Porous Metal-Organic Frameworks with Chelating Multiamine Sites for Selective Adsorption and Chemical Conversion of Carbon Dioxide

Article abstract of DOI:10.1021/acs.inorgchem.7b03099

A combination of carbon dioxide (CO₂) capture and chemical fixation in a one-step process is attractive for chemists and environmentalists. In this work, by incorporating chelating multiamine sites to enhance the binding affinity toward CO

Full text of DOI:10.1021/acs.inorgchem.7b03099

Article
Cite This: Inorg. Chem. XXXX, XXX, XXX−XXX
pubs.acs.org/IC
Porous Metal−Organic Frameworks with Chelating Multiamine Sites
for Selective Adsorption and Chemical Conversion of Carbon Dioxide
Dan Zhao, Xiao-Hui Liu, Jin-Han Guo, Hua-Jin Xu, Yue Zhao, Yi Lu,* and Wei-Yin Sun*
Coordination Chemistry Institute, State Key Laboratory of Coordination Chemistry, School of Chemistry and Chemical Engineering,
Nanjing National Laboratory of Microstructures, Collaborative Innovation Center of Advanced Microstructures, Nanjing University,
Nanjing 210023, China
*
S Supporting Information
ABSTRACT: A combination of carbon dioxide (CO ) capture and chemical
2
fixation in a one-step process is attractive for chemists and environmentalists. In
this work, by incorporating chelating multiamine sites to enhance the binding
affinity toward CO , two novel metal−organic frameworks (MOFs) [Zn (L)(2,6-
2
2
NDC) (H O)]·1.5DMF·2H O (1) and [Cd (L)(2,6-NDC) ]·1.5DMF·2H O
2
2
2
2
2
2
1
1
(
2) (L = N -(4-(1H-1,2,4-triazole-1-yl)benzyl)-N -(2-aminoethyl)ethane-1,2-
diamine, 2,6-H NDC = 2,6-naphthalenedicarboxylic acid, DMF = N,N-
2
dimethylformamide) were achieved under solvothermal conditions. Both 1 and
2
possess high selectivity for adsorption of CO over CH at room temperature
2 4
under atmospheric pressure. Moreover, 1 has one-dimensional tubular channels
decorated with multiactive sites including NH2 groups and coordination
unsaturated Lewis acid metal sites, leading to efficient catalytic activity for
chemical fixation of CO by reaction with epoxides to give cyclic carbonates
2
under mild conditions.
14
INTRODUCTION
desired. To reach the target for capture and conversion of
■
CO , MOFs should have crucial features including high
stability, adsorption capacity, and selectivity for CO2.
2
Carbon dioxide (CO ), as a continuing increasing greenhouse
2
1
5
gas, mainly originates from burning of fossil fuels and now has
1
,2
Therefore, design and construction of new MOFs with such
features is an important but challenge task for capture and
become one of the greatest environmental concerns.
Development of green processes for promising CO capture
and fixation is a pressing task. Much effort has been made in the
2
16
conversion of CO2.
past few years to capture and fix CO using varied porous
Following these considerations, a triazole tripodal ligand with
2
3
4
5
1
materials such as zeolites, organic polymers, ionic liquids,
a chelating multiamine site, namely, N -(4-(1H-1,2,4-triazole-1-
6
and metal−organic frameworks (MOFs). Furthermore, it has
1
yl)benzyl)-N -(2-aminoethyl)ethane-1,2-diamine (L), was used
been recognized that conversion of adsorbed CO into high
17
2
to prepare new MOFs. The incorporation of a chelating
value-added species is very significant from both industrial and
multiamine site and triazole group not only enriches the
coordination fashion of L but also enhances the binding affinity
toward CO . In this work, two porous MOFs [Zn (L)(2,6-
academic standpoints. However, the chemical fixation of CO is
2
difficult due to its high thermodynamic stability and kinetic
2
2
inertness, even though CO is an inexpensive, nontoxic, and
2
7
NDC) (H O)]·1.5DMF·2H O (1) and [Cd (L)(2,6-NDC) ]·
renewable C1 feedstock. Inspiringly, porous MOFs have
2
2
2
2
2
designable architectures and facile pore functionalization, and
1.5DMF·2H O (2) (2,6-H NDC = 2,6-naphthalenedicarboxylic
2 2
accordingly can be used for efficient conversion of CO into
acid, DMF = N,N-dimethylformamide) were achieved. Both 1
and 2 show selectively adsorption of CO over CH at 273 and
2
8
9
valuable chemicals such as urea derivatives, cyclic carbonates,
2
4
1
0
and formic acid. Particularly, cyclic carbonates as important
industrial intermediates are manufactured by highly toxic
phosgene, and thus an alternative and green route is required.
2
98 K under atmospheric pressure. In addition, 1 possesses
one-dimensional (1D) tubular channels decorated with
abounding active sites: NH -groups and unsaturated coordina-
2
Cycloaddition of CO with epoxides produces cyclic carbonates
2
tion metal sites generated by the removal of coordinated water
molecules, leading to efficient catalytic activity for chemical
fixation of CO2 by reaction with epoxides to give cyclic
carbonates under mild conditions.
without other byproducts and is a green process and atom
11,12
economy reaction.
Varied homogeneous catalysts have
been employed for the preparation of cyclic carbonates;
however, high temperature and high pressure are needed for
1
3
the reactions. As an ideal goal, efficient and reusable
heterogeneous catalysts working under mild reaction conditions
with high selectivity and a simple workup procedure are
Received: December 8, 2017
©
XXXX American Chemical Society
A
DOI: 10.1021/acs.inorgchem.7b03099
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EXPERIMENTAL SECTION
Table 1. Crystallographic Data and Structure Refinements
for 1 and 2
■
Preparation of [Zn (L)(2,6-NDC) (H O)]·1.5DMF·2H O (1). A
2
2
2
2
mixture of Zn(ClO ) ·6H O (37.23 mg, 0.1 mmol), L (13.01 mg, 0.05
4
2
2
compound
1
2
mmol), 2,6-H NDC (21.61 mg, 0.1 mmol), and NaOH (0.41 mg, 0.01
2
chemical formula
formula weight
temperature/K
crystal system
space group
a/Å
C H N O Zn
C H N O Cd
mmol) was stirred in a DMF/H O mixed solvent (5 mL, v/v: 4/1).
37 34
6
9
2
37 32
6
8
2
2
Then the mixture was transferred and sealed in a Teflon reactor (20
mL) and heated at 120 °C for 3 days. Colorless crystals of 1 were
isolated in 47% yield after being cooled to room temperature. Anal.
Calcd for C41.5H48.5N O Zn : C, 50.70; H, 4.97; N 10.68%. Found:
837.44
913.48
293(2)
293(2)
triclinic
monoclinic
7.5
12.5
2
P2 /n
1
P1
̅
−1
C, 50.65; H, 4.98; N, 10.65%. IR (KBr pellet, cm ): 3286 (w), 3177
w), 1683 (w), 1662 (w), 1608 (s), 1584 (s), 1518 (m), 1498 (w),
393 (w), 1354 (s), 1277 (w), 1199 (w), 1188 (w), 1138 (w), 1088
w), 1007 (w), 984 (w), 955 (w), 926 (w), 886 (w), 857 (w), 792 (s),
13.385(2)
13.338(2)
25.365(4)
90
10.362(2)
10.417(2)
21.282(4)
78.838(3)
84.996(3)
76.052(3)
2185.2(7)
2
(
1
(
6
b/Å
c/Å
α/°
β/°
γ/°
volume/Å3
71 (w), 643 (w), 576 (w), 480 (m).
93.990(3)
90
Preparation of [Cd (L)(2,6-NDC) ]·1.5DMF·2H O (2). The title
2
2
2
complex was achieved by the same procedure used for synthesis of 1,
except that Cd(ClO ) ·6H O (41.9 mg, 0.1 mmol) was utilized instead
4517.1(12)
4
4
2
2
of Zn(ClO ) ·6H O. Yellow block crystals of 2 were achieved in 40%
Z
4
2
2
yield. Anal. Calcd for C41.5H46.5N O Cd : C, 47.06; H, 4.43; N,
−3
7.5
11.5
2
D /g cm
μ/mm−1
1.231
1.388
c
−1
9
3
1
.92%. Found: C, 47.12; H, 4.38. N, 9.90%. IR (KBr pellet, cm ):
317 (m), 3264 (m), 1674 (s), 1606 (s), 1549 (s), 1526 (w), 1493 (s),
397 (s), 1356 (s), 1279 (m), 1225 (w), 1198 (w), 1138 (w), 1067
w), 998 (w), 978 (w), 791 (s), 670 (m), 572 (w), 479 (m), 446 (m).
Procedures for Cycloaddition of CO with Epoxides. All the
reactions were performed under carbon dioxide atmosphere unless
otherwise stated. The reactions with corresponding catalyst were
carried out using sealed test tubes (10 mL) with magnetic stirrers. A
1.114
1.024
F(000)
1720
912
reflections collected
unique reflections
parameters
restraints
28573
10357
525
12303
7641
(
2
478
31
0
GOF
1.054
1.067
rubber bladder containing CO (0.1 MPa) was used to control the
R1
R1 = 0.0583
R1 = 0.0419
2
,
ab
reaction tube pressure. The cycloaddition reactions were checked by
thin-layer chromatography (TLC) using silica gel plates (GF254).
After being cooled to room temperature, the gas in the reaction tube
was released slowly. The final target products were isolated using flash
chromatography (EtOAc/n-hexane = 1:3).
wR [I > 2σ (I)]
wR = 0.1627
2
wR = 0.1222
2
2
R1
R1 = 0.1025
R1 = 0.0526
wR (all data)
wR = 0.1853
wR = 0.1393
2
2
2
a
b
2
2
2 1/2
R = ∑∥F | − |F ∥/∑|F |. wR = |∑w(|F | − |F | )|/∑|w(F ) |
where w = 1/[σ (F ) + (aP) + bP]. P = (F + 2F )/3.
,
1
0
c
0
2
0
c
0
2
2
2
2
2
c
0
0
RESULTS AND DISCUSSION
■
2
Crystal Structure of [Zn (L)(2,6-NDC) (H O)]·1.5DMF·
noncoordinated DMF molecules per formula of 1. After these
2
2
2
H O (1). Crystal structural analysis revealed that 1 crystallizes
solvent molecules were removed, the void volume is
approximately 1248.8 Å per 4517.2 Å unit cell, and the void
ratio is found to be 27.6%.
2
3
3
in monoclinic space group P2 /n (Table 1) and the asymmetric
1
unit of 1 contains two crystallographically independent Zn(II)
2−
atoms, one ligand L, two 2,6-NDC , and one coordinated aqua
molecule. As exhibited in Figure 1a, Zn1 is six-coordinated by
three chelating N atoms (N1, N2, and N3) from one L and
Crystal Structure of [Cd (L)(2,6-NDC) ]·1.5DMF·2H O
2
2
2
(2). When Cd(ClO ) ·6H O was used instead of Zn(ClO ) ·
4
2
2
4 2
6H O without a change of other reaction conditions, 2 with a
2
three carboxylate O ones (O1, O2, and O3) from two different
2
different structure was isolated. The results of structural analysis
,6-NDC2 ligands to form distorted octahedral coordination
−
show that 2 crystallizes in the triclinic space group P1
rather
̅
geometry, while Zn2 is surrounded by three carboxylate O
than monoclinic P2 /n in 1 (Table 1). As shown in Figure 2a,
1
2−
atoms (O4, O6, and O8) from three 2,6-NDC moieties and
one O (O1W) from coordinated aqua molecule to give a
distorted tetrahedral coordination geometry. The Zn−N bond
lengths fall in the range of 2.059(4)−2.353(3) Å, and the Zn−
O ones are from 1.933(3) to 2.552(3) Å (Table S1 in
Supporting Information), which are well-matched to those in
the asymmetric unit of 2 has two crystallographically
independent Cd(II) atoms. Cd1 is surrounded by N O
3
3
coordination donor set, comprised of three multiamine N
atoms (N1, N2, and N3) from L and three carboxylate O ones
2
−
(O1, O2, and O3A) from two distinct 2,6-NDC , while Cd2 is
seven-coordinated by six O atoms (O3, O4, O5, O6, O7, and
1
8
2−
the reported Zn(II) complexes.
O8) from three carboxylate groups of three 2,6-NDC and
2
−
It is notable that 2,6-NDC in 1 presents three different
one triazole N (N6) from L to form distorted pentagonal
bipyramidal coordination geometry. The Cd−N and Cd−O
bond lengths are in the ranges of 2.251(5)−2.461(4) Å and
2.317(5)−2.499(4) Å, respectively (Table S1 in Supporting
Information), which are close to the Cd−N and Cd−O bond
distances appearing in the previously reported Cd(II) frame-
coordination modes (Figure S1 in Supporting Information).
2
−
2
1
1
1
1
0
1
1
0
2
(
,6-NDC ligands with (μ -η :η )-(μ -η :η ) and (μ -η :η )-
1
1
0
μ -η :η ) coordination modes connect Zn2 atoms to generate
a two-dimensional (2D) network (Figure 1b), while the one
1
1
1
1
1
1
with (μ -η :η )-(μ -η :η ) coordination mode links Zn1 atoms
19
to extend the 2D network into a three-dimensional (3D)
works.
In 2, 2,6-NDC ligands act as bridging linker with (μ -
2
2−
1
architecture with large channels of 14.38 × 30.87 Å (Figure
1
1
1
1
1
2
2
1
2
1
2
1
c). Subsequently, L uses its chelating N atoms to coordinate
η :η )-(μ -η :η ) and (μ -η :η )-(μ -η :η ) coordination modes
(Figure S2 in Supporting Information) to link Cd(II) to give a
3D Cd-NDC framework with channels possessing a diameter of
10.42 Å (Figure 2b). In addition, L acts as bridging ligand to
join two Cd(II) and fills into the channel of the Cd-NDC
framework to generate the final 3D net of 2 (Figure 2c,d). The
with Zn1 as terminal ligand and filled into the Zn-NDC 3D
architecture to give the final 3D framework of 1 with 15.9 ×
2
1
4.4 Å 1D channels (Figure 1d,e). The PLATON was utilized
to estimate the solvent molecule accessible volume since there
are one coordinated and two free water, and one and a half
B
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Figure 1. (a) Coordination environment of Zn(II) in 1 with ellipsoids drawn at the 30% probability level. Hydrogen atoms and noncoordinated
solvent molecules are omitted for clarity. (b) Zn2-NDC 2D network in 1. (c) 3D Zn-NDC architecture in 1. (d) Part of the 3D framework of 1. (e)
Space-filling view of the 3D structure of 1.
calculated void volume after the solvent molecules are removed
is 584.6 Å per unit cell with a void volume ratio of 26.8%.
PXRD and Thermal Stability. The phase purity of the
methylene blue (MB), and rhodamine B (RhB) (Figure S5 in
Supporting Information) were employed to examine the
adsorption abilities of 1 and 2.
3
bulky 1 and 2 was confirmed by powder X-ray diffraction
The desolvated sample 1′ or 2′ (10 mg) was suspended in
−1
(
PXRD) measurements, and the results are provided in Figure
aqueous solution of MO, MB, or RhB (10 mg L , 20 mL) at
25 °C under dark conditions, and UV−vis absorption
spectroscopy was used to monitor the dye adsorption. As a
result, 1′ exhibits better adsorption ability than 2′ for MO
compared with MB and RhB. MO was effectively removed after
20 h from aqueous solution in 1′ which was supported by the
color change from yellow to nearly colorless, and UV−vis
spectra at different time intervals indicated that the
concentration of MO in aqueous solution changed from the
S3 in the Supporting Information. The good consistency of the
PXRD patterns between the as-synthesized bulky sample and
the corresponding simulated one confirms the purity of 1 and
2. Thermogravimetric analysis (TGA) was involved in the
evaluation of the thermal stability of the frameworks. As shown
in Figure S4 in Supporting Information, 1 displays a 16.41%
weight loss from 30 to 220 °C, corresponding to the release of
the solvent including free and coordinated water and DMF
molecules (calcd 16.63%), and the framework starts to
decompose from about 300 °C. MOF 2 loses its weight of
initial 20 mg g− to 2 mg g (Figure 3a,b). Although the color
1
−1
variation of MO solution in 2′ was less obvious, it was still
−1
1
3.53% between 30−300 °C originated from the removal of the
producing a good adsorption amount (11.2 mg g ) for MO
(Table S2 in Supporting Information). For the MB and RhB
solutions, as shown in Figure 3c−f, the UV spectra of 1′ and 2′
indicated almost no uptake and color variation for the blue MB
noncoordinated solvent molecules (calcd 13.75%), followed by
the decomposition of the framework.
Dyes Adsorption. On the basis of the fact that there are
large void volumes (27.6% for 1; 26.8% for 2) in 1 and 2, dye
molecular adsorption in solution can be expected. Before
adsorption measurements, the solvent molecules in 1 or 2 were
exchanged by acetone for 48 h, then desolvation was performed
at 130 °C for 10 h, and the corresponding desolvated samples
solution (adsorption amount is 1 mg g− for 1′; 3 mg g for
1
−1
−1
2′) and rose RhB solution (adsorption amount is 1.2 mg g for
−1
1′; 1.5 mg g for 2′) (Tables S3 and S4 in Supporting
Information). The differences in adsorption properties of these
three dye molecules might result from the size fitting between
the channels of the framework and the dye molecules. The
better adsorption ability of 1′ over 2′ toward MO could be
attributed to the appropriate pore size of 1′. In addition to the
molecular size, electrostatic interactions between the frame-
1
′ and 2′ were obtained. The exclusion of solvent molecules
and the maintaining of the framework were confirmed by TG
and PXRD data (Figures S3 and S4 in Supporting
Information). Dye molecules such as methyl orange (MO),
C
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Figure 2. (a) Crystal structure of 2 with ellipsoids drawn at the 30% probability level. For clarity, hydrogen atoms, free DMF and water molecules are
omitted. (b) 3D Cd-NDC architecture in 2. (c) 3D framework of 2. (d) Space-filling view of the 3D structure of 2.
works and dye molecules may also contribute to selectively
adsorption of dye molecules. The electrostatic interactions
between the triazole group of L in 1′ and the anionic dye MO
might be helpful for adsorption, while in the case of MB, much
less adsorption was observed probably due to the cationic
hysteresis loop in the CO sorption profiles and incomplete
2
22
desorption imply strong adsorbate−adsorbent interactions. It
is noteworthy that 1′ exhibited type-I N sorption isotherms at
2
3
−1
77 K with a value of 20.54 cm g , but almost no N
2
adsorption was observed for 2′ at 77 K. The Brunauer−
2
0
charge of MB.
Emmett−Teller (BET) surface area of 1′ calculated from the
2
−1
3
To further understand the intrinsic of dye adsorption, kinetic
studies were carried out. Typically, MO was employed as a
representative dye to examine the adsorption characteristics of
N sorption data is 79 m g with a pore volume of 0.03 cm
2
−
1
g . According to Horvath−Kawazoe (HK) model, the pore
size distribution curve based on N adsorption isotherm at 77 K
2
1
′ and 2′, and the results are given in Figures S6 and S7 in
shows the main size range of 12.4 Å (Figure S10 in Supporting
Information), agreeing with that of the crystal structure.
As we know, the separation of CO from CH in the
Supporting Information. The adsorption kinetic studies were
performed at 25 °C under neutral conditions. Figures S8 and
S9 in Supporting Information show the adsorption kinetics
curves for 1′ and 2′ as a function of time. 1′ shows better
uptake than 2′ to MO and is best fitted by a pseudo-first-order
model rather than a pseudo-second-order, while the adsorption
of MO by 2′ is closely in accord with a pseudo-second-order
2
4
precombustion process for natural gas is essential because of
23
the pipeline corrosion caused by acidic CO2. Therefore, the
CO and CH adsorption isotherms at the 273 and 298 K
2
4
under 1 bar were tested. As shown in Figure 4b,d, the maximal
sorption values of 1′ at ambient pressure for pure CO and
2
2
21
3
−1
3
kinetic process based on the good R value (Table 2).
CH are 21.34 and 8.61 cm g at 273 K; 11.17 and 0.08 cm
4
−
1
Gas Adsorption. The porosity of the frameworks further
g
at 298 K, respectively. For 2′, the corresponding values at
inspired us to investigate their gas uptake capacities. The
ambient pressure for pure CO and CH are 13.83 and 2.06
2 4
3
−1
3
−1
sorption performances of the activated samples 1′ and 2′ for N
cm g at 273 K; 9.30 and 0.04 cm g at 298 K, respectively.
Apparently, the results imply that 1′ and 2′ can selectively
adsorb CO over CH at 273 and 298 K.
2
at 77 K, CO at 195, 273, and 298 K, and CH at 273 and 298
2
4
K, are discussed below.
2
4
As shown in Figure 4a,c, the amounts of CO uptake for 1′
In the interest of evaluating the separation abilities of 1′ and
2′ for CO at different temperature, the CO /CH selectivity
2
3
−1
and 2′ are 41.95 and 60.66 cm g at the 195 K under 1 bar
2
2
4
and exhibited typical type-I gas uptake isotherms. The
for CO −CH mixtures at a general feed composition of landfill
2
4
D
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Figure 3. Adsorption capability of 1′ and 2′ toward MO (a) and (b), MB (c) and (d), and RhB (e) and (f) in an aqueous solution.
Table 2. Characteristic Parameters of the Adsorption of MO
high CO /CH selectivities of 32.6, 40.1, and 42.5 at 273 K,
2 4
for 1′ and 2′
28.6, 33.8, and 35.7 at 298 K for the mixtures with 50, 10, and
5
% CO components, respectively. The values of 2′ lie in the
2
model
Parameters
1′
2′
11.2
upper region of the reported MOFs (Table S5 in Supporting
adsorption
kinetic
pseudo-first-order q , (mg g−1) 19.5
e Exp
Information), which are comparable to those of [Zn(mtz)2],
q , (mg g−1)
UTSA-49, and [Co (tzpa)(OH)(H O) ] but surpass the values
19.1
11.3
2
2
2
e Cal
25
k1 (h−1)
R2
reported in major MOFs under similar conditions.
The significant selectivity of 1′ and 2′ for CO over CH and
0.1116
0.9799
0.086
0.9207
11.4
2
4
pseudo-second-
order
qe,Exp (mg g−1) 19.8
N is attributed to the existence of multiple CO -philic sites in
2 2
channels such as amino groups and the open metal sites, which
form specific interactions with CO2 due to the larger
quadrupole moment and higher polarizability value of CO2
qe,Cal (mg g−1)
19.1
11.3
k2
0.0114
0.0213
1
(
g mg− h−1
)
R2
relative to that of CH and N . To determine the binding
4
2
0.9272
0.9528
affinity, the adsorption enthalpies (Q ) for CO were calculated
st
2
by the virial model using the data of CO isotherms at 273 and
gas (CO /CH = 50:50) and natural gas (CO /CH = 10:90
2
2
4
2
4
2
98 K (Figures S13 and S14 in Supporting Information). The
and 5:95) was analyzed using the ideal adsorbed solution
theory (IAST) model (Figures S11 and S12 in Supporting
values given in Table 3 were estimated from the CO uptake at
2
2
4
the lowest measured loading. For 1′ and 2′, the initial Q values
Information). As shown in Figure 5a−d, the CO /CH
st
2
4
selectivities of 1′ at 100 kPa are 3.4, 2.5, and 3.4 at 273 K;
.1, 2.5, and 2.5 at 298 K for the mixtures with 50, 10, and 5%
CO components, respectively, while 2′ at 100 kPa displays
of adsorption enthalpies were determined as 23.3 and 28.1 kJ
−
1
6
mol , which are reasonable values compared with the
previously reported MOFs under the same conditions (Table
2
E
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Figure 4. Adsorption isotherms of N at 77 K, CO at 195, 273, and 298 K and CH at 273 and 298 K for 1′ (a) and (b), 2′ (c) and (d) (filled shape,
2
2
4
adsorption; open shape, desorption).
Figure 5. CO /CH selectivity for CO /CH binary mixtures with CO /CH = 50/50 (a), CO /CH = 10/90 (b), and CO /CH = 5/95 (c) CO ,
2
4
2
4
2
4
2
4
2
4
2
respectively. (d) Comparison of selectivity sorption at 100 kPa.
26
S6 in Supporting Information). The higher Q values indicate
Catalytic Cycloaddition of CO with Epoxides. MOFs
st
2
the stronger interactions between the adsorbed gas molecules
and the frameworks. Adsorption enthalpies decrease with
increasing loading, implying that there are preferentially
as heterogeneous catalysts for chemical fixation of CO to cyclic
2
carbonates have been demonstrated but under high pressure
28
(>2 MPa). TG and PXRD curves of desolvated sample 1′
27
binding sites in the frameworks.
showed that the coordinated aqua molecules were completely
F
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2
9
Table 3. CO and CH Uptakes of 1′ and 2′ and Heat of
previously (Table S7 in Supporting Information). Small
decreases in the conversion were observed when the methyl
was substituted by electron-withdrawing substituents (1b and
2
4
Adsorption Values of CO
2
CH
−1
4
a
3
−1
a
3
−1
1c), and the TON and TOF values are 2300 and 1150 h for
CO uptake /cm g
uptake /cm g
2
1
2
b and 2225 and 1113 h− for 2c, respectively. It is noteworthy
273 K
298 K
Qst (kJ mol−1)
273 K
298 K
that these TON and TOF values are also larger than the ones
for the previously reported MOF catalysts (Table S8 in
1
2
′
′
21.34
13.83
11.17
9.30
23.3
28.1
8.61
2.06
0.08
0.04
30
Supporting Information).
a
At 0.1 MPa.
Considering the large pore width (12.4 Å) calculated by the
HK method based on the N sorption data of 1′. Therefore, to
2
removed, and the framework maintained well (Figures S3 and
confirm the selective accommodation and activation of
reactants by 1′, epoxides with large size were used to identify
the selectivity of 1′, and the catalytic reactions were performed
under the optimized conditions (Table 4, entries 4−7).
Substrate tert-butyl glycidyl ether (1d) gave the corresponding
product (2d) in good yield (91%) with TON and TOF of 2275
S4 in Supporting Information). The high CO uptake and the
2
exposed sites of Zn(II) in the framework of 1′ encourage us to
examine its activity as heterogeneous catalyst for the cyclo-
addition reactions of CO with epoxides.
2
The reactions were performed with epoxide (10 mmol),
−1
CO , and NBu Br (1.20 mol %) as cocatalyst at 80 °C and
2
4
and 1517 h , respectively. Glycidyl phenyl ether (1e) almost
completely converted into the corresponding product (2e)
within 1 h with the corresponding TOF value of 2450 h− per
Zn2 cluster. Notably, the conversion of 1e to 2e gives the
highest TOF value within the reported MOF catalysts (Table
atmospheric pressure (0.1 MPa), while the loading of the
1
catalyst is 0.04 mol % based on the Zn2 ions. Remarkably, 1′
exhibits high efficiency for the CO cycloaddition especially
2
with small-sized epoxides (Table 4, entries 1−3); for example,
the conversion of 1,2-epoxybutane (1a) to 1,2-butylene
carbonate (2a) finished within 2 h. The turnover number
30,31
S9 in Supporting Information).
The width of the substrate,
substituted by naphthalene (1f), was further increased, and the
corresponding product 2f could also be detected with the
(
1
TON) and turnover frequency (TOF) values are 2400 and
200 h , respectively, which are larger than the ones reported
−1
−1
corresponding TOF value of 510 h . However, further increase
a
Table 4. Catalyzed Coupling of CO with Epoxides
2
a
b
Reaction conditions: Substrates (10 mmol), NBu Br (0.12 mmol, 1.2 mol %), catalyst 1′ (0.004 mmol, 0.04 mol %, based on Zn2). Isolated yield.
4
c
d
TON = (moles of product)/(moles of catalyst). TOF = TON/T.
G
DOI: 10.1021/acs.inorgchem.7b03099
Inorg. Chem. XXXX, XXX, XXX−XXX

Inorganic Chemistry
Article
of the substrate size, substituted by triphenylmethyl (1g), gave
no desired product because of the large size (over 12.4 Å) and
the large steric effect from the triphenylmethyl group. The
results are in accordance with the fact that this substrate-
selective reaction occurs in the channels rather than the surface
of 1′.
AUTHOR INFORMATION
Corresponding Authors
(Y.L.) E-mail: luyi@nju.edu.cn. Fax: +86 25 89682309.
(W.-Y.S.) E-mail: sunwy@nju.edu.cn.
ORCID
Yi Lu: 0000-0002-8767-7801
Wei-Yin Sun: 0000-0001-8966-9728
Notes
■
*
*
The CO cycloaddition with 1,2-epoxybutane was used to
2
examine the recyclability of the catalyst, and the results show
that 1′ can be reused at least 3 times without remarkable
change of its catalytic activity (Figure S15 in Supporting
Information). In addition, PXRD and IR (Figure S16 in
Supporting Information) data confirm no structural variation of
The authors declare no competing financial interest.
ACKNOWLEDGMENTS
■
1
′ after the catalytic reactions.
We gratefully acknowledge the National Natural Science
Foundation of China (Grant Nos. 21331002, 21573106, and
21671097) and the National Basic Research Program of China
(Grant No. 2017YFA0303500) for financial support of this
work. This work was also supported by a Project Funded by the
Priority Academic Program Development of Jiangsu Higher
Education Institutions.
A possible catalytic reaction mechanism is given in Figure
S17 in Supporting Information. According to the previously
8
,32
reported works,
the cycloaddition reaction of epoxide with
CO starts from the binding of the epoxide with the open site
2
of Zn(II) in 1′, in which the Lewis acidic Zn(II) can activate
epoxide toward nucleophilic substitution. In the second step,
−
the epoxy ring is opened by attacking of Br originated from
the cocatalyst NBu Br to the terminal C atom of the epoxide.
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DOI: 10.1021/acs.inorgchem.7b03099
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