A Thermally and Chemically Stable Copper(II) Metal-Organic Framework with High Performance for Gas Adsorption and Separation

Article abstract of DOI:10.1021/acs.inorgchem.1c00357

A versatile microporous metal-organic framework (MOF), {[Cu(TIA)]·1.5CH3OH}n (Cu-1), was successfully obtained via the solvothermal reaction of cuprous(II) salt with the bifunctional ligand 3-(1H-1,2,4-triazol-1-yl)isophthalic acid. Single-crystal X-ray diffraction studies indicate that Cu-1 contains an apo three-dimensional skeleton and two types of one-dimensional channels. The framework of Cu-1 has excellent acid-alkali resistance and thermal stability, which is stable in a pH = 2-13 aqueous solution and an 260 °C air environment. In addition, the microporous copper MOF shows very high uptakes of CO2 (180 cm3·g-1) and C2H2 (113 cm3·g-1) at 273 K and displays excellent adsorption selectivity for small molecular gases. The ideal adsorbed solution theory selectivity values for C2H2/C2H4, CO2/CH4, and CO2/N2 are 2, 9, and 22 at 298 K, respectively. At the same time, breakthrough experiments for CO2/CH4, CO2/N2, and C2H2/C2H4 were further conducted to verify the efficient separation performances.

Full text of DOI:10.1021/acs.inorgchem.1c00357

pubs.acs.org/IC
Article
A Thermally and Chemically Stable Copper(II) Metal−Organic
Framework with High Performance for Gas Adsorption and
Separation
Zhi Long Ma, Pu Xu Liu, Zhong Yi Liu, Jia Jun Wang,* Li Bo Li,* and Li Tian*
Cite This: Inorg. Chem. 2021, 60, 6550−6558
Read Online
sı
*
Metrics & More
Article Recommendations
Supporting Information
ACCESS
ABSTRACT: A versatile microporous metal−organic framework (MOF), {[Cu(TIA)]·1.5CH3OH}n (Cu-1), was successfully
obtained via the solvothermal reaction of cuprous(II) salt with the bifunctional ligand 3-(1H-1,2,4-triazol-1-yl)isophthalic acid.
Single-crystal X-ray diffraction studies indicate that Cu-1 contains an apo three-dimensional skeleton and two types of one-
dimensional channels. The framework of Cu-1 has excellent acid-alkali resistance and thermal stability, which is stable in a pH = 2−
13 aqueous solution and an 260 °C air environment. In addition, the microporous copper MOF shows very high uptakes of CO2
(180 cm3·g−1) and C2H2 (113 cm3·g−1) at 273 K and displays excellent adsorption selectivity for small molecular gases. The ideal
adsorbed solution theory selectivity values for C2H2/C2H4, CO2/CH4, and CO2/N2 are 2, 9, and 22 at 298 K, respectively. At the
same time, breakthrough experiments for CO2/CH4, CO2/N2, and C2H2/C2H4 were further conducted to verify the efficient
separation performances.
indicate that the selective capture of CO2 by porous materials
is an environmentally friendly and low-energy-consumption
method. In comparison with inorganic porous materials,
metal−organic frameworks (MOFs) are considered to be
promising materials for CO2 adsorption.4−6
On the other hand, ethylene, as one of the most important
feedstocks, has been widely used in the synthesis of industrial
products such as fibers, rubber, plastics, and so on.7 In
industry, ethylene is usually prepared by cracking petroleum
and oxidative coupling of CH4 in natural gas; accordingly, a
trace amount of acetylene (ca. 1%) as an impurity is mixed
with ethylene.8 A trace amount of acetylene in ethylene can
make the catalyst poisonous in the ethylene polymerization
INTRODUCTION
■
Following the rapid development of industry, the greenhouse
effect caused by carbon dioxide (CO2) emission has become
more and more serious.1 It has been estimated that more than
half of the world’s CO2 emissions is exhausted from power
plants. If the postconsumption CO2 can be directly captured
from the flue gases before emission, the greenhouse effect will
certainly be suppressed. Therefore, it is of utmost important to
capture, store, and transform CO2 economically and
efficiently.2 In addition, natural gas, as an important fossil
fuel, is mainly composed of methane (CH4), which is
considered to be the most promising alternative energy
owing to its high energy conversion efficiency and low
environmental impact. However, the CO2 existence in CH4
is a big problem, which not only sharply decreases the
combustion calorific value but also causes terrible corrosion of
the transmission pipeline, even in a small or trace
concentration.3 Therefore, the removal of CO2 from natural
gas is particularly important for its industrial application value.
The latest developments of separation techniques and methods
Received: February 4, 2021
Published: April 16, 2021
https://doi.org/10.1021/acs.inorgchem.1c00357
© 2021 American Chemical Society
Inorg. Chem. 2021, 60, 6550−6558
6550

Inorganic Chemistry
pubs.acs.org/IC
Article
Figure 1. (a) Linkage of Cu2(COO)4 moieties with a TIA2− ligand in Cu-1. (b) 3D framework of Cu-1 viewed along the 001 direction. (c)
Structural detail of interpenetrating channels with dimensions of 6.9 × 5.7 and 7.9 × 3.8 Å2, respectively, viewed along the [110] direction. (d)
Topology network of the Cu-1 framework.
process by forming metal acetylides; therefore, it is critically
important to deeply purify ethylene and thoroughly remove
acetylene.9,10 However, unsaturated C2 hydrocarbons have
similar physical and chemical properties and make separation
even more difficult. In industry, cryogenic distillation at high
pressure is usually used to separate light hydrocarbons, or
solvent extraction and catalytic hydrogenation are used. These
two methods either need high energy consumption or are
accompanied by environmental pollution.11 Therefore, it is
urgent to find a separation method with high efficiency and low
energy consumption.
MOFs, also known as porous coordination polymers, have
been paid much attention because of their outstanding
capabilities in the areas of gas deposition and segregation,
luminescence, interfacial catalysis, and biomedicine.12−16
Compared with traditional porous materials such as activated
carbon, molecular sieve, etc., the frame structure, pore shape
and size, and functionalities of the MOFs could be regulated at
the molecular level.17−22 These excellent properties have
stimulated considerable research work on exploring their
functions in gas selective adsorption and separation. In the
recent 2 decades, MOFs have exhibited potential applications
in CO2 capture,23−37 light hydrocarbon separation,38−44 and so
on. Because of the special relationship between the structure
and functionalization of MOF materials, MOFs can be
designed and tuned by the suitable adjustment and selection
of bridging linkers and metal units to meet the functional
requirements. However, it is still a challenge to develop the
MOF materials, which not only are able to capture CO2 from
the fuel gases and but also can adsorb a trace amount of
acetylene in ethylene. Because in practical application, the
adsorption materials are required to have excellent adsorption
performance and selectivity and at the same time can tolerate
water and acid gas, which are always mixed in fuel and natural
gases.26,45−48 Chemists found that high-valence conjugated
carboxylic acid ligands can be used to synthesize water-stable
MOFs.49 In addition, metal clusters, such as M2(COO)2 (M =
Cu2+, Zn2+, Co2+, and Ni2+), as secondary building units
(SBUs) can always be formed when organic ligands containing
carboxyl groups are used.50 MOFs containing metal clusters as
SBUs are always accompanied by permanent porosity and
excellent sorption performance.51−54 What is more, on the
basis of the theory of hard−soft acid−base, the MOFs formed
by a combination of the soft base containing an azolate ring
(such as pyrazolates, imidazolates, triazolates, and tetrazolates)
and the bivalent transition soft acid metal ions (such as Cu2+,
Zn2+, Mn2+, and Ni2+) are more stable.49 Bearing this in mind,
a multifunctional ligand, 3-(1H-1,2,4-triazol-1-yl)isophthalic
acid (H2TIA), was selected in our study. As expected, a porous
MOF, namely, {[Cu(TIA)]·1.5CH3OH}n (Cu-1), which
contains the SBU of Cu2(COO)2, was successfully obtained.
Cu-1 not only has exceptional thermal and chemical stability
6551
https://doi.org/10.1021/acs.inorgchem.1c00357
Inorg. Chem. 2021, 60, 6550−6558

Inorganic Chemistry
pubs.acs.org/IC
Article
Figure 2. Stability of Cu-1: (a) PXRD patterns of the MOF Cu-1 after being soaked in different pH aqueous solutions for 48 h; (b) PXRD curves
of the MOF Cu-1 after being heated at different temperatures for 2 h.
Figure 3. (a) N2 sorption isotherms of Cu-1 at 77 K. (b) Pore distribution of Cu-1 based on the density functional theory model.
such as C2H2, C2H4, and C2H6 were measured on a Micromeritics
ASAP 2460 analyzer.
but also has two different sizes of micropores. Further study
found that Cu-1 showed extraordinary adsorption capacities
for CO2 (180 cm3·g−1 at 273 K) and C2H2 (113 cm3·g−1) as
well as good CO2/CH4, CO2/N2, and C2H2/C2H4 gas
selectivity.
RESULTS AND DISCUSSION
■
Crystal Structure Descriptions of Cu-1. Single-crystal X-
ray diffraction analysis revealed that Cu-1 crystallizes in the
orthorhombic Pbcn space group (Table S1), and the free
methanol content of Cu-1 was further determined by the
recognized means of SQUEEZE, elemental analysis, and
thermogravimetry. In Cu-1, each asymmetric unit is composed
of one Cu2+ ion, one TIA2− anion, and one and a half free
methanol molecules. As displayed in Figure 1a, the central
Cu2+ ion existed in a pentacoordinated mode surrounded by
four carboxylic O atoms and one triazole N atom from five
different TIA2− ligands to form a square-pyramidal config-
uration. Four μ2-η1:η1-carboxyl bridges come from four distinct
TIA2− ligands connected two Cu2+ ions to form a binuclear
paddle-wheel [Cu2(COO)4] moiety with a Cu−Cu separation
of 2.668(1) Å (Figure 1a). The CuII−O bond lengths vary
from 1.960(3) to 2.027(4) Å, while the Cu−N bond distance
is 2.129(4) Å (Table S2). In Cu-1, the dihedral angles formed
between the triazolyl ring, the two carboxylate groups, and the
central phenyl ring in the same TIA2− ligand are 19.160(2)°,
28.345(2)°, and 24.920(2)°, respectively. The paddle-wheel
[Cu2(COO)4] moieties are further connected by carboxylate
groups and triazole N atoms from around the TIA2− anions to
form a three-dimensional (3D) framework (Figure 1b), with
approximately rectangle dimensional channels with side
lengths of about 6.9 × 5.7 Å exist along the c direction and
EXPERIMENTAL SECTION
■
Materials. Commercial reactants and solvents were directly used
without any further pretreatment, except that the solvent dimethyl
sulfoxide (DMSO) needs to be tried by 4 Å molecular sieve and
distilled under vacuum conditions. 3-(1H-1,2,4-Triazol-1-yl)-
isophthalic acid (H2TIA) was synthesized based on the method
provided in the literature.55
Preparation of {[Cu(TIA)]·1.5CH3OH}n (Cu-1). H2TIA (11.7 mg,
0.05 mmol), Cu(NO3)2·3H2O (24.2 mg, 0.1 mmol), 4,4′-PBY (7.8
mg, 0.05 mmol), and 5 mL of methanol were added in a 15 mL
reactor in turn, and then the mixture was heated at 120 °C for 4 days.
After that, the autoclave was cooled to room temperature at a rate of
1.5 °C·h−1. Blue rectangular crystals of Cu-1 (10.16 mg) were
obtained (yield 65% based on H2TIA). Elem anal. Calcd for
C11.5H11CuN3O5.5 (342.78): C, 40.29; H, 3.23; N, 12.26. Found: C,
40.66; H, 3.05; N, 12.32. IR (KBr pellet): 3446 (b), 3389 (b), 3127
(s), 1708 (s), 1627 (m), 1427 (m), 1364 (s), 1207 (w), 1135 (s),
1076 (m), 983 (w), 845 (w), 664 (m), 539 (s) cm−1.
Activation of Cu-1 and Gas Sorption Measurements. The
synthesized sample of Cu-1 was activated at 70 °C for 10 h in vacuum
conditions. N2 sorption isotherms were obtained from 0 to 1 bar at 77
K with liquid nitrogen by a volumetric method on a Micromeritics
ASAP 2020HD88 surface area and pore analyzer. The low-pressure
gas sorption data of CH4, CO2, and N2 were carried out on the same
instruments, whereas the adsorption isotherms of light hydrocarbons
6552
https://doi.org/10.1021/acs.inorgchem.1c00357
Inorg. Chem. 2021, 60, 6550−6558

Inorganic Chemistry
pubs.acs.org/IC
Article
Figure 4. (a) CO2, CH4, and N2 sorption isotherms of Cu-1 at 273 and 298 K. (b) C2H2, C2H4, and C2H6 sorption isotherms of Cu-1 at 273 and
298 K.
irregular channels with an approximate size of 7.9 × 3.8 Å2
along the [110] direction (Figure 1b,c). With the help of
PLATON, the solvent-accessible void space of Cu-1 was
calculated as 53.7%, which was occupied by free methanol
molecules. From the perspective of topology, the TIA2− ligands
can be regarded as 3-connected nodes, and the paddle wheel
can be simplified as 6-connected nodes (Figure 1d). Therefore,
the structure of Cu-1 can be described as a new 3,6-connected
apo framework.
It is worth noting that the channel wall of Cu-1 is modified
by polar triazole rings that can be regarded as active sites,
which can strengthen the interactions between the framework
and the polar gases of small molecules such as CO2 and C2H2.
Thus, the adsorption capacity and selectivity of these gases can
be enhanced.
Stabilities of Cu-1. Powder X-ray diffraction (PXRD) and
thermogravimetric analysis (TGA) experiments were con-
ducted to confirm the stability of the MOF Cu-1. As can be
seen from Figure 2a, the framework of Cu-1 has outstanding
acid−base stability, which can remain invariant in a wide range
of pH = 2−13. In addition, the temperature-dependent PXRD
pattern (Figure 2b) and TGA curve (Figure S2) confirm that
the framework also has excellent thermal stability, which can
withstand high temperature up to 260 °C, and the structure of
Cu-1 starts to collapse when the temperature is above 300 °C.
Therefore, Cu-1 has excellent thermal and chemical stability,
which is the basis for the following adsorption and separation
experiments.
excellent CO2 uptake capacity of 128.77 cm3·g−1 at 298 K and
1 bar, which is higher than the reported recorded value of bio-
MOF-11 (92 cm3·g−1).56 In addition, the CO2 loading at 273
K and 1 bar of Cu-1 is 180.05 cm3·g−1; it also set a very
excellernt value for CO2 adsorption compared with the
reported highest uptake of NOTT-101 (164 cm3·g−1).57,58
The excellent adsorption properties of Cu-1 for CO2 can be
ascribed to its higher surface area, multiple pores, the matching
effect of micropoles, the size of the CO2 molecule, and the
introduction of 1H-triazole rings in H2TIA, which can
strengthen the affinity between the framework and CO2.
Furthermore, Cu-1 exhibits a low adsorption capacity for CH4
(41.37 cm3·g−1 at 273 K and 26.07 cm3·g−1 at 298 K) and N2
(11.46 cm3·g−1 at 273 K and 9.81 cm3·g−1 at 298 K) under the
condition of 1 bar. For the sake of detecting the interaction
between gases and the framework of the MOF Cu-1, the
isoteric heat of adsorption (Qst) of CO2, N2, and CH4 was
obtained based on the adsorption isotherms at 273 and 298 K
with the help of a virial equation. As exhibited in Figure 5, the
Gas Sorption Properties. N2 sorption−desorption
isotherms of the activated Cu-1 were obtained to verify the
permanent porosity. The results are exhibited in Figure 3, a
typical reversible type I isotherm behavior with a breakthrough
uptake at P/P0 < 0.01, explaining the characteristics of the
micropores. At 77 K, the maximum uptake of N2 reached 270
cm3·g−1, and the corresponding Brunauer−Emmett−Teller
(BET) and Langmuir surface areas were calculated as 766 and
1117 m2·g−1, respectively. In addition, it can be seen in Figure
3b that there exist two kinds of pore systems. The large BET
surface areas and various pore sizes inspire us to study the Cu-
1 adsorption performance for small-molecule gases, such as
CO2, N2, CH4, and C2 hydrocarbons (C2H2, C2H4, and C2H6).
The single-component sorption isotherms of CO2, CH4, and
N2 for Cu-1 at 273 and 298 K up to 1 bar (Figure 4) were
collected to explore the abilities for adsorption and separation
for these gases. As presented in Figure 4a, Cu-1 has a very
Figure 5. Qst relationship of CO2, C2H2, C2H4, C2H6, CH4, and N2
adsorption for Cu-1 estimated from virial expression fits at 273 and
298 K.
Qst value of CO2 near zero loading is 27.6 kJ·mol−1; it slowly
rises to 32 kJ·mol−1 following and increase of the adsorption
capacity. For CH4 and N2, the zero-loading Qst values are 16.4
and 16.3 kJ·mol−1, respectively (Figure 5).
It is well-known that the selective adsorption and separation
of light hydrocarbons play a vital role in the development of
petrochemical enterprises. Considering the microporous
characteristics of the MOF Cu-1, single components of C2
hydrocarbons (C2H2, C2H4, and C2H6) were also carried out at
6553
https://doi.org/10.1021/acs.inorgchem.1c00357
Inorg. Chem. 2021, 60, 6550−6558

Inorganic Chemistry
pubs.acs.org/IC
Article
Figure 6. Results of the AIMD simulations, showing the adsorption sites for (a) CO2 and (b) C2H2 in the MOF Cu-1.
Figure 7. IAST selectivities at 298 K: (a) CO2/CH4 and CO2/N2; (b) C2H2/C2H4.
273 and 298 K with pressures from 0 to 1 bar. As shown in
Figure 4b, Cu-1 also displays high adsorption capacities for C2
hydrocarbons, and the corresponding uptakes are 112.88 cm3·
g−1 and 5.04 mmol·g−1 for C2H2, 84.95 cm3·g−1 and 3.79
mmol·g−1 for C2H4, and 79.11 cm3·g−1 and 3.53 mmol·g−1 for
C2H6 at 273 K. The adsorption capacity of Cu-1 at 298 K is
basically similar to that of 273 K, which are 95.68 cm3·g−1 and
4.27 mmol·g−1 for C2H2, 68.06 cm3·g−1 and 3.04 mmol·g−1 for
C2H4, and 57.99 cm3·g−1 and 2.59 mmol·g−1 for C2H6 at 298
K, respectively. The uptake for C2H2 at 298 K is higher than
those of the famous MOFs UTSA-30059 (76.4 cm3·g−1, 3.41
mmol·g−1), SIFSIX-3-Zn10 (86.5 cm3·g−1, 3.86 mmol·g−1), and
NTU-6560 (75.4 cm3·g−1, 3.36 mmol·g−1). Similarly, the
interactions between the gases and MOF materials are also
measured by calculation of the isosteric heat of adsorption
(Qst) at 273 and 298 K; the values of Qst at low coverage are 30
kJ·mol−1 (C2H2), 27.3 kJ·mol−1 (C2H4), and 26.3 kJ·mol−1
(C2H6) (Figure 5).
In order to theoretically explore the excellent adsorption
properties of the complexes for CO2 and acetylene, the
distribution of CO2 and C2H2 molecules in Cu-1 at 300 K
were confirmed by ab initio molecular dynamics (AIMD)
simulations. As exhibited in Figure 6, the reason is that C2H2
and CO2 can have such a strong force with the framework by
C−H···O and C−H···N interactions between guests and hosts.
The O atoms in the CO2 molecule interact with the
microporous channel walls through the strong interaction of
C10−H10···O [H···O, 2.52 Å < 2.72 Å, the sum of van der
Waals radii of the O (1.52 Å) and H (1.20 Å) atoms] and the
weak interaction of C5−H5···O (H···O, 2.82 Å). Similarly, H
atoms in acetylene form strong interactions with O and N
atoms in the micropores through CH···O (2.61 Å) and
CH···N (2.55 Å). Further, the simulated values of Qst for
CO2 and C2H2 are 22.21 and 23.53 kJ·mol−1, respectively. On
the basis of the above calculation results, it is precisely because
the O atoms on polar CO of CO2 and acidic H atom in
acetylene can form stronger interactions with the channel
walls, resulting in better adsorption capacities for CO2 and
C2H2.
Inspired by the extremely high adsorption capacity of Cu-1
for CO2 compared with CH4 or N2, as well as the excellent
uptake of C2H2 toward C2H4, the ideal adsorbed solution
theory (IAST) was used to obtain the selectivity value.
Complex Cu-1 displays a fairly high selectivity value of 22 at
298 K and 1 bar conditions with CO2/N2 mixed in a 15:85
molar ratio, which is higher than those of some reported
MOFs.61−63 In addition, a selectivity product of 9 for CO2/
CH4 at 298 K with the same mole ratio mixtures is achieved
(Figure 7a); the selectivity value for CO2/CH4 (50:50) is
higher than some recently reported MOFs at the same
condition.23,25,36,61−64 For binary mixtures of C2H2/C2H4, the
adsorption selectivity in ratios of 50:50 (v/v) and 1:99 (v/v) at
6554
https://doi.org/10.1021/acs.inorgchem.1c00357
Inorg. Chem. 2021, 60, 6550−6558

Inorganic Chemistry
pubs.acs.org/IC
Article
Figure 8. Simulated breakthrough curves of MOF Cu-1 for separation at 298 K: (a) N2/CO2 (90:10); (b) CH4/CO2 (50:50); (c) C2H4/C2H2
(99:1).
298 K were 2.18 and 2.09, respectively (Figure 7b), which is
better than the famous NOTT-30042 and MOF-7465 systems.
Breakthrough Experiments. In order to detect the
feasibility of the MOF Cu-1 in the actual gas purification
process, dynamic breakthrough experiments were conducted
by different ratios of CO2/N2 (10:90), CO2/CH4 (50:50), and
C2H2/C2H4 (1:99) mixed gases passing through a packed
column containing 744 mg of solid Cu-1 with a flow rate of 2
mL·min−1 at 298 K. The results exhibit that not only can CO2
be effectively separated from the mixed gases of CO2/N2
(10:90) and CO2/CH4 (50:50) but also acetylene can be
effectively separated from a C2H2/C2H4 (1:99) mixture
(Figure 8a−c). For the CO2/N2 (10:90) mixture, it only
takes 253 s for nitrogen to pass through the fixed bed, whereas
the elution of CO2 gas needs 33 min. For a CO2/CH4 (50:50)
mixed gas, CH4 gas needs 600 s to break through the fixed bed,
but CO2 gas takes an additional 39 min. The breakthrough
experiments further verified the feasibility that the MOF Cu-1
can serve as an adsorbent in the purification of natural gas and
selectively capturing CO2 from fuel gas in industry. In addition,
the same test of the MOF Cu-1 to C2H2/C2H4 (1:99) mixture
shows that pure ethylene was first detected from the outflow
gas, and acetylene was not detected at this period of time. After
20 min, the acetylene adsorption capacity reached saturation
and broke through the adsorbent (Figure 8c). The results
confirm that the MOF Cu-1 can also be used in the deep
purification of ethylene in industrial production.
CONCLUSIONS
■
In summary, a versatile microporous MOF Cu-1 was
successfully obtained based on the bifunctional ligand
H2TIA, which not only has excellent acid-alkali resistance
and thermal stability but also possesses polar micropores,
which can match CO2 and C2H2 molecules very well. The
microporous MOF shows very high uptakes of CO2 and C2H2.
In addition, it displays good CO2/CH4, CO2/N2, and C2H2/
C2H4 selectivity, which was also confirmed by breakthrough
experiments. The high adsorption capacity for CO2 and high
selectivities of CO2/CH4 and CO2/N2 make it a possible ideal
substitute for capturing postconsumption CO2 and purifying of
natural gas. What is more, the excellent uptake for C2H2 and
the corresponding breakthrough experiment suggest its
application prospect in the deep purification of ethylene in
petrochemical enterprises.
ASSOCIATED CONTENT
■
sı
* Supporting Information
The Supporting Information is available free of charge at
https://pubs.acs.org/doi/10.1021/acs.inorgchem.1c00357.
6555
https://doi.org/10.1021/acs.inorgchem.1c00357
Inorg. Chem. 2021, 60, 6550−6558

Inorganic Chemistry
Computational methods, physical measurements, syn-
pubs.acs.org/IC
Article
(4) Sumida, K.; Rogow, D. L.; Mason, J. A.; McDonald, T. M.;
Bloch, E. D.; Herm, Z. R.; Bae, T.-H.; Long, J. R. Carbon dioxide
capture in metal-organic frameworks. Chem. Rev. 2012, 112, 724−781.
(5) Xiang, S.; He, Y.; Zhang, Z.; Wu, H.; Zhou, W.; Krishna, R.;
Chen, B. Microporous metal-organic framework with potential for
carbon dioxide capture at ambient conditions. Nat. Commun. 2012, 3,
954.
thesis of H2TIA, crystallographic data, PXRD, TGA,
other sorption properties, and calculation of Qst (PDF)
Accession Codes
CCDC 2060840 contains the supplementary crystallographic
data for this paper. These data can be obtained free of charge
via www.ccdc.cam.ac.uk/data_request/cif, or by emailing
data_request@ccdc.cam.ac.uk, or by contacting The Cam-
bridge Crystallographic Data Centre, 12 Union Road,
Cambridge CB2 1EZ, UK; fax: +44 1223 336033.
(6) Zhang, Z. J.; Yao, Z. Z.; Xiang, S. C.; Chen, B. L. Perspective of
microporous metal-organic frameworks for CO2 capture and
separation. Energy Environ. Sci. 2014, 7, 2868−2899.
(7) Sundaram, K. M.; Shreehan, M. M.; Olszewski, E. F. Kirk−
Othmer Encyclopedia of Chemical Technology, 4th ed.; Wiley, 1995; pp
877−915.
AUTHOR INFORMATION
Corresponding Authors
■
(8) Ren, T.; Patel, M. K.; Blok, K. Steam Cracking and Methane to
Olefins: Energy Use, CO2 Emissions and Production Costs. Energy
2008, 33, 817−833.
Jia Jun Wang − Tianjin Key Laboratory of Structure and
Performance for Functional Molecules, College of Chemistry,
Tianjin Normal University, Tianjin 300387, P. R. China;
Email: hxxywjj@tjnu.edu.cn
(9) Li, J.; Jiang, L.; Chen, S.; Kirchon, A.; Li, B.; Li, Y.; Zhou, H. C.
Metal-organic framework containing planar metal-binding sites:
efficiently and cost-effectively enhancing the kinetic separation of
C2H2/C2H4. J. Am. Chem. Soc. 2019, 141, 3807−3811.
(10) Cui, X.; Chen, K.; Xing, H.; Yang, Q.; Krishna, R.; Bao, Z.; Wu,
H.; Zhou, W.; Dong, X.; Han, Y.; Li, B.; Ren, Q.; Zaworotko, M. J.;
Chen, B. Pore chemistry and size control in hybrid porous materials
for acetylene capture from ethylene. Science 2016, 353, 141−144.
(11) Sholl, D. S.; Lively, R. P. Seven chemical separations to change
the world. Nature 2016, 532, 435−437.
Li Bo Li − College of Chemistry and Chemical Engineering,
Shanxi Key Laboratory of Gas Energy Efficient and Clean
Utilization, Taiyuan University of Technology, Taiyuan
030024, Shanxi, China; orcid.org/0000-0001-7147-
9838; Email: lilibo908@hotmail.com
Li Tian − Tianjin Key Laboratory of Structure and
Performance for Functional Molecules, College of Chemistry,
Tianjin Normal University, Tianjin 300387, P. R. China;
orcid.org/0000-0003-1121-8331; Email: lilytianli@
hotmail.com
(12) Li, L. B.; Lin, R. B.; Krishna, R.; Li, H.; Xiang, S. C.; Wu, H.; Li,
J. P.; Zhou, W.; Chen, B. L. Ethane/ethylene separation in a metal-
organic framework with iron-peroxo sites. Science 2018, 362, 443−
446.
(13) Lan, T. H.; Li, L. B.; Chen, Y.; Wang, X. Q.; Yang, J. F.; Li, J. P.
Opportunities and critical factors of porous metal-organic frameworks
for industrial light olefins separation. Mater. Chem. Front. 2020, 4,
1954−1984.
(14) Cui, W. G.; Zhang, G. Y.; Hu, T. L.; Bu, X. H. Metal-organic
framework-based heterogeneous catalysts for the conversion of C1
chemistry: CO, CO2 and CH4. Coord. Chem. Rev. 2019, 387, 79−120.
(15) Wang, T.; Lin, E.; Peng, Y. L.; Chen, Y.; Cheng, P.; Zhang, Z. J.
Rational design and synthesis of ultramicroporous metal-organic
frameworks for gas separation. Coord. Chem. Rev. 2020, 423, 213485.
(16) Cui, W. G.; Hu, T. L.; Bu, X. H. Metal-organic framework
materials for the separation and purification of light hydrocarbons.
Adv. Mater. 2020, 32, 1806445.
Authors
Zhi Long Ma − Tianjin Key Laboratory of Structure and
Performance for Functional Molecules, College of Chemistry,
Tianjin Normal University, Tianjin 300387, P. R. China
Pu Xu Liu − College of Chemistry and Chemical Engineering,
Shanxi Key Laboratory of Gas Energy Efficient and Clean
Utilization, Taiyuan University of Technology, Taiyuan
030024, Shanxi, China
Zhong Yi Liu − Tianjin Key Laboratory of Structure and
Performance for Functional Molecules, College of Chemistry,
Tianjin Normal University, Tianjin 300387, P. R. China
Complete contact information is available at:
https://pubs.acs.org/10.1021/acs.inorgchem.1c00357
(17) Liao, P. Q.; Huang, N. Y.; Zhang, W. X.; Zhang, J. P.; Chen, X.
M. Controlling Guest Conformation for Efficient Purification of
Butadiene. Science 2017, 356, 1193−1196.
(18) Zhao, J. P.; Xu, J.; Han, S. D.; Wang, Q. L.; Bu, X. H. A
Niccolite Structural Multiferroic Metal-Organic Framework Possess-
ing Four Different Types of Bistability in Response to Dielectric and
Magnetic Modulation. Adv. Mater. 2017, 29, 1606966.
(19) Adil, K.; Belmabkhout, Y.; Pillai, R. S.; Cadiau, A.; Bhatt, P. M.;
Assen, A. H.; Maurin, G.; Eddaoudi, M. Gas/vapour Separation Using
Ultra-Microporous Metal-Organic Frameworks: Insights into the
Structure/Separation Relationship. Chem. Soc. Rev. 2017, 46, 3402−
3430.
Notes
The authors declare no competing financial interest.
ACKNOWLEDGMENTS
■
This work was financially supported by the National Natural
Science Foundation of China (Grants 21371133 and
21922810) and the Science & Technology Development
Fund of Tianjin Education Commission for Higher Education
(Grant 2020KJ008).
(20) Reed, D. A.; Keitz, B. K.; Oktawiec, J.; Mason, J. A.; Runcevski,
T.; Xiao, D. J.; Darago, L. E.; Crocella, V.; Bordiga, S.; Long, J. R. A
spin transition mechanism for cooperative adsorption in metal-organic
frameworks. Nature 2017, 550, 96−100.
(21) Li, B.; Wen, H.-M.; Cui, Y. J.; Zhou, W.; Qian, G. D.; Chen, B.
L. Emerging multifunctional metal-organic framework materials. Adv.
Mater. 2016, 28, 8819−8860.
(22) Lian, X. Z.; Fang, Y.; Joseph, E.; Wang, Q.; Li, J. L.; Banerjee,
S.; Lollar, C.; Wang, X.; Zhou, H.-C. Enzyme-MOF (metal-organic
framework) composites. Chem. Soc. Rev. 2017, 46, 3386−3401.
(23) Zhang, D. S.; Zhang, Y. Z.; Zhang, X.; Wang, F.; Zhang, J.; Hu,
H.; Gao, J.; Yan, H.; Liu, H. L.; Ma, H. Y.; Geng, L. L.; Li, Y. W.
Nanocage-Based Porous Metal-Organic Frameworks Constructed
REFERENCES
■
(1) Ding, M.; Flaig, R. W.; Jiang, H.-L.; Yaghi, O. M. Carbon capture
and conversion using metal-organic frameworks and MOF-based
materials. Chem. Soc. Rev. 2019, 48, 2783−2828.
(2) Lee, C. K.; Liu, S. S.; Juang, L. C.; Wang, C. C.; Lin, K. S.; Lyu,
M. D. Application of titanate nanotubes for dyes adsorptive removal
from aqueous solution. J. Hazard. Mater. 2007, 147, 997−1005.
(3) Yousef, A. M.; El-Maghlany, W. M.; Eldrainy, Y. A.; Attia, A.
Low-temperature distillation process for CO2/CH4 separation: a
study for avoiding CO2 freeze-out. J. Heat Transfer 2018, 140,
042001.
6556
https://doi.org/10.1021/acs.inorgchem.1c00357
Inorg. Chem. 2021, 60, 6550−6558

Inorganic Chemistry
pubs.acs.org/IC
Article
from Icosahedrons and Tetrahedrons for Selective Gas Adsorption.
ACS Appl. Mater. Interfaces 2019, 11, 20104−20109.
Isostructural Mixed-Metal Organic Frameworks (M’MOFs) for Their
Highly Selective Separation of Chiral and Achiral Small Molecules. J.
Am. Chem. Soc. 2012, 134, 8703−8710.
(40) Hu, T. L.; Wang, H.; Li, B.; Krishna, R.; Wu, H.; Zhou, W.;
Zhao, Y.; Han, Y.; Wang, X.; Zhu, W.; Yao, Z.; Xiang, S.; Chen, B.
Microporous Metal-Organic Framework with Dual Functionalities for
Highly Efficient Removal of Acetylene from Ethylene/Acetylene
Mixtures. Nat. Commun. 2015, 6, 7328−7335.
(41) Li, B.; Cui, X.; O’Nolan, D.; Wen, H.-M.; Jiang, M.; Krishna,
R.; Wu, H.; Lin, R.-B.; Chen, Y.-S.; Yuan, D.; Xing, H.; Zhou, W.;
Ren, Q.; Qian, G.; Zaworotko, M. J.; Chen, B. An Ideal Molecular
Sieve for Acetylene Removal from Ethylene with Record Selectivity
and Productivity. Adv. Mater. 2017, 29, 1704210.
(42) Yang, S.; Manuel, A.; Callear, S. K.; Campbell, S. I.; Tang, C.
C.; Schröder, M.; Ramirez-Cuesta, A. J.; Newby, R.; Garcia-Sakai, V.
Supramolecular Binding and Separation of Hydrocarbons within a
Functionalized Porous Metal-Organic Framework. Nat. Chem. 2015,
7, 121−129.
(43) Jin, G. X.; Niu, X.; Wang, J.; Ma, J. P.; Hu, T. L.; Dong, Y. B.
APPT-Cd MOF: Acetylene Adsorption Mechanism and Its Highly
Efficient Acetylene/Ethylene Separation at Room Temperature.
Chem. Mater. 2018, 30, 7433−7437.
(44) Sun, F. Z.; Yang, S. Q.; Krishna, R.; Zhang, Y. H.; Xia, Y. P.;
Hu, T. L. Microporous Metal-Organic Framework with a Completely
Reversed Adsorption Relationship for C2 Hydrocarbons at Room
Temperature. ACS Appl. Mater. Interfaces 2020, 12, 6105−6111.
(45) Liang, L.; Liu, C.; Jiang, F.; Chen, Q.; Zhang, L.; Xue, H.; Jiang,
H. L.; Qian, J.; Yuan, D.; Hong, M. Carbon dioxide capture and
conversion by an acid-base resistant metal-organic framework. Nat.
Commun. 2017, 8, 1233.
(46) Datta, S. J.; Khumnoon, C.; Lee, Z. H.; Moon, W. K.; Docao,
S.; Nguyen, T. H.; Hwang, I. C.; Moon, D.; Oleynikov, P.; Terasaki,
O.; Yoon, K. B. CO2 capture from humid flue gases and humid
atmosphere using a microporous coppersilicate. Science 2015, 350,
302−306.
(24) Bien, C. E.; Chen, K. K.; Chien, S.-C.; Reiner, B. R.; Lin, L.-C.;
Wade, C. R.; Ho, W. S. W. Bioinspired Metal-Organic Framework for
Trace CO2 Capture. J. Am. Chem. Soc. 2018, 140, 12662−12666.
(25) Yu, M. H.; Zhang, P.; Feng, R.; Yao, Z. Q.; Yu, Y. C.; Hu, T. L.;
Bu, X. H. Construction of a Multi-Cage-Based MOF with a Unique
Network for Efficient CO2 Capture. ACS Appl. Mater. Interfaces 2017,
9, 26177−26183.
(26) Nandi, S.; Collins, S.; Chakraborty, D.; Banerjee, D.;
Thallapally, P. K.; Woo, T. K.; Vaidhyanathan, R. Ultralow Parasitic
Energy for Postcombustion CO2 Capture Realized in a Nickel
lsonicotinate Metal-Organic Framework with Excellent Moisture
Stability. J. Am. Chem. Soc. 2017, 139, 1734−1737.
(27) Moreau, F.; da Silva, I.; Al Smail, N. H.; Easun, T. L.; Savage,
M.; Godfrey, H. G.; Parker, S. F.; Manuel, P.; Yang, S.; Schroder, M.
Unravelling exceptional acetylene and carbon dioxide adsorption
within a tetra-amide functionalized metal-organic framework. Nat.
Commun. 2017, 8, 14085.
(28) Zhang, Z. J.; Nguyen, H. T. H.; Miller, S. A.; Ploskonka, A. M.;
DeCoste, J. B.; Cohen, S. M. Polymer-Metal-Organic Frameworks
(polyMOFs) as Water Tolerant Materials for Selective Carbon
Dioxide Separations. J. Am. Chem. Soc. 2016, 138, 920−925.
(29) Chen, K. J.; Yang, Q. Y.; Sen, S.; Madden, D. G.; Kumar, A.;
Pham, T.; Forrest, K. A.; Hosono, N.; Space, B.; Kitagawa, S.;
Zaworotko, M. J. Efficient CO2 Removal for Ultra-Pure CO
Production by Two Hybrid Ultramicroporous Materials. Angew.
Chem., Int. Ed. 2018, 57, 3332−3336.
(30) Ding, N.; Li, H. W.; Feng, X.; Wang, Q. Y.; Wang, S.; Ma, L.;
Zhou, J. W.; Wang, B. Partitioning MOF-5 into Confined and
Hydrophobic Compartments for Carbon Capture under Humid
Conditions. J. Am. Chem. Soc. 2016, 138, 10100−10103.
(31) Zhao, X.; Bu, X.; Zhai, Q.-G.; Tran, H.; Feng, P. Pore Space
Partition by Symmetry-Matching Regulated Ligand Insertion and
Dramatic Tuning on Carbon Dioxide Uptake. J. Am. Chem. Soc. 2015,
137, 1396−1399.
(32) Ma, Y. S.; Matsuda, R.; Sato, H.; Hijikata, Y.; Li, L. C.; Kusaka,
S.; Foo, M.; Xue, F. F.; Akiyama, G.; Yuan, R. X.; Kitagawa, S. A
Convenient Strategy for Designing a Soft Nanospace: An Atomic
Exchange in a Ligand with Isostructural Frameworks. J. Am. Chem.
Soc. 2015, 137, 15825−15832.
(33) Millward, A. R.; Yaghi, O. M. Metal-Organic Frameworks with
Exceptionally High Capacity for Storage of Carbon Dioxide at Room
Temperature. J. Am. Chem. Soc. 2005, 127, 17998−17999.
(34) Yang, L.; Cui, X.; Zhang, Y.; Wang, Q.; Zhang, Z.; Suo, X.;
Xing, H. Anion Pillared Metal-Organic Framework Embedded with
Molecular Rotors for Size-Selective Capture of CO2 from CH4 and
N2. ACS Sustainable Chem. Eng. 2019, 7, 3138−3144.
(35) Liu, X. P.; Xiao, Z. Y.; Xu, J.; Xu, W. B.; Sang, P. P.; Zhao, L.
M.; Zhu, H. Y.; Sun, D. F.; Guo, W. Y. A NbO-type copper metal-
organic framework decorated with carboxylate groups exhibiting
highly selective CO2 adsorption and separation of organic dyes. J.
Mater. Chem. A 2016, 4, 13844−13851.
(36) Chand, S.; Pal, A.; Saha, R.; Das, P.; Sahoo, R.; Chattaraj, P. K.;
Das, M. C. Two Closely Related Zn(II)-MOFs for Their Large
Difference in CO2 Uptake Capacities and Selective CO2 Sorption.
Inorg. Chem. 2020, 59, 7056−7066.
(47) Liang, W.; Bhatt, P. M.; Shkurenko, A.; Adil, K.; Mouchaham,
G.; Aggarwal, H.; Mallick, A.; Jamal, A.; Belmabkhout, Y.; Eddaoudi,
M. A Tailor-Made Interpenetrated MOF with Exceptional Carbon-
Capture Performance from Flue Gas. Chem. 2019, 5, 950−963.
(48) Liao, P.-Q.; Chen, H.; Zhou, D.-D.; Liu, S.-Y.; He, C.-T.; Rui,
Z.; Ji, H.; Zhang, J.-P.; Chen, X.-M. Monodentate hydroxide as a
super strong yet reversible active site for CO2 capture from
highhumidity flue gas. Energy Environ. Sci. 2015, 8, 1011−1016.
(49) Yuan, S.; Feng, L.; Wang, K.; Pang, J.; Bosch, M.; Lollar, C.;
Sun, Y.; Qin, J.; Yang, X.; Zhang, P.; Wang, Q.; Zou, L.; Zhang, Y.;
Zhang, L.; Fang, Y.; Li, J.; Zhou, H.-C. Stable Metal-Organic
Frameworks: Design, Synthesis, and Applications. Adv. Mater. 2018,
30, 1870277.
(50) Farha, O. K.; Eryazici, I.; Jeong, N. C.; Hauser, B. G.; Wilmer,
̈
C. E.; Sarjeant, A. A.; Snurr, R. Q.; Nguyen, S. T.; Yazaydin, A. O.;
Hupp, J. T. J. Am. Chem. Soc. 2012, 134, 15016.
(51) Catarineu, N. R.; Schoedel, A.; Urban, P.; Morla, M. B.;
Trickett, C. A.; Yaghi, O. M. Two Principles of Reticular Chemistry
Uncovered in a Metal Organic Framework of Heterotritopic Linkers
and Infinite Secondary Building Units. J. Am. Chem. Soc. 2016, 138,
10826−10829.
(52) Ren, G. J.; Chang, Z.; Xu, J.; Hu, Z.; Liu, Y. Q.; Xu, Y. L.; Bu, X.
H. Construction of a polyhedron decorated MOF with a unique
network through the combination of two classic secondary building
units. Chem. Commun. 2016, 52, 2079−2082.
(37) Wu, D.; Liu, C. P.; Tian, J. Y.; Jiang, F. L.; Yuan, D. Q.; Chen,
Q. H.; Hong, M. C. Acid-Base-Resistant Metal-Organic Framework
for Size-Selective Carbon Dioxide Capture. Inorg. Chem. 2020, 59,
13542−13550.
(38) Xiang, S.-C.; Zhang, Z.; Zhao, C.-G.; Hong, K.; Zhao, X.; Ding,
D.-R.; Xie, M.-H.; Wu, C.-D.; Das, M. C.; Gill, R.; Thomas, K. M.;
Chen, B. Rationally Tuned Micropores within Enantiopure Metal-
Organic Frameworks for Highly Selective Separation of Acetylene and
Ethylene. Nat. Commun. 2011, 2, 204.
(53) Eddaoudi, M.; Moler, D. B.; Li, H.; Chen, B.; Reineke, T. M.;
O’Keeffe, M.; Yaghi, O. M. Modular chemistry: Secondary building
units as a basis for the design of highly porous and robust metal-
organic carboxylate frameworks. Acc. Chem. Res. 2001, 34, 319−330.
(54) Schoedel, A.; Li, M.; Li, D.; O’Keeffe, M.; Yaghi, O. M.
Structures of Metal-Organic Frameworks with Rod Secondary
Building Units. Chem. Rev. 2016, 116, 12466−12535.
(39) Das, M. C.; Guo, Q.; He, Y.; Kim, J.; Zhao, C.-G.; Hong, K.;
Xiang, S.; Zhang, Z.; Thomas, K. M.; Krishna, R.; Chen, B. Interplay
of Metalloligand and Organic Ligand to Tune Micropores within
(55) Park, J.; Li, J. R.; Carolina Sanudo, E.; Yuan, D. Q.; Zhou, H. C.
̃
A porous metal-organic framework with helical chain building units
6557
https://doi.org/10.1021/acs.inorgchem.1c00357
Inorg. Chem. 2021, 60, 6550−6558

Inorganic Chemistry
pubs.acs.org/IC
Article
exhibiting facile transition from micro- to meso-porosity. Chem.
Commun. 2012, 48, 883−885.
(56) An, J.; Geib, S. J.; Rosi, N. L. High and Selective CO2 Uptake
in a Cobalt Adeninate Metal-Organic Framework Exhibiting
Pyrimidine- and Amino-Decorated Pores. J. Am. Chem. Soc. 2010,
132, 38−39.
(57) Chen, B.; Ockwig, N. W.; Millward, A. R.; Contreras, D. S.;
Yaghi, O. M. High H2 adsorption in a microporous metal-organic
framework with open metal site. Angew. Chem., Int. Ed. 2005, 44,
4745−4749.
(58) Lin, X.; Jia, J.; Zhao, X. B.; Thomas, K. M.; Blake, A. J.; Walker,
G. S.; Champness, N. R.; Hubberstey, P.; Schröder, M. High H2
adsorption by coordination-framework materials. Angew. Chem., Int.
Ed. 2006, 45, 7358−7364.
(59) Lin, R.-B.; Li, L.; Wu, H.; Arman, H.; Li, B.; Lin, R.-G.; Zhou,
W.; Chen, B. Optimized Separation of Acetylene from Carbon
Dioxide and Ethylene in a Microporous Material. J. Am. Chem. Soc.
2017, 139, 8022−8028.
(60) Dong, Q. B.; Zhang, X.; Liu, S.; Lin, R. B.; Guo, Y. A.; Ma, Y.
S.; Yonezu, A.; Krishna, R.; Liu, G. P.; Duan, J. G.; Matsuda, R.; Jin,
W. Q.; Chen, B. L. Tuning Gate-Opening of a Flexible Metal-Organic
Framework for Ternary Gas Sieving Separation. Angew. Chem., Int. Ed.
2020, 59, 22756−22762.
(61) Zheng, B. S.; Yang, Z.; Bai, J. F.; Li, Y. Z.; Li, S. H. High and
selective CO2 capture by two mesoporous acylamide-functionalized
rht-type metal-organic frameworks. Chem. Commun. 2012, 48, 7025−
7027.
(62) Lu, Z.; Meng, F.; Du, L.; Jiang, W.; Cao, H.; Duan, J.; Huang,
H.; He, H. A. Free Tetrazolyl Decorated Metal-Organic Framework
Exhibiting High and Selective CO2 Adsorption. Inorg. Chem. 2018, 57,
14018−14022.
(63) Pal, A.; Chand, S.; Boquera, J. C.; Lloret, F.; Lin, J. B.; Pal, S.
C.; Das, M. C. Three Co(II) Metal-Organic Frameworks with Diverse
Architectures for Selective Gas Sorption and Magnetic Studies. Inorg.
Chem. 2019, 58, 6246−6256.
(64) King, S. C.; Lin, R. B.; Wang, H.; Arman, H. D.; Chen, B. Two-
dimensional metal-organic frameworks for selective seperation of
CO2/CH4 and CO2/N2. Mater. Chem. Front. 2017, 1, 1514−1519.
(65) Bloch, D.; Queen, W. L.; Krishna, R.; Zadrozny, J. M.; Brown,
C. M.; Long, J. R. Hydrocarbon Separations in a Metal-Organic
Framework with Open Iron(II) Coordination Sites. Science 2012, 335,
1606−1610.
6558
https://doi.org/10.1021/acs.inorgchem.1c00357
Inorg. Chem. 2021, 60, 6550−6558