A Stable Mesoporous Zr-Based Metal Organic Framework for Highly Efficient CO2 Conversion

Article abstract of DOI:10.1021/acs.inorgchem.9b00701

With the help of modulator synthesis method, a mesoporous Zr-based metal-organic framework, [Zr₆O₄(OH)₈(H₂O)₄(TADIBA)₄]·24DMF·45H₂O (DMF = N,N-dimethylformamide, H₂TAD

Full text of DOI:10.1021/acs.inorgchem.9b00701

Article
pubs.acs.org/IC
Cite This: Inorg. Chem. XXXX, XXX, XXX−XXX
A Stable Mesoporous Zr-Based Metal Organic Framework for Highly
Efficient CO2 Conversion
Xiaodong Sun, Jiaming Gu, Yang Yuan, Chengyang Yu, Jiantang Li, Hongyan Shan, Guanghua Li,
and Yunling Liu*
State Key Laboratory of Inorganic Synthesis and Preparative Chemistry, College of Chemistry, Jilin University, Changchun 130012,
P. R. China
S
* Supporting Information
ABSTRACT: With the help of modulator synthesis method,
a mesoporous Zr-based metal−organic framework,
[Zr6O4(OH)8(H2O)4(TADIBA)4]·24DMF·45H2O (DMF =
N,N-dimethylformamide, H2TADIBA = 4,4′-(2H-1,2,4-tria-
zole-3,5-diyl) dibenzoic acid), namely, JLU-MOF58, was
successfully constructed. JLU-MOF58 having reo topology is
constructed by the bent ligands with Lewis basic sites and 8-
connected Zr6 clusters with Lewis and Brønsted acid sites. It
not only possesses two types of mesoporous cages: octahedral
and cuboctahedral (2.76 and 4.10 nm), with a pore volume of
1.76 cm3 g−1, but also displays excellent chemical stability in
acid and base aqueous phase. Benefiting from the Brønsted
and Lewis acid sites, Lewis basic sites, excellent chemical stability, and the mesoporous cages incorporated in the framework,
JLU-MOF58 can be regarded as a remarkably efficient heterogeneous catalyst that exhibits excellent catalytic efficiency for CO2
conversion.
active sites of the microporous MOF, thus resulting in low
catalytic efficiency;41−44 (3) high operating pressures (>3
MPa) and temperatures (>100 °C) are still often required for
cyclic carbonate production, which will increase the cost
considering the energy and capital input.45,46 Herein, design
and synthesis of stable mesoporous MOFs, which are able to
do cycloaddition of CO2 with epoxides under relatively mild
conditions, are urgently demanded and still have great
challenges.47−50 In this case, Zr-MOFs, which possess ultrahigh
surface area and outstanding thermal and chemical stabilities,
make great contributions to overcome this problem.40 As is
known, most of the Zr-MOFs that are constructed by ditopic
carboxylate ligands are 12-connected.51−57 However, Zr-MOFs
with lower connectivity have their unique advantages in CO2
conversion, because the reduced connectivity in Zr-MOFs not
only generates additional space for the formation of
mesopores, which is convenient for the diffusion of larger
substrates, but also provide high densities of Lewis and
Brønsted acid sites for CO2 conversion.58−63
INTRODUCTION
■
Carbon dioxide (CO2), a kind of anthropogenic greenhouse
gas, is considered to be the culprit of the global warming,
which has been listed as the greatest environmental issue
influencing our daily life.1−3 However, CO2 is also an abundant
C1 resource, which can be used to produce many valuable
chemical feedstocks.4−8 Therefore, developing effective CO2
capture and conversion (CCC) technology is proved to be an
alternative sustainable method for eliminating the adverse
effect of greenhouse gas.9,10 Cycloaddition of CO2 with
different kinds of epoxides to synthesis cyclic carbonates,
which are precursors for synthesizing polycarbonates and other
chemicals, is considered as an effective method for CO2
conversion.11−13 Herein, many kinds of heterogeneous
catalysts have been prepared for cycloaddition of CO2 with
epoxides. However, due to high chemical stability of the CO
bond of CO2, the reaction can only be triggered under high
temperature (>100 °C) and pressure (>3 MPa).14−18
In recent years, metal−organic frameworks (MOFs),
because of their high surface areas, adjustable pore sizes, and
surface chemistry, were widely studied as a new type of
heterogeneous catalyst for CO2 conversion through cyclo-
addition of CO2 with epoxides.19−36 However, as a kind of
heterogeneous catalyst, MOFs materials always suffer from
some problems: (1) chemical stability remains a significant
obstacle hindering MOFs for practical applications, especially
in catalysis;37−40 (2) confinement effect of the channel size
always restricts the diffusion of some larger substrates to the
On the basis of the above considerations, we employed a
bent ligand with Lewis basic sites and highly stable Zr6 clusters
for the assembly of Zr-MOF. As expected, an 8-connected
mesoporous Zr-MOF [Zr6O4(OH)8(H2O)4(TADIBA)4]·
24DMF·45H2O (DMF = N,N-dimethylformamide,
H2TADIBA = 4,4′-(2H-1,2,4-triazole-3,5-diyl) dibenzoic
Received: March 11, 2019
© XXXX American Chemical Society
A
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Figure 1. (a) From a topology point of view, H2TADIBA ligand can be simplified as linear rod, and 8-connected Zr6 clusters can be simplified as
cube; (b) two types of mesoporous cages in the framework of JLU-MOF58: octahedral and cuboctahedral ones with diameters of 2.76 and 4.10 nm
between the opposite Zr6 clusters; (c) ball-and-stick view of the JLU-MOF58 along [100] direction; (d) polyhedron view of the framework along
[100] direction. Color scheme: carbon = gray; oxygen = red; zirconium = dark green.
hot ethanol for 12 h (change fresh ethanol every 2 h), to remove all
guest molecules from MOFs. Afterward, supercritical CO2 treatment
was performed to activate the samples.
acid) (JLU-MOF58) with reo topology was successfully
constructed. JLU-MOF58 not only contains two types of
mesoporous cages: octahedral and cuboctahedral (2.76 and
4.10 nm), with a pore volume of 1.76 cm3 g−1, but also could
maintain excellent chemical stability in aqueous phase with
wide range of pH values (from 1 to 9). Given the presence of
excellent stability, mesopores, Lewis and Brønsted acid sites
and Lewis basic sites, JLU-MOF58 exhibits remarkable
catalytic efficiency for CO2 conversion under a mild condition.
Synthesis of JLU-MOF58. H2TADIBA (6 mg, 0.03 mmol), ZrCl4
(12 mg, 0.05 mmol), modulator (acetic acid, 0.3 mL, 0.16 mmol), and
DMF (1 mL) were mixed together into a 20 mL vial. The vial was
sealed and heated in the 120 °C oven for 2 d. Then the mixture was
cooled to the room temperature. Colorless cubic block-shaped crystals
were synthesized (70% yield, calculated based on H2TADIBA ligand).
Elemental analysis (wt %) data for JLU-MOF58: found: C, 34.75; H,
6.32; N, 11.02, calculated: C, 35.45; H, 6.65; N, 10.95. The purity of
the as-synthesized product was verified by the excellent similarity
between the experimental and simulated PXRD patterns of JLU-
MOF58 (Figure S1).
Single-Crystal X-ray Crystallography. Bruker D8 venture
diffractometer, with graphite-monochromated Mo Kα (λ = 0.710 73
Å), was utilized to collect the crystallographic data of JLU-MOF58 at
room temperature. The framework of JLU-MOF58 was solved
through direct methods and refined by full-matrix least-squares on F2
using SHELXTL-2014.64 First, all the non-hydrogen atoms were
determined in difference Fourier maps and refined anisotropically.
Then the hydrogen atoms of the H2TADIBA ligand were generated
theoretically and refined isotropically. The SQUEEZE routine in
PLATON was used to remove the highly disordered guest molecules,
and the results were appended in the CIF file. Finally, the formula of
JLU-MOF58 was calculated based on the crystallographic data,
elemental data, and thermogravimetric analysis data. Crystal
parameters of JLU-MOF58 were presented in Tables S1 and S2.
The CCDC number of JLU-MOF58 is 1870852, and the topology
information was calculated by TOPOS 4.0 software.65
EXPERIMENTAL SECTION
■
Materials and Methods. All chemicals, which are reagent grade,
were purchased from chemical companies. C, H, and N elemental
analysis was tested by utilizing the vario MICRO (Elementar)
instrument. Powder X-ray diffraction (PXRD) data were performed
on Rigaku D/max-2550 diffractometer (λ = 1.5418 Å) over the 2θ
ranging from 2.5 to 40°. PerkinElmer Optima 3300 Dv spectrometer
was utilized to analyze the inductively coupled plasma (ICP) data.
Thermogravimetric analyses (TGA) data were collected on a TGA
Q500 thermogravimetric analyzer (30 to 800 °C, 10 °C min−1).
Shimadzu GCMS-QP 2010 plus was used to collect the gas
chromatography−mass spectrometry (GC-MS) data (injector temper-
ature 250 °C, TR-wax-ms, 30 m × 0.25 mm × 0.25 μm). The N2
adsorption measurements were tested on the Micromeritics ASAP
2420. The alkane gas and CO2 adsorption data were collect from the
Micromeritics 3-Flex. To activate the samples, as-synthesized JLU-
MOF58 (∼50 mg) was washed by fresh DMF to remove unreacted
ligand, metal salt, and acetic acid. Then the samples were washed by
B
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Figure 2. (a) PXRD patterns of the JLU-MOF58 samples after being soaked in acid and alkaline aqueous solutions (pH = 1 to 9) for 3 d; (b) N2
adsorption isotherms of JLU-MOF58 after soaking in HCl (pH = 1), NaOH (pH = 9), and H2O aqueous solutions for 24 h; (inset) pore size
distribution plot of JLU-MOF58 calculated using nonlocalized density functional theory method.
Catalytic Performance of JLU-MOF58. All the catalytic
reactions were tested in a 10 mL sealed test tube containing catalysts
(0.05, 0.1, and 0.2 mol % calculated based on the activated JLU-
MOF58 molecular weight), epoxide (10 mmol), and cocatalyst of
tetra-n-tert-butylammonium bromide (TBAB, 0.1, 0.3, and 0.5 mol
%). Then the reaction tube was purged of air with CO2 four times
under 1 atm. After the CO2 was introduced, the reaction mixtures
were stirred under a relatively mild condition (25 and 80 °C for
propylene oxide and larger epoxides, respectively) for specific times.
The catalysts were then recycled by centrifugation and prepared for
the next cycle experiment. The final products were detected by GC-
MOF58 viewed along [100], [101], and [111] directions
illustrated that it had empty skeleton (Figure S3).
The solvent-accessible volume of JLU-MOF58 was calcu-
lated to be 169 497 Å3 per unit cell, which counts for ∼75% of
the cell volume. Because of the large cavities and high porosity
of the framework, JLU-MOF58 must be carefully activated
with supercritical CO2. As shown in Figure 2b, typical type IV
N2 adsorption isotherm of JLU-MOF58 exhibits an increase at
a relative pressure of P/P0 = 0.13, corresponding to a
mesoporous cage of 2.5 nm in JLU-MOF58. The Brunauer−
Emmett−Teller (BET) and Langmuir surface areas are
calculated to be 3663 and 6808 m2 g−1, respectively. The
BET surface area surpasses many reported Zr-MOFs (Table
S3). The experimental total pore volume is 1.76 cm3 g−1 for
JLU-MOF58, which is close to the theoretical value (2.17 cm3
g−1). Remarkably, JLU-MOF58 possesses not only large
mesopores but also excellent thermal and chemical stabilities.
The high collapse temperature (∼450 °C), which can be
confirmed by TGA curves and the temperature-dependent
PXRD patterns of JLU-MOF58, reveals its excellent thermal
stability (Figure S2). As shown in Figure 2a, the material
structure can also be well-maintained after being immersed in
acid and base aqueous solutions (pH = 1 to 9). Moreover, N2
adsorption isotherms of the samples, which were treated by
water and strong acid solutions, further indicated that JLU-
MOF58 possessed remarkable chemical stability. The excellent
stability of this Zr-MOF is due to the high positive charge
density on Zr (IV), which can generate strong interactions
between the ligand carboxylates and metal clusters.40
After the permanent porosity was established, the CO2
sorption ability of JLU-MOF58 was investigated first. As
illustrated in Figure S6, the CO2 uptake values of JLU-MOF58
are determined to be 49 and 28 cm3 g−1 at 273 and 298 K
under 1 bar, respectively. Because of the empty skeleton of the
JLU-MOF58 framework, there were no multiple interactions
between CO2 molecules and the framework. Herein the CO2
uptake value of JLU-MOF58 was lower. At zero loading, the
isosteric heat (Qst) of CO2 for the JLU-MOF58 is 19 kJ mol−1.
Because of the high density of Lewis and Brønsted acid sites,
Lewis basic sites, excellent chemical stability, and the
mesoporous cages in the framework, we intend to evaluate
the catalytic performance of JLU-MOF58 for cycloaddition of
1
MS with the peak area normalization method and determined by H
NMR.
RESULTS AND DISCUSSION
■
Single X-ray crystallographic analysis reveals that JLU-MOF58
crystallizes in cubic space group Fm3m with the lattice
̅
parameter a = 60.912(7) Å. The total framework is
constructed by 8-connected Zr6 cluster and bent aromatic
ditopic carboxylates (H2TADIBA) with Lewis basic sites. As is
known, combining Zr6 clusters and dicarboxylate ligands
usually generates classical 12-connected UiO-series
MOFs.51−57 However, in JLU-MOF58, eight edges of the
Zr6 octahedral cluster are bridged by carboxylates, and the
remaining sites are occupied by terminal −OH and H2O
molecules. Consequently, the Zr6 clusters become 8-connected
nodes with the symmetry reduced from Oh to D4h (Figure 1a).
From a topology point of view, H2TADIBA ligand can be
simplified as linear rod, and 8-connected Zr6 clusters can be
simplified as cube. Herein, the whole framework is 8-
connected with reo topology (Figure 1c,d). Because of the
reduced connectivity, which can potentially provide additional
space, two kinds of mesoporous cages, octahedral and
cuboctahedral, are formed in JLU-MOF58 (Figure S4). As
shown in Figure 1b, the octahedral cage consists of six 8-
connected Zr6 clusters and 12 bent ligands with 2.76 nm
between the opposite Zr6 clusters. The cuboctahedral cage is
constructed by six square and eight triangular windows with a
4.10 nm inner pore size. Therefore, the octahedral cages
connected with cuboctahedral cages by sharing the edges of
the triangular windows to construct a mesoporous framework.
Connolly surface area and space-filling models of the JLU-
C
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CO2 with different kinds of epoxides. Taking advantage of the
mesoporous cages in JLU-MOF58, transforming styrene oxide,
a larger substrate, with CO2 into styrene carbonate was
selected as a typical reaction. To optimize the reaction
conditions, a series of control tests were performed (Table S4).
When the reactions were performed in the absence of JLU-
MOF58 or TBAB, only a small amount of substrate were
converted (Table 1, entries 5 and 6). While combining both
Table 1. Cycloaddition of CO2 with Styrene Epoxide under
Different Conditions
entry
catalysts
time, h conversion, % selectivity, % yield, %
1
2
3
4
5
6
7
JLU-MOF58
JLU-MOF58
JLU-MOF58
JLU-MOF58
no catalyst
no TBAB
12
24
24
24
24
24
24
68
99
85
94
28
31
28
95
96
97
94
75
72
58
65
95
82
88
21
22
16
a
b
c
Figure 3. A possible cooperative catalytic mechanism for cyclo-
addition of styrene oxide and CO2 catalyzed by JLU-MOF58/TBAB.
The blue ball represents the Br− of TBAB, and light blue cube
represents the Lewis basic sites of the framework. The parts selected
by the dotted line (red and blue) represent the Lewis and Brønsted
acid sites in the framework. Color code: Zr = green, O = red, H =
white, and C = gray.
ligand
a
Reaction conditions: styrene oxide (10 mmol), JLU-MOF58 (0.1
mol %), and TBAB (nBu4NBr, 5 mol %) (1 atm CO2, 80 °C).
Catalytic performance was tested by H NMR and GC-MS. JLU-
b
1
c
facilitated by binding the oxygen atom of epoxide with the
Lewis acidic zirconium site and forming hydrogen bonds
between the (−OH) group of Zr6 cluster and oxygen atom of
epoxide. Then, the Br− of TBAB as nucleophiles attacks the
polarized ring, forming an opened ring, and exists in the form
of intermediate oxygen anion. Subsequently, it rapidly reacts
with the contiguous CO2 molecules, which have been activated
by Lewis basic sites of the H2TADIBA ligand in the
framework, to generate alkycarbonate anions. Finally, the
cycloaddition reaction is achieved through the ring-closing
step, and TBAB could be recycled simultaneously. The
mesoporous cages of JLU-MOF58 could also boost the
diffusion of the substrates and products, thus promoting the
cycloaddition reaction. In summary, the whole cycloaddition
reaction is synergistically promoted by the Lewis, Brønsted
acid and basic sites incorporated in the mesoporous frame-
work.
Encouraged by the excellent catalytic performance of JLU-
MOF58 for styrene oxide, another four epoxides with different
sizes and ring tension substrates were selected to further study
the effect of spatial confinement effect on catalytic efficiency
under the optimized conditions. As expected, because of the
presence of large mesoporous cages in the frameworks, the
catalysis performance of JLU-MOF58 is not influenced by the
size or shape of the substrates. As shown in Table 2, JLU-
MOF58 exhibited outstanding catalytic activity for different
sizes and shape substrates, from the smallest substrate: PO
(95% yield, 4.2 × 2.6 Å) to the largest substrate: glycidyl 2-
methylphenyl ether (yield: 81%, 9.8 × 5.2 Å). It is worth
mentioning that, due to the pore size restriction in micro-
porous MOFs, only a few works evaluated the catalytic
performance for cycloaddition of benzyl phenylglycidyl ether.
However, because of the mesopores, JLU-MOF58 is proved to
be an efficient catalyst for this reaction with a high yield of
90%, which is comparable to many well-known MOF
MOF58 (0.05 mol %). TBAB (1 mol %).
JLU-MOF58 and TBAB as a binary catalyst (Table 1, entry 2),
styrene oxide was efficiently converted into styrene carbonate
(Table 1, entries 2, 3, and 4), which indicates the critical role
of JLU-MOF58 and TBAB (cocatalyst) during the cyclo-
addition reaction. After the factor of time was further
optimized, along with the amount of catalyst and cocatalyst
(Table 1, entries 1, 2, 3, and 4), JLU-MOF58 efficiently
converted CO2 with a high yield of 95% and a remarkable
turnover frequency (TOF) value of 40 under the reaction
conditions of catalyst (0.1 mol %) and cocatalyst (5 mol %) at
a relatively mild condition (1 atm and 80 °C) for 24 h (Table
S4). Because of the pore size restriction, only a few MOF
materials exhibit high performance for transforming styrene
oxide. However, because of the presence of mesopores in JLU-
MOF58, its catalytic performance is comparable to many
reported Zr-MOFs and other metal-based MOFs under the
similar conditions, such as Zr-based MOF-892, MOF-893,58
PCN-700,66 Zr(H4L),67 and other metal-based Gea-MOF-1,68
Hf-NU-1000,69 and Cu-TPTC-NH2
materials (Table
20
S5).70−72 Compared with Gea-MOF-1, JLU-MOF58 could
promote the progress of the reaction at a relatively mild
condition.
According to previous reports, when MOF materials act as
heterogeneous catalyst for cycloaddition of CO2 reaction, the
Lewis/Brønsted acid sites in the framework could fix and
polarize the epoxide. If there exist Lewis basic sites in the
framework, it would polarize the carbon dioxide and promote
the reaction.73−77 Herein, a possible cooperative catalytic
mechanism for the cycloaddition of CO2 with epoxide into
cyclic carbonate is proposed. As illustrated in Figure 3, the
overall reaction consists of four steps. First, the reaction is
initiated by polarizing the epoxide ring, which is synergistically
D
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a
Table 2. Cycloaddition of CO2 and Different-Size Epoxides Catalyzed by JLU-MOF58 under the Optimum Conditions
a
Reaction conditions: different-size epoxide (10 mmol), catalyst (JLU-MOF58, 0.1 mol %), and cocatalyst (TBAB, 5 mol %) under 1 atm PCO2 for
1
24 h (25 and 80 °C for propylene oxide and larger epoxides, respectively). Catalytic performances were tested by H NMR.
materials, such as (I−)Meim-UiO-66,71 FJI-C10,10 and Cu-
TPTC-NH2 (Table S6).
The regenerative performance is very important for a
ASSOCIATED CONTENT
■
20
S
* Supporting Information
The Supporting Information is available free of charge on the
catalyst; when the cost of material synthesis is considered,
ACS Publications website at DOI: 10.1021/acs.inorg-
the recycling experiments for the CO2 cycloaddition of styrene
chem.9b00701.
oxide were conducted. As shown in Figure S15, after six rounds
of circulation, JLU-MOF58 could be successfully recycled
Gas sorption data, TGA, PXRD, 1H NMR data,
without any significant loss in its catalytic activity, which
indicates the excellent practicability of the JLU-MOF58.
Meanwhile, the ICP-optical emission spectrometry (OES)
analysis and the PXRD patterns of the six times recycled
samples further confirmed that JLU-MOF58 was an efficient
and reusable heterogeneous MOF catalyst (Figure S16).
additional structural figures, and crystallographic data
(PDF)
Accession Codes
CCDC 1870852 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.
CONCLUSIONS
■
In conclusion, by using the modulator synthesis approach, we
design and construct a Zr-based MOF containing two types of
mesoporous cages (2.76 and 4.10 nm) with reo topology.
Although MOFs with high surface areas tend to decompose,
JLU-MOF58 exhibits excellent chemical stability in acid and
alkaline aqueous. Given the presence of chemical stability,
Lewis and Brønsted acid sites, and basic sites incorporated in
the mesoporous framework, JLU-MOF58 exhibits efficient
catalytic performance and outstanding recyclability for CO2
cycloaddition with epoxides under a relatively mild condition.
Herein, design and synthesis of such Zr-MOFs owing
mesoporous cages are highly desirable for CO2 fixation in
the field of global climate treatment.
AUTHOR INFORMATION
■
Corresponding Author
*E-mail: yunling@jlu.edu.cn.
ORCID
Jiantang Li: 0000-0002-8963-5402
Guanghua Li: 0000-0003-3029-8920
Yunling Liu: 0000-0001-5040-6816
Notes
The authors declare no competing financial interest.
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ACKNOWLEDGMENTS
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The authors gratefully acknowledge the financial support of the
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