The uptake amount of C2H2 at room temperature in
ZJU-13a is higher than those of some well-known
MOFs such as ZJU-26a (84 cm3•g1),[29] UTSA-50 (91
cm3•g1),[4] MOF-5 (26 cm3•g1),[27] UTSA-33a (84
cm3•g1),[50] Cu2(NDC)2(DABCO) (97 cm3•g1),[51] and
Zn2(NDC)2(DABCO) (106 cm3•g1),[51] which is
＋
attributed to the open Cu2 sites and optimized pore
sizes resulting in the efficient sorption of acetylene
molecules in ZJU-13a micropores.
160
140
120
100
80
273 K
C2H2
CO2
Figure 1 X-ray single crystal structure of ZJU-13, indicating (a)
two types of cage along the c axes of about 7.2 Å and 6×20 Å2
in diameter; (b) the structure viewed along the a axes indicating
the window openings of about 2 Å and 2.6×5.8 Å2, respectively;
(c) the structure viewed along the c axes showing the window
openings of about 3 Å.
.
60
40
20
CH4
800
0
The fresh as-synthesized sample of ZJU-13 was
washed with DMF and guest-exchanged with
dry-acetone and vacuumed at 80 ℃ for 2 h to obtain
the activated ZJU-13a. The N2 sorption-desorption
0
200
400
600
Absolute pressure/mmHg
298 K
isotherm at 77
K
was measured by utilizing
120
Micromeritics ASAP 2020 surface area analyzer. The
result shows that ZJU-13a displays a typical reversible
Type-I sorption behavior with the saturation uptake of
277.1 cm3•g1 (Figure 2). The Brunauer-Emmett-Teller
(BET) and Langmuir surface areas are 1056 m2•g1 and
1075 m2•g1 by BET equation and Langmuir equation
calculation, respectively (Figure S3). ZJU-13a has a
pore volume of 0.427 cm3•g1.
C2H2
CO2
100
80
60
40
20
0
.
CH4
The permanent porosity, optimized pore size and
0
200
400
600
800
300
250
Absolute pressure/mmHg
Figure 3 C2H2 (black), CO2 (red) and CH4 (blue) adsorption
isotherms of ZJU-13a at 273 K and 298 K. Solid symbols: ad-
sorption, open symbols: desorption.
.
200
150
100
50
The adsorption enthalpies of ZJU-13a for C2H2,
CO2, and CH4 are calculated by the virial expression.
The adsorption data were fitted by the following equa-
tion:
m
n
0
1


0.0
0.2
0.4
0.6
0.8
1.0
ln p  ln N 
 
ai  Ni  bj  N j
(1)






T
 i0
j0
Pressure (p/p0)
Figure 2 N2 sorption isotherm at 77 K for ZJU-13a.
The isosteric heat of adsorption, Qst, is defined as
Chin. J. Chem. 2017, XX, 1—5
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www.cjc.wiley-vch.de
3

Duan et al.
FULL PAPER
follows:
180
160
140
120
100
80
m
273 K
298 K
C2H2/CH4 = 50:50
Qst  R ai Ni
(2)

i0
where N is the adsorption capacity of adsorbate, p is the
pressure, R is the Planck constant of 8.314 mol1•K1, T
is the temperature, ai, bj are the virial coefficients.
The isosteric heats of adsorption for C2H2, CO2, and
CH4 49.7 kJ•mol1, 33 kJ•mol1, and 20 kJ•mol1, re-
spectively (Figure 4). The adsorption enthalpy for C2H2
(49.7 kJ•mol1) in ZJU-13a is far greater than those of
most MOFs materials and is comparable to those of
60
40
20
0
0
20
40
60
80
100
120
MMOF-74 (M＝Fe, Mg, Co) and UTSA-60 with open
＋
metal sites,[52] which further indicates the open Cu2
Pressure/kPa
sites and optimized pore size can improve the affinity
between framework and acetylene molecules.
18
16
14
12
10
8
C2H2/CO2 = 50:50
273 K
298 K
6
4
2
0
0
20
40
60
80
100
120
Pressure/kPa
Figure 5 The adsorption selectivities predicted by IAST of
ZJU-13a for C2H2/CH4 and C2H2/CO2 at 273 K and 298 K, re-
spectively.
Figure 4 The isosteric heats of adsorption with error bars of
C2H2, CO2 and CH4 on ZJU-13a.
separation in the near future.
Such large differences of adsorption capacities and
adsorption enthalpies for C2H2, CO2, and CH4 enable us
to calculate the separation selectivity for C2H2/CH4 and
C2H2/CO2 by using Ideal Adsorbed Solution Theory
(IAST). The mixture adsorption isotherms and separa-
tion selectivity at different temperature and pressures for
C2H2/CH4 (50∶50) and C2H2/CO2 (50∶50) are shown
in Figure 5 and Figure S4. The IAST calculation dis-
plays that the separation selectivities of C2H2/CH4 are
estimated to be 170 and 74 at 1 kPa at 273 K and 298 K
and then rapidly dropdown to 68－80 and 20－25, re-
spectively, which are higher than those of MFM-202a[38]
and the crystal without －OH residues (Figure S5). To
the best of our knowledge, the C2H2/CH4 separation
selectivity at room temperature is one of the highest of
reported MOFs materials at present.[6,29,36,38,50,53-56] The
separation selectivities of ZJU-13a are calculated to be
17 and 12.5 for C2H2/CO2 at very low pressure at 273 K
and 298 K, then both reduce to 4－5. Such good separa-
tion selectivities for C2H2/CH4 and C2H2/CO2 indicate
open metal sites and optimized pore size can improve
the interaction with the framework and the acetylene
molecules. This work demonstrats ZJU-13a is a pro-
spective microporous MOF material for selective gas
Conclusions
In conclusion, we have successfully prepared a novel
microporous MOF Cu2DDPD (ZJU-13a) with
＋
optimized pore sizes and open Cu2
sites. These
features enable the activated ZJU-13a to exhibit high
separation selectivity for C2H2/CH4 of 74 and C2H2/CO2
of 12.5 at 1 kPa at room temperature and the values in
the plateau regions are 20－5 and 4－5, respectively. It
is expected that this microporous MOFs material will
have the application potential for selective gas
separation in industry in the future.
Acknowledgement
The authors gratefully acknowledge financial
support from National Natural Science Foundation of
China (Nos. 51602087, 51472217and 51432001) and
Zhejiang Provincial Natural Science Foundation (No.
LZ15E020001).
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