A Cationic Zinc-Organic Framework with Lewis Acidic and Basic Bifunctional Sites as an Efficient Solvent-Free Catalyst: CO2 Fixation and Knoevenagel Condensation Reaction

Article abstract of DOI:10.1021/acs.inorgchem.8b01713

A novel two-dimensional cationic framework [Zn₂(TCA)(BIB)_2.5]·(NO₃) (1) (H₃TCA = tricarboxytriphenyl amine, BIB = 1,3-bis(imidazol-1-ylmethyl)benzene) was successfully achieved. Compound 1 not only presents a mo

Full text of DOI:10.1021/acs.inorgchem.8b01713

Article
Cite This: Inorg. Chem. XXXX, XXX, XXX−XXX
pubs.acs.org/IC
A Cationic Zinc−Organic Framework with Lewis Acidic and Basic
Bifunctional Sites as an Efficient Solvent-Free Catalyst: CO Fixation
2
and Knoevenagel Condensation Reaction
†
†
Cheng Yao, Shaolin Zhou, Xiaojing Kang, Yang Zhao, Rui Yan, Yan Zhang, and Lili Wen*
Key Laboratory of Pesticide & Chemical Biology of Ministry of Education, College of Chemistry, Central China Normal University,
Wuhan, 430079, China
*
S Supporting Information
ABSTRACT: A novel two-dimensional cationic framework
[
Zn (TCA)(BIB) ]·(NO ) (1) (H TCA = tricarboxytri-
2 2.5 3 3
phenyl amine, BIB = 1,3-bis(imidazol-1-ylmethyl)benzene)
was successfully achieved. Compound 1 not only presents a
moderate affinity toward CO molecules, but it also displays
2
good catalytic performance and substrate selectivity toward
both CO2 conversion with epoxides and Knoevenagel
condensation under solvent-free environments, taking advant-
age of the Lewis acidity endowed by lower four-coordinated
Zn(II) centers and Lewis basicity originated from the amines
3−
within TCA . More importantly, the bifunctional heteroge-
neous catalyst compound 1 shows easy recovery and reuse
without an obvious decrease of activity. Strikingly, compound
1
exhibits good catalytic efficiency for CO coupled with propylene oxide forming propylene carbonate even at ambient
2
temperature under 1 atm pressure. To the best of our knowledge, compound 1 is presented to be the first cationic MOF holding
great promise as a heterogeneous solvent-free catalyst toward both CO epoxidation and Knoevenagel condensation reaction.
2
INTRODUCTION
Knoevenagel reaction, the Lewis basic sites would support the
formation of a C−C bond between aldehydes or ketones and a
methylene group containing active hydrogen atoms. Moreover,
chemical and thermal durability is a prerequisite for heteroge-
neous catalysts in practical implementation.
■
Carbon dioxide (CO ) is suspected to be the primary
greenhouse gas causing global warming and a consequent series
of environmental problems over the past decades. In this
2
1
regard, CO activation and efficient conversion into value-added
2
Taking inspiration from the above consideration, by employ-
chemicals are imperative and attractive, given that CO is
2
ing the ligands tricarboxytriphenyl amine (H TCA, Scheme S1)
3
recognized to be a nontoxic, economic, and renewable C1
2
and 1,3-bis(imidazol-1-ylmethyl)benzene (BIB) to assemble
with Zn(II) ions, a novel two-dimensional (2D) cationic
framework [Zn (TCA)(BIB) ]·(NO ) (1) was successfully
building block. Particularly, the coupling of epoxides with CO
2
into cyclic carbonates is regarded as one of the most promising
2
2.5
3
protocols for CO utilization in terms of green chemistry and
2
3
achieved. Remarkably, compound 1 incorporates lower four-
coordinated Zn(II) centers functioning as Lewis acidic sites and
the accessible N-donor of triphenylamine acting as Lewis basic
atomic economy. The target cyclic carbonates have extensive
4
applications as chemical intermediates and battery electrolytes.
Meanwhile, Knoevenagel condensation, as an important C−C
coupling reaction, has been extensively utilized for the
preparation of fine chemicals and pharmaceutical products.
Owing to permanent porosities, facile tunability, and
functional pore surface, metal−organic frameworks (MOFs)
might be ideal catalysts in a heterogeneous system. Up to now,
centers and CO -philic groups. Impressively, as an ideal
2
5
heterogeneous Lewis acid/base bifunctional catalyst, compound
1 offers great performance and substrate selectivity as well as
satisfactory recyclability for both the chemical transformation of
CO2 to cyclic carbonates and Knoevenagel condensation
reactions under mild conditions. More interestingly, 1 is able
6
7
,8
even though a variety of MOFs were demonstrated as fine
9
−13
to catalyze the cycloaddition of propylene oxide with CO even
2
catalysts for CO chemical fixation
or Knoevenagel
2
1
4−18
under ambient pressure and temperature with good efficiency.
Until now, compound 1 represents the first cationic MOF-based
condensation,
there is still a need to rationally construct
highly effective MOFs as catalysts for such transformations
especially under mild reaction conditions, so as to lower the
energy consumption and production costs. In principle, a
heterogeneous solvent-free catalyst toward both CO epox-
2
idation and Knoevenagel condensation.
promising heterogeneous catalyst for CO epoxidation features
2
selective CO capture capacity as well as abundant Lewis/
Received: June 21, 2018
2
Brønsted acid or base to activate epoxide/CO . In the case of
2
©
XXXX American Chemical Society
A
DOI: 10.1021/acs.inorgchem.8b01713
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Inorganic Chemistry
Article
EXPERIMENTAL SECTION
■
Synthesis of [Zn (TCA)(BIB) ]·(NO ) (1). A mixture of H TCA
2
2.5
3
3
(
(
4.9 mg, 0.01 mmol), BIB (11.90 mg, 0.05 mmol), Zn(NO )·6H O
3
2
14.8 mg, 0.10 mmol), N,N′-dimethylacetamide (DMA, 2 mL), and
EtOH (1 mL) was placed in a 5 mL glass vial, which was heated at 110
C for 2 days. After cooling to ambient temperature, yellowish block
crystals were collected with a yield of 42% (based on H TCA). FT-IR
°
3
−
1
(
KBr, cm ): 3431m, 3128w, 1599s, 1523w, 1378s, 1315s, 1276m,
1169m, 1093m, 1023w, 948w, 840w, 784m, 721w, 658m, 524w, 442w.
RESULTS AND DISCUSSION
Crystal Structure. Compound 1 crystallizes in the
orthorhombic space group Pnnm (Table 1). The asymmetric
■
Table 1. Crystallographic Data for Compound 1
1
empirical formula
formula weight
cryst syst
space group
a (Å)
C H N O Zn
56 47 12 9
2
1162.84
orthorhombic
Pnnm
23.3735(9)
25.8030(11)
22.9869(9)
13863.5(10)
8
b (Å)
c (Å)
3
V (Å )
Z
D (g cm−3)
1.114
0.746
c
μ (mm−1)
no. of reflns collected/unique
R1 [I > 2σ (I)]
68557/12540
0.0623
wR (all data)
2
0.1823
II
unit of 1 includes two crystallographically independent Zn ions,
3
−
one TCA anion, two and a half BIB ligands, as well as two
−
NO3 counteranions respective with a half occupancy (Figure
II
S1a). Both Zn ions exhibit a similar tetrahedral coordination
sphere but different coordination environments. As shown in
Figure 1a, the Zn1 was surrounded by two carboxylate O atoms
from different TCA3− moieties and two N atoms from separate
BIB bridges, whereas the Zn2 was coordinated by one
carboxylate O atom and three N atoms from two distinct BIB
linkers. The Zn−O and Zn−N bond distances are in the range
1
(
.963(3)−1.982(3) and 1.984(4)−2.036(4) Å, respectively
Table S1). Each TCA3 anion is attached to three Zn ions in
−
I
I
monodentate coordination mode, and each BIB is linked to two
II
Zn centers with two terminal imidazole moieties taking a cis-
configuration, affording a 2D cationic skeleton charge-balanced
−
by free NO3 anions (Figure 1b). Compound 1 has open
2
channels along the a axis of ca. 6.5 × 7.9 Å (regardless of the
−
van der Waals radii), which were filled with guest NO3 anions
Figure 1. Compound 1: (a) the coordination environment around ZnII
and solvent molecules. The total solvent-accessible space
(
(
the H atoms are omitted for clarity); (b) the 2D cationic framework;
c) the topological representation: cyan, purple, and blue spheres
3
accounts for ∼29.5% (4084.5 Å ) per unit cell by PLATON
1
9
3−
II
analysis. By simplification of TCA moieties and Zn2 as well
represent Zn1, Zn2, and N1 nodes, respectively. Symmetry code: #1
−1/2 + x, 3/2 − y, 3/2 − z.
II
as Zn1 centers as 3-, 3-, and 4-connected nodes, respectively,
the skeleton of 1 adopts a (3, 3, 4) trinodal net with the
topological point symbol of (6 )(6 .8)(6 .8.10) (Figure 1c).
The resulting adjacent 2D framework is further cross-linked via
π···π interactions between the benzene rings of BIB linkers, with
separations of 3.589(4) and 3.765(4) Å, which might contribute
to the stabilization of compound 1 (Figure S1b).
2
0
3
2
4
(Figure S2). Moreover, compound 1 still retains single
crystallinity after solvent treatment (cyclohexane, toluene,
CH Cl , isopropanol, acetone, EtOH, CH OH, CH CN,
2
2
3
3
DMF, and H O) for 72 h under room temperature.
2
Gas Adsorption. The PXRD profile of the fresh sample at
ambient temperature is coincident with the simulated one from
the single-crystal data, indicative of good phase purity of bulk 1
Furthermore, no obvious loss of crystallinity for compound 1
was found in a wide pH range of 2−14 (Figure S3). The high
chemical stability of compound 1 may benefit from the increased
B
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Inorganic Chemistry
coordinative bond strength between the Zn and imidazole-
based BIB ligand. The as-synthesized 1 was soaked in
methanol, and then, it was treated by supercritical CO2
activation. The desolvated sample’s PXRD pattern suggested
that the pristine structure was preserved after the activation
Article
II
nature. The Brunauer−Emmett−Teller surface area of 1 was
21
2
fitted to be ∼504 m /g.
For compound 1, the maximum CO uptakes are 72.8 (273
K) and 48.4 cm /g (298 K) under 1 bar, as well as very little N
2
3
2
capture under the same conditions (Figure 2b). In order to gain
more insights into the interaction between the adsorbate and the
framework, the adsorption heat of CO (Q ) for 1 at zero
process (Figure S2). As shown in Figure 2, the CO sorption
2
2
st
isotherm at 195 K of the activated 1 featured a typical type I
adsorption isotherm, verifying the permanent microporous
2
2
coverage was found to be 29.0 kJ/mol by a virial method,
based on the sorption isotherms at 273 and 298 K (Figure 2c).
The observed value surpassed those of recently reported cationic
MOFs, such as [Zn (L)(bpb) ]·(NO )·(DMF) ·(H O) (23.5
2
2
3
3
2
4
kJ/mol), [Zn (L)(dpe) ](NO )·(DMF) ·(H O) (20.5 kJ/
mol) (L = 1,3-bis(3,5-dicarboxyphenyl)imidazolium, bpb =
,4-bis(4-pyridyl)benzene, dpe = 1,2-di(4-pyridyl) ethylene),
2
2
3
3
2
2
23
1
24
and FJU-14-BF (18.8 kJ/mol). The strong charge-induced
4
forces between the positively charged host and guest CO
2
2
5
molecules alongside the interactions between the Lewis
26
basic amines involved in the framework of 1 and the acidic
CO molecules within the pores are critical for the considerable
2
uptake of CO2.
Catalytic Cycloaddition of CO to Epoxides. Noticeably,
2
despite no open metal sites in the channels, the lower four-
coordinated Zn(II) centers within the cationic framework of 1
could behave as available Lewis acidic sites. On account of the
high affinity to CO and the incorporation of Lewis acid sites of
2
Zn(II) ions as well as the superior chemical stability of the MOF,
detailed catalytic performance of compound 1 in CO chemical
2
fixation was exploited both at 1 and 10 atm, respectively. The
CO2 cycloaddition with epichlorohydrin at atmospheric
pressure has been utilized as a model reaction to screen the
optimal conditions. After detailed investigations, the optimum
conditions were set at 80 °C for 4 h with compound 1 (0.01
mmol) and tetra-n-tertbutylammonium bromide (nBu NBr,
4
0
.02 mmol) as cocatalysts under a solvent-free environment
(
Table S2). It should be noted that almost no cyclic carbonates
were detected when pure 1 was chosen as catalyst (Table S3,
entry 1), while nBu NBr alone led to a low catalytic efficiency
4
with 34% yield (Table S3, entry 2) under the employed
experimental conditions. Strikingly, in the presence of
compound 1 together with n-Bu NBr as a binary catalytic
4
system, epichlorohydrin was almost completely converted to the
corresponding carbonate (>99% yield, Table S3, entry 3),
highlighting the remarkable synergistic effect of 1 and nBu NBr
4
in the promoting of the CO epoxidation reaction under mild
2
conditions. Except for the cyclic carbonates, no other side
products are found, suggesting the exclusively high selectivity of
compound 1.
The catalytic generality over compound 1 can be further
extended to several typical epoxide substrates with variable
dimensions (Table 2). Under the optimized conditions, the
chemical fixation of CO to the smaller substrates, such as
2
epibromohydrin and 1,2-epoxyhexane, gave decent yields
comparable to that of epichlorohydrin (>99% yield, Table 2,
entries 1−3). Nevertheless, in the case of bulky substrates, such
as 1,2-epoxyethylbenzene and glycidyl phenyl ether, the yields of
the desired products were sharply reduced to 51.3 and 59.5%,
respectively (Table 2, entries 4 and 5). The poor catalytic
efficiency toward larger substrates may be attributed to the
higher steric hindrance of the reactants with limited diffusion
27
through the channels of compound 1 during the reaction.
These results manifest that compound 1 exhibits a size-selective
catalysis to a certain degree. Notably, as illustrated in Figure 3,
significantly improved yields of the respective carbonates for the
Figure 2. (a) CO adsorption isotherm for 1 at 195 K. (b) CO and N
2
sorption isotherms of 1 at 273 and 298 K. (c) Isosteric heat of
2
2
adsorption for CO in 1.
2
C
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Article
Table 2. Cycloaddition of CO and Epoxides Catalyzed by
Compound 1 at 1 atm
(0.1 mmol) with 10 atm pressure of CO at 80 °C. As illustrated
2
2
a
in Table 3, the substrates epichlorohydrin and epibromohydrin
were completely transformed to the corresponding carbonates
within 4 h with a turnover number (TON) of 250. Strikingly, the
1,2-epoxyethylbenzene and glycidyl phenyl ether (Table 3,
entries 4 and 5) were also catalyzed over compound 1 in high
conversion rates of 95.5 and 96.1% after 4 h, with a TON of 225
and 230, respectively. Remarkably, as compared to the CO2
epoxidation that happened at 1 atm (Table S4), about 4 times of
the TON values for 1,2-epoxyethylbenzene and glycidyl phenyl
ether were reached with the same amount of catalyst 1 at 10 atm,
revealing that the increasing CO pressure was beneficial for the
2
epoxidation reaction.
Easy separation and activation as well as recyclability are of
paramount importance for heterogeneous catalyst. Catalyst
compound 1 recovered from the reaction mixture was
thoroughly washed with CH Cl and air-dried and then used
2
2
as a catalyst without additional activation treatments. Further,
the reusability of compound 1 was examined, using epichlor-
ohydrin as the example at both 1 and 10 atm. Within four
catalytic runs, high yields of 99.5−98% (1 atm) and 99.5−87%
(
(
10 atm) were maintained, suggesting retention of the activity
Figure S7). Moreover, PXRD analyses evidence the structural
integrity of compound 1 after at least four times (Figure S8).
Remarkably, at 1 atm of CO atmosphere and ambient
2
temperature, compound 1 reveals great catalytic performance
for CO coupled with propylene oxide forming propylene
2
a
Reaction conditions: epoxide (2 mmol), compound 1 (0.01 mmol),
carbonate, with a yield of 83% for 48 h and a TON of 207
(Figure 4), which is high and comparable to that for USTC-253-
and nBu NBr (0.02 mmol), CO (1 atm), 80 °C.
4
2
28
TFA with Lewis/Brønsted acid sites under similar conditions
but lesser amounts of catalyst in our case. The results showed 1
not only could efficiently catalyze the CO chemical fixation
2
under high temperature and a high/atmospheric pressure
environment, but it also presents high performance under
ambient conditions, originating from the existence of Lewis acid
sites and high CO enrichment capability in 1. As far as we know,
2
only rare MOFs are capable of accomplishing CO cycloaddition
2
29
conversion under ambient temperature and pressure to date.
As illustrated in Scheme S2, a tentative synergistic catalytic
mechanism is proposed for the cycloaddition of epoxide and
CO into cyclic carbonate catalyzed by compound 1 and
2
nBu NBr.
4
Knoevenagel Condensation Reaction. Interestingly, the
Lewis base triphenylamine sites are uniformly located in the
framework of compound 1, which make it applicable for the
heterogeneous Knoevenagel condensation reaction. For a
typical experiment, benzaldedyde (1 mmol) and malononitrile
Figure 3. Yields of corresponding carbonates after 4 h (green) and 12 h
red) of reactions under 1 atm with compound 1 applied as catalyst.
(
(
2 mmol) along with the catalyst compound 1 (0.003 mmol)
larger substrates of 1,2-epoxyethylbenzene and glycidyl phenyl
ether were achieved, up to 90 and 96% with the unchanged
quantity of catalyst and reaction temperature but the reaction
time extending to 12 h.
As depicted in Figure S6, no further reaction was observed
after catalyst compound 1 was filtered off right after reaction for
proceeded at 60 °C for 1 h under solvent-free conditions, giving
a 99% yield of 2-benzylidenemalononitrile as the only product
−
1
with a high turnover frequency (TOF) of 167 h (Table 4, entry
1). In parallel studies, when the reaction proceeded without
compound 1, only trace conversion was achieved (Table S6,
entry 2). Besides, poor yields of 2-benzylidenemalononitrile
were achieved with Zn(NO ) ·6H O and ligands H TCA or BIB
1
h at 80 °C, confirming the catalytically active sites for CO2
3 2
2
3
conversion into cyclic carbonates located on 1. Additionally,
as catalysts (Table S6, entries 3−5). Those control experiments
clearly reveal that compound 1 played a crucial role in the
Knoevenagel condensation reaction.
inductively coupled plasma (ICP) results revealed no leaching of
II
Zn in this reaction system occurred, further verifying a typical
heterogeneous catalyst nature.
To further investigate the substrate scope, a series of
benzaldehyde derivatives with malononitrile were expanded
under identical conditions. It is generally accepted that the
electron-deficient benzaldehyde derivatives are more reactive
than those with electron-rich groups in the Knoevenagel
The CO epoxidation over compound 1 was also explored
2
under high pressure. In a typical procedure, the catalytic reaction
was carried out in an autoclave reactor using epoxides (10
mmol) as substrates, compound 1 (0.02 mmol), and nBu NBr
4
D
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Inorganic Chemistry
Article
a
Table 3. Cycloaddition of CO and Epoxides Catalyzed by Compound 1 at 10 atm
2
a
b
Reaction conditions: epoxide (10 mmol), compound 1 (0.02 mmol), and nBu NBr (0.1 mmol), CO (10 atm), 80 °C. Moles of epoxides
4
2
consumed per mole of Zn(II).
8
−11). The substrates of hexanaldehyde and cyclohexanecar-
baldehyde afforded the corresponding products in good yields of
3 and 90%, whereas 4-phenylbenzaldehyde and cinnamalde-
hyde only gave moderate yields of 77 and 58%. Moreover, after
5 min of the condensation reaction of benzaldehyde and
9
1
malononitrile, compound 1 was separated from the reaction
mixture, resulting in the complete shutdown of the reaction
(
Figure S9). The observation indicates that the catalysis over 1 is
heterogeneous.
Further, the recyclability of compound 1 was tested by
utilizing benzaldehyde as a substrate. Compound 1 was simply
collected by filtration after the completeness of the condensation
reaction and washed using methanol, which can be used for the
successive run. Notably, over 95% conversion of benzaldehyde
was kept even after four recycles. The results revealed that
compound 1 possesses easy recovery without losing obvious
activity (Figure S10a). At the same time, the PXRD patterns
corroborate that the skeleton of compound 1 remained
unaltered after recycles (Figure S10b).
Figure 4. Catalytic conversion of CO coupled with various epoxides
2
over compound 1. Reaction conditions: epoxide (20.0 mmol),
compound 1 (0.04 mmol), nBu NBr (2.00 mmol), CO (1 atm), 25
4
2
°C, 48 h.
To our knowledge, only scarce MOFs have been reported to
be capable of efficiently catalyzing Knoevenagel condensation
condensation because nucleophilic addition is considered as a
rate-determining step. As anticipated, benzaldehyde deriva-
14,31
under solvent-free conditions hitherto.
Inspiringly, com-
30
pound 1 presents superior catalytic activity with very limited
loading of catalyst under solvent-free environments (Table 5),
which could be a new valuable MOF family member to catalyze
Knoevenagel condensation reactions.
tives bearing electron-withdrawing groups (−Cl, −CN, −NO )
2
reached nearly full conversion (>99%) with the highest TOF
−
1
value of 167 h (Table 4, entries 2−4). In comparison, electron-
donating benzaldehyde derivatives (−CH , −CH CH ,
3
2
3
−
OCH ) obtained relatively lower yields of the corresponding
3
CONCLUSIONS
condensation products (Table 4, entries 5−7) varying from 95
to 78 to 60%. Evidently, the benzaldehyde derivatives gave a
decreased conversion in the order of −OCH < −CH CH <
■
In summary, by the self-assembly of the ligands H TCA and BIB
with Zn(II) ions, a novel 2D cationic framework [Zn (TCA)-
3
3
2
3
2
−
CH , which is reasonable, since −OCH is known to be of the
(BIB) ]·(NO ) (1) was successfully fabricated. Remarkably,
3
3
2.5
3
strongest electron-donating nature among them. Moreover,
hexanaldehyde, cyclohexanecarbaldehyde, 4-phenylbenzalde-
hyde, and cinnamaldehyde were also evaluated (Table 4, entries
compound 1 features Lewis acid Zn(II) and Lewis base
triphenylamine on the internal surfaces as well as good CO2
enrichment capability, thus enabling both CO epoxidation and
2
E
DOI: 10.1021/acs.inorgchem.8b01713
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Inorganic Chemistry
Article
a
Table 4. Knoevenagel Condensation Reaction of Benzaldehyde Derivatives with Malononitrile Catalyzed by Compound 1
a
b
Reaction conditions: aldehydes (1 mmol), malononitrile (2 mmol), compound 1 (0.003 mmol), 1 h, 60 °C. Moles of condensation product per
mole of tricarboxytriphenyl amine in compound 1 per hour.
Table 5. Summary of the Catalytic Activity toward Knoevenagel Condensation Reaction over Various MOFs
MOFs
catalyst (mol %)
solvent
temperature (°C)
time (h)
yield (%)
ref
compound 1
Cd (tipp)(bpdc) ]·(DMA)·(H O)
9
0.3
0.6
3
1
1
60
60
35
23
25
25
1
1
6
2
2
2
>99
>99
80.9
97
90
99
this work
[
14
15
32
33
34
3
2
2
FJI-C2
UiO-66-NH-RNH2
Zn (L)(H O) ]·(DMF) ·(H O) ]
toluene
toluene
[
CH Cl2
2
2
2
5
2
4
2
UiO-67-diamine
6
DMF
Knoevenagel condensation reaction with high activity and
substrate selectivity under solvent-free environments. Moreover,
the recyclability and truly heterogeneous nature of the catalyst
for the reactions have also been illuminated. Strikingly,
compound 1 herein can efficiently catalyze CO coupled with
2
propylene epoxide to afford propylene carbonate with a high
yield even under ambient conditions. To our knowledge,
compound 1 is the first cationic MOF as a promising
F
DOI: 10.1021/acs.inorgchem.8b01713
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Inorganic Chemistry
Article
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AUTHOR INFORMATION
Corresponding Author
E-mail: wenlili@mail.ccnu.edu.cn.
■
*
(7) (a) Lan, G.-X.; Zhu, Y.-Y.; Veroneau, S. S.; Xu, Z.-W.; Micheroni,
ORCID
D.; Lin, W.-B. Electron Injection from Photoexcited Metal-Organic
Framework Ligands to Ru-2 Secondary Building Units for Visible-
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Frameworks: Versatile Materials for Heterogeneous Photocatalysis.
Lili Wen: 0000-0002-8639-2978
Author Contributions
†
C.Y. and S.Z. contributed equally.
Notes
ACS Catal. 2016, 6, 7935−7947. (c) Corma, A.; García, H.; Llabres i
́
The authors declare no competing financial interest.
Xamena, F. X. Engineering Metal Organic Frameworks for Heteroge-
neous Catalysis. Chem. Rev. 2010, 110, 4606−4655. (d) Huang, Y.-B.;
Liang, J.; Wang, X.-S.; Cao, R. Multifunctional Metal−Organic
Framework Catalysts: Synergistic Catalysis and Tandem Reactions.
Chem. Soc. Rev. 2017, 46, 126−157.
ACKNOWLEDGMENTS
This work was granted financial support from the National
Nature Science Foundation of China (grants 21771072 and
■
(
8) (a) Jiao, L.; Wang, Y.; Jiang, H.-L.; Xu, Q. Metal−Organic
Frameworks as Platforms for Catalytic Applications. Adv. Mater. 2017,
703663. (b) Islamoglu, T.; Goswami, S.; Li, Z.-Y.; Howarth, A. J.;
2
1371065), Self-Determined Research Funds of CCNU from
the Colleges’ Basic Research and Operation of MOE (grant
1
CCNU17QN0020), and the 111 Project (grant B17019).
Farha, O. K.; Hupp, J. T. Postsynthetic Tuning of Metal−Organic
Frameworks for Targeted Applications. Acc. Chem. Res. 2017, 50, 805−
813. (c) Xiong, G.; Chen, X.-L.; You, L.-X.; Ren, B.-Y.; Ding, F.;
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