Metal-Organic Framework with Rich Accessible Nitrogen Sites for Highly Efficient CO2 Capture and Separation

Article abstract of DOI:10.1021/acs.inorgchem.9b00182

A novel microporous metal-organic framework (FJU-44), with abundant accessible nitrogen sites on its internal surface, was constructed from the tetrapodal tetrazole ligand tetrakis(4-tetrazolylphenyl)ethylene (H₄TTPE) and copper chloride. Notably, the CO₂ uptake capacity (83.4 cm³/g, at 273 K and 1 bar) in the activated FJU-44a is higher than most of tetrazolate-containing MOF materials. Particularly, FJU-44a exhibits superior adsorption selectivity of CO₂/N₂ (278-128) and CO₂/CH₄ (44-16), which is comparable to some well-known CO₂ capture materials. Furthermore, the fixed-bed breakthrough experiment indicates that the postcombustion flue gas flow over a packed column with FJU-44a adsorbents can be effectively separated.

Full text of DOI:10.1021/acs.inorgchem.9b00182

Article
pubs.acs.org/IC
Cite This: Inorg. Chem. XXXX, XXX, XXX−XXX
Metal−Organic Framework with Rich Accessible Nitrogen Sites for
Highly Efficient CO2 Capture and Separation
Yingxiang Ye, Heng Zhang, Liangji Chen, Shimin Chen, Quanjie Lin, Fangfang Wei,*
Zhangjing Zhang,* and Shengchang Xiang
Fujian Provincial Key Laboratory of Polymer Materials, College of Chemistry and Materials Science, Fujian Normal University, 32
Shangsan Road, Fuzhou 350007, P. R. China
S
* Supporting Information
ABSTRACT: A novel microporous metal−organic frame-
work (FJU-44), with abundant accessible nitrogen sites on its
internal surface, was constructed from the tetrapodal tetrazole
ligand tetrakis(4-tetrazolylphenyl)ethylene (H4TTPE) and
copper chloride. Notably, the CO2 uptake capacity (83.4
cm3/g, at 273 K and 1 bar) in the activated FJU-44a is higher
than most of tetrazolate-containing MOF materials. Partic-
ularly, FJU-44a exhibits superior adsorption selectivity of
CO2/N2 (278−128) and CO2/CH4 (44−16), which is
comparable to some well-known CO2 capture materials.
Furthermore, the fixed-bed breakthrough experiment indicates
that the postcombustion flue gas flow over a packed column
with FJU-44a adsorbents can be effectively separated.
instance, the polytetrazolate-based MOFs (FJU-56 and
[NC2H8]4Cu5(BTT)3) incorporated with rich uncoordinated
nitrogen atoms show high stabilities and superior CO2
adsorption performances.33,39
INTRODUCTION
■
As a class of fascinating crystalline porous materials, metal−
organic frameworks (MOFs),1 also known as porous
coordination polymers (PCPs),2 have received considerable
attention as potentially valuable gas storage,3−6 separation,7−18
sensing,19−21 proton conducting,22−24 and catalyst materi-
als,25−28 attributed to their rich structural tunability, high
surface areas, and unique pore structures and surfaces. Over
the past two decades, the scientists have designed and
constructed a large number of novel MOF materials, mainly
focused on the use of carboxyl and/or pyridine ligands.
Nowadays, there is growing interest in fabricating MOFs by
using azolates linkers, because the strong metal−nitrogen (M−
N) bonds often endow excellent thermal and chemical
stabilities to the host frameworks.29−34 However, among the
various azolates (e.g., imidazole, pyrazole, triazole and
tetrazole) ligands, the tetrazolate ligands might be the most
promising candidates in the construction of versatile MOFs,
owing to their high number of donor N sites capable of
adopting different bridging or chelating coordination modes.35
For example, a series of polytetrazolate-based MOFs,
Mn3 [(Mn4 Cl)3 (BTT)8 ]2 , Cu(BDT)(DMF), and
Zn3(BDT)3(DMF)4(H2O)2,36,37 were constructed by the
Long group, in which the ligands display similar pyrazolate
coordination modes. Furthermore, Bu and co-workers reported
a chiral microporous MOF [Zn(dtp)],38 in which the
tetrazolate linker exhibits the similar imidazolate coordination
modes. On the other hand, the decoration of the open N
atoms into the pore surfaces of MOFs can significantly
improve the gas uptake capacity, especially for CO2. For
On the basis of the above considerations, we are particularly
fascinated by ligands containing multiple tetrazole groups,
because such ligands can realize high connectivity and a high
proportion of accessible N atoms simultaneously. However, at
present, only a few polytetrazole ligands possessing four
tetrazole groups have been reported, and they are mainly
focused on tetraphenylmethane, adamantane, and porphyrin as
organic scaffolds.40−42 In this study, we design and synthesize a
new polytetrazole linker, tetrakis(4-tetrazolylphenyl)ethylene
(H4TTPE, Scheme S1, Figure 1a), on the basis of the following
considerations: the partially twisted ethyl core and multiple
rotational phenyl rings would result in a nonplanar
configuration of the ligand, which facilitates the fabrication
of highly connected porous structures. Then, a novel
microporous MOF ([Cu2Cl(HTTPE)(H2O)]·xG, FJU-44)
was successfully constructed from the H4TTPE ligand and a
Cu(II) ion under solvothermal conditions. It is worth
mentioning that the 1D rhombic channel of FJU-44 was
decorated with abundant uncoordinated nitrogen atoms, which
is beneficial to gas capture and separation. As expected, the
activated FJU-44a shows a moderately high uptake value of
CO2 and excellent selective capture ability for CO2/CH4 and
CO2/N2, and more importantly, the CO2/N2 selectivity is
Received: January 18, 2019
© XXXX American Chemical Society
A
DOI: 10.1021/acs.inorgchem.9b00182
Inorg. Chem. XXXX, XXX, XXX−XXX

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Figure 1. Structure of FJU-44 showing (a) the organic ligand H4TTPE and (b) the coordination mode of the copper(II) atoms. (c) 3D open
framework with two types of 1D rhombic channel viewed along the crystallographic c-axis. (d) Illustration of the pore aperture sizes of FJU-44
viewed along the crystallographic c-axis. Cross section of the two types of channel surfaces viewed along (e) the crystallographic a- and (f) b-axes.
Color code: Cu, orange; C, dark gray or gray; Cl, green; O, red; N, blue. Hydrogen atoms and solvent molecules have been omitted for clarity.
comparable to some top-performing CO2 capture materials.43
Moreover, the dynamic breakthrough experiment shows that
the simulated postcombustion flue gas (mainly containing CO2
and N2) can be effectively separated by a packed column
containing FJU-44a solids.
analysis and thermogravimetric analysis (TGA) (Figures S3
and S4). The PXRD diffraction patterns of the as-synthesized
sample matched well with the simulated one from the single-
crystal data. To explore the permanent porosity, the newly
synthesized FJU-44 was solvent-exchanged with dry CH2Cl2 to
remove the high boiling point guest molecules, and then
degassed overnight at 80 °C to give a guest-free sample of FJU-
44a. The PXRD profile of the activated FJU-44a exhibited no
appreciable changes compared with the as-synthesized sample,
confirming that the structural integrity was fully retained after
activation (Figure S4).
RESULTS AND DISCUSSION
■
The solvothermal reaction of CuCl2 and H4TTPE in DMF
solution at 85 °C for 3 days gave the blue rod-shaped crystals
of FJU-44. Single-crystal X-ray structural analysis revealed that
FJU-44 crystallizes in the monoclinic P2/m space group. As
shown in Figure 1b, there are three crystallographically
independent Cu(II) ions all exhibiting six-connected octahe-
dral coordination geometries. The Cu1 atom lying on an
inversion center is surrounded by four nitrogen atoms from
four TTPE ligands, and two axially positioned oxygen atoms
from bridging water molecules. The Cu2 atom is surrounded
by four N atoms from four TTPE ligands, one O atom and one
Cl atom, forming a distorted octahedral geometry. The
coordination mode of the Cu3 atom is like that of Cu1,
except the two axially positioned O atoms changed to the Cl
atoms. Notably, the Cu atoms were connected by the bridging
of μ2-Cl and μ2-O atoms to form a 1D inorganic zigzag chain
[(Cu2Cl(H2O))n]n+. Then, such 1D chains were further
connected to four neighboring chains by the TTPE ligands
to assemble a three-dimensional open framework (Figure 1c).
The resulting structure contains two types of 1D rhombic
channels with the pore aperture sizes of 10.2 × 6.0 Å2 and 5.0
× 4.9 Å2, respectively, along the crystallographic c-axis (Figure
1d). It was worth noting that there are abundant uncoordi-
nated nitrogen atoms toward the pore surfaces (Figure 1e,f),
which will facilitate the gas selective adsorption and separation.
Topologically, if the CuN4X2 (X = Cl or O) unit and TTPE
ligand are both simplified as four-connected nodes, the host
framework of FJU-44 displays a rare (4,4)-connected network
with a point symbol of (4.64.8)2(42.62.82) (mog topology,
Figure S1).44 Without the free solvent molecules taken into
consideration, the total accessible void volumes in FJU-44 are
estimated to be 44.8%, as calculated by the PLATON/
SQUEEZE program.45
Next, we collect the 77 K N2 adsorption isotherm of FJU-
44a (Figure 2), in which the isotherm shows a type-I
Figure 2. 77 K N2 sorption isotherms of FJU-44a. Inset: pore size
distribution (PSD) of FJU-44a.
adsorption behavior with the maximum N2 uptake value of
217 cm3/g, and the pore volume is calculated to be 0.34 cm3/g.
The Langmuir and Brunauer−Emmett−Teller (BET) surface
areas of FJU-44a were up to 898.1 and 629.5 m2/g,
respectively, which are comparable to that of [(NC2H8)4Cu5-
(BTT)3] (701 m2/g)39 and CPF-6 (599 m2/g)46 but
significantly larger than UTSA-57a (206.5 m2/g)47 among
the same type of MOF materials. With analysis based on the
no-local density functional theory (NLDFT) model, FJU-44a
displays a bimodal pore size distribution with the centers of 6.8
and 13.6 Å, respectively.
The phase purity of the bulk sample was verified by powder
X-ray diffraction (PXRD), and further confirmed by elemental
B
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Figure 3. (a) 273 K and (b) 296 K CO2, CH4, and N2 adsorption isotherms of FJU-44a.
Figure 4. (a−c) Mixture adsorption isotherms and adsorption selectivity of FJU-44a for CO2/N2 (15/85) and CO2/CH4 (50/50) at 296 K as
predicted by IAST. (d) The CO2 and CH4 isosteric heat of adsorption (Qst) in FJU-44a.
Establishment of permanent porosity, suitable pore space,
and abundant accessible N atoms toward the pore surface
makes us determine that FJU-44a might have good perform-
ances for carbon capture and separation. At 1 bar, the uptake
amounts of CO2 are 53.2 and 83.4 cm3/g at 296 and 273 K,
respectively (Figures 3). At ambient conditions, the CO2
uptake value in FJU-44a is lower than the those of the M-
MOF-74 (179.5 cm3/g)48 series with various open metal sites,
but the adsorbed CO2 is comparable to NENU-520a (60 cm3/
g)49 and [(NC2H8)4Cu5(BTT)3] (52 cm3/g),39 and much
higher than those of UTSA-57a (35 cm3/g)47 and LIFM-WZ-3
(29.5 cm3/g)50 in the same type of tetrazolate-based MOFs.
For comparison, the uptakes amount of CH4 and N2 are very
low at 296 K, with the values of 11.3 cm3/g and 2.7 cm3/g
only.
and 296 K. As shown in Figure 4d, the zero coverage
enthalpies are 40.4 kJ/mol for CO2 and 22.2 kJ/mol for CH4.
Notably, the adsorption enthalpy of CO2 in FJU-44a is
stronger than that of zeolite NaX (34 kJ/mol),43 and some
typical metal azolate framework materials such as ZTF-1 (25.4
kJ/mol), MAF-66 (26.0 kJ/mol), and UTSA-49 (27.0 kJ/
mol).51−53 Moreover, the Qst value for methane in FJU-44a is
comparable to those of Cu-TDPAT (20.7 kJ mol−1),54 FJI-C4
(20.8−23.1 kJ mol−1),55 and UTSA-36a (24.4 kJ mol−1).56
The high uptake capacity and adsorption enthalpy of CO2,
accompanying the remarkable CO2/CH4 and CO2/N2
adsorption selectivity, may be reasonable evidence of the fact
that CO2 has stronger interactions with the uncoordinated N
atoms, due to its larger polarizability and quadrupole moment.
The widespread approach based on the ideal adsorbed
solution theory (IAST)57 is adopted to calculate the
adsorption selectivity of CO2/N2 (15%:85%) and CO2/CH4
(50%:50%) at different pressures (Figure 4a,b). At 296 K and
To determine the CO2 and CH4 adsorption affinities in FJU-
44a, the coverage-dependent isosteric heat of adsorption (Qst)
was calculated on the basis of the adsorption isotherms at 273
C
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Figure 5. Experimental breakthrough curves for (a) CO2/N2 (15%:85%) gas mixtures and (b) the cycling test for CO2/N2 (15%:85%) gas mixtures
in a packed column with FJU-44a adsorbent at 296 K and 1 bar.
100 kPa, the IAST selectivity for CO2/N2 in FJU-44a is up to
128 (Figure 4c), comparable to top-performing CO2 capture
materials MgMOF-74 (182) and NaX (146),43 and signifi-
cantly higher than those of other well-known MOFs, such as
ZnMOF-74 (87.7), Bio-MOF-11 (80), and Cu-TDPAT
(58).43 The IAST selectivity (16) for CO2/CH4 is comparable
to those of some famous MOFs, Fe2(dobdc) (20.2), MOF-5
(15.5), and Cu-TDPAT (13.8).43 Similarly, at 273 K, the IAST
selectivity of FJU-44a lies in the ranges from 827 to 187 and
92 to 23 for CO2/N2 and CO2/CH4 (Figure S10). Thus, the
high selectivity endows FJU-44a with the unfolding of the
superior separation proficiency toward gas mixtures of CO2/N2
and CO2/CH4.
It is well-known that carbon dioxide (CO2) is one of the
chief perpetrators of the greenhouse effect, mainly from the
combustion of coal, oil, and natural gas. Meanwhile, carbon
capture and separation (CCS) technology is one of the most
effective strategies to reduce CO2 in the atmosphere.58,59 To
assess the feasibility of FJU-44a to capture CO2 from the
postcombustion flue gas (CO2/N2) in the actual processes, we
implement dynamic breakthrough experiments, in which the
CO2/N2 (15%:85%) mixed gases flow through a packed
column containing solid adsorbent FJU-44a under ambient
conditions. As shown in Figure 5a, the CO2/N2 mixed gases
can be effectively separated by FJU-44a, in which N2 was initial
eluted and quickly reached pure grade, whereas CO2 was not
detected until after a period of time (∼11 min g−1). On the
basis of the breakthrough curve, the dynamic CO2 capture
capacity and separation factor (αCO2/N2) in FJU-44a for CO2/
N2 gas mixtures were calculated to be 183 mmol/kg and 9.5,
respectively. To ensure the recyclability and facile regeneration
of FJU-44a, we thus performed multiple dynamic break-
through experiments. Figure 5b shows that the dynamic uptake
capacities of CO2 and separation performances toward CO2/
N2 gas mixtures remain steady after three cycling tests, further
demonstrating that FJU-44a is one of the promising candidates
for carbon capture and separation.
experiments indicate that postcombustion flue gas flow over a
packed column with FJU-44a solid can be effectively
separated. This work demonstrates that the strategy for
constructing pore surfaces with rich accessible nitrogen
atoms will promote the design and synthesis of novel MOF
materials for other challenging gas separations in the future.
ASSOCIATED CONTENT
* Supporting Information
The Supporting Information is available free of charge on the
ACS Publications website at DOI: 10.1021/acs.inorg-
chem.9b00182.
■
S
Experimental section, additional structural figures, FT-IR
spectrum, TGA curve, PXRD patterns, and gas
adsorption isotherms (PDF)
Accession Codes
CCDC 1890650 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.
AUTHOR INFORMATION
Corresponding Authors
*E-mail: wfanfan@fjnu.edu.cn.
*E-mail: zzhang@fjnu.edu.cn.
■
ORCID
Yingxiang Ye: 0000-0003-3962-8463
Zhangjing Zhang: 0000-0003-1264-7648
Shengchang Xiang: 0000-0001-6016-2587
Notes
The authors declare no competing financial interest.
ACKNOWLEDGMENTS
■
This work was financially supported by the National Natural
Science Foundation of China (21673039, 21573042, and
21273033), Fujian Science and Technology Department
(2018J07001, 2016J01046, and 2014J06003). Y.Y. gratefully
acknowledges the support of the China Scholarship Council.
CONCLUSIONS
■
In conclusion, we have successfully constructed a new
polytetrazolate-based MOF (FJU-44), with abundantly acces-
sible nitrogen atoms on its internal surface. Notably, FJU-44a
displays a moderately high uptake value for CO2 and
outstanding CO2/N2 and CO2/CH4 adsorption selectivities,
which are comparable to those of some top-performing CO2
capture materials. Furthermore, the dynamic breakthrough
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