Design and Assembly of a Hierarchically Micro-and Mesoporous MOF as a Highly Efficient Heterogeneous Catalyst for Knoevenagel Condensation Reaction

Article abstract of DOI:10.1021/acs.cgd.0c00636

A 3D hierarchically micro-and mesoporous MOF, [Tb6(μ3-OH)8·(2-FBA)2·(H2O)6·(DCBA)2]·10DMF·4H2O (namely, Tb-DCBA), was successfully constructed by the coordination self-assembly process between H4DCBA linker and Tb6 hexanuclear cluster. By virtue of preferable physicochemical stability, high surface area, multiple porosity, and abundant amino functional groups, Tb-DCBA is not merely considered as a greatly potential heterogeneous catalyst for Knoevenagel condensation reaction, but also has remarkable repeatability for reusing at least four times. It is worth noting that micro-and mesoporous MOF is still an urgent and enormous challenge, because such MOFs are difficult to synthesize and determine precise structures, and always possess relatively poor stability to limit their practical applications. Hence, this work creates a scarce opportunity for a hierarchically micro-and mesoporous MOF for investigating its catalytic performance.

Full text of DOI:10.1021/acs.cgd.0c00636

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Article
Design and Assembly of a Hierarchically Micro- and
Mesoporous MOF as a Highly Efficient Heterogeneous
Catalyst for Knoevenagel Condensation Reaction
Kun Cai, Wenjun Tan, Nian Zhao, and Hongming He
Cryst. Growth Des., Just Accepted Manuscript • DOI: 10.1021/acs.cgd.0c00636 • Publication Date (Web): 09 Jun 2020
Downloaded from pubs.acs.org on June 14, 2020
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Design and Assembly of a Hierarchically Micro- and
Mesoporous MOF as a Highly Efficient
Heterogeneous Catalyst for Knoevenagel
Condensation Reaction
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Kun Cai,†, ‖ Wenjun Tan,†, ‖ Nian Zhao§ and Hongming He*,‡
†
Key Laboratory of Micro-Nano Materials for Energy Storage and Conversion of Henan
Province, Institute of Surface Micro and Nano Materials, College of Advanced Materials and
Energy, Xuchang University, Henan 461000, People’s Republic of China
‡
Tianjin Key Laboratory of Structure and Performance for Functional Molecules, College of
Chemistry, Tianjin Normal University, Tianjin 300387, People’s Republic of China
§
Institute for Advanced Materials, Hubei Normal University, Huangshi 435002, People’s
Republic of China
‖
Henan Joint International Research Laboratory of Nanomaterials for Energy and Catalysis,
Xuchang University, Xuchang, Henan 461000, People’s Republic of China
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ABSTRACT
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A
3D
hierarchically
micro-
and
mesoporous
MOF,
[Tb6(μ3-OH)8·(2-
9
FBA)2·(H2O)6·(DCBA)2]·10DMF·4H2O (namely Tb-DCBA), was successfully constructed by
the coordination self-assemble process between H4DCBA linker and Tb6 hexanuclear cluster. By
virtue of preferable physicochemical stability, high surface area, multiple porosity, and abundant
amino functional groups, Tb-DCBA is not merely considered as a greatly potential
heterogeneous catalyst for Knoevenagel condensation reaction, but also has remarkable
repeatability for reusing at least four times. It is worth noting that micro- and mesoporous MOF
is still an urgent and enormous challenge, because such MOFs are difficult to synthesize and
determine their precise structures, and always possess relatively poor stability to limit their
practical applications. Hence, this work creates a scarce opportunity for a hierarchically micro-
and mesoporous MOF for investigating its catalytic performance.
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INTRODUCTION
Metal–organic frameworks (MOFs),1,2 as a booming sort of inorganic-organic hybrid porous
crystal materials, have been drawn large quantity of interest and become a research focus in
chemistry and material science in recent years, which is not only attributed to their abundant and
fascinating structures3-5 but also their potential applications in gas sorption,6,7 luminescent
sensor,8,9 heterogeneous catalysis,10-13 and optical device14,15. MOFs are constructed by the
coordination self-assemble process of metal-containing secondary building units (SBUs) and
bridging organic linkers with N or O-donors.16 Compared with other porous materials including
mesoporous silica, activated carbon, and zeolite, porous MOF materials have various unique
properties, such as high surface area, adjustable pore, and attractive performance, resulting in
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vouchsafing the accurate layout of skeleton structure and regulating porous microenvironment at
molecular or even atomic level.17,18 Pore sizes in MOFs are in the wide range from angstrom to
nanometer, leading to their widespread applications as host materials in capturing and separating
small or large guest species.19-22 Up to now, most MOFs only have microporous structures with
pore size diameters under 2 nm, which is in favour of absorbing small gas or molecule;
nevertheless, microporous MOFs are restricted to the adhibition for large molecules due to the
smaller pore size than the molecular dimension of molecules. Recently, numerous efforts have
been focused on designing and preparation mesoporous MOFs, including template, large organic
linker or metal cluster, and post treatment.23-27 On the other hand, the poor physicochemical
stability of MOFs are directly limited their potential research fields because of their reversible
and weak nature of coordination bond.28,29 Some efficient strategies have been developed to
increase the strength of skeleton to enhance the stability.30-33 Especially, high-connected
multicores as SBUs have high universality and effectiveness to construct mesoporous MOFs
with inherent stability, but it is obviously hard to construct such MOFs due to relative harsh
synthetic conditions. Rare-earth (RE) hexanuclears have been reported by Prof. Mohamed
Eddaoudi to illustrate the availability of such RE hexanuclears for constructing stable MOFs.34,35
Among all application fields, heterogeneous catalysis is a significantly vital and useful research
hotspot for MOFs. Compared with homogeneous catalysts,36,37 heterogeneous catalysts have
been widely used in many fields due to size-selectivity, recyclability, and easy purify.38-41 The
catalysis efficiency can be remarkably accelerated by mesoporous MOFs, because mesoporous
structures can directly facilitate the diffusion of substrates and products. Knoevenagel
condensation reaction, as a common organic reaction, is an effective mean to synthesis
ponderable C–C coupling intermediate chemicals, which can be conventionally catalyzed by
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Lewis basic homogeneous catalysts.42 Amino group (–NH2) is a general Lewis basic site, which
can be decorated on the porous surface to catalyze Knoevenagel condensation reaction.43-46
Hence, it is eagerly desirable to create a mesoporous MOF decorating –NH2 as a highly efficient
heterogeneous catalyst for Knoevenagel condensation reaction with excellent stability.
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Considering these above points together, we designed and synthesized an amino-functional
linker 4'',6'-diamino-5',5''-bis(4-carboxyphenyl)-[1,1':3',1'':3'',1'''-quaterphenyl]-4,4'''-dicarboxylic
acid (namely H4DCBA) by a Suzuki coupling reaction in Scheme 1, which is self-assembled
with Tb6 hexanuclear cluster to successfully construct a three-dimensional (3D) hierarchically
micro- and mesoporous MOF, [Tb6(μ3-OH)8·(2-FBA)2·(H2O)6·(DCBA)2]·10DMF·4H2O (Tb-
DCBA). The resultant sample has preferable physicochemical stability, multiple porosity, and
affluent amino group simultaneously, leading in catalyzing Knoevenagel condensation reaction
with preferable recyclability.
NH2
NH2
Br
Br
COOCH3
CH3COOH
Br2
+
T
o
l
B
u
e
P
d
HO
OH
n
e
Br
Br
(
£
P
P
¬
E
NH2
NH2
h
t
O
3
)
4
H
£
¬
H
2
O
H3COOC
COOCH3
HOOC
COOH
NH2
NH2
NaOH£¬THF£¬EtOH£¬H2O
HCl
NH2
NH2
H3COOC
COOCH3
HOOC
COOH
Scheme 1. Synthesis of organic linker H4DCBA.
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Experimental Section
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Methods and Materials. All the chemical reagents were obtained from commercial sources and
used without further purification. Powder X-ray-diffraction (PXRD) patterns were acquired on a
Scintag X1 diffractometer with Cu-Kα (λ = 1.5418 Å) at 40 kV, 40 mA in the range of 4-50°
(2θ). Thermogravimetric analyses (TGA) for all measurements were carried on a Perkin-Elmer
TGA thermogravimetric analyser under air flow at a heating rate of 10 °C min–1 in the range of
30-800 °C. Elemental analyses (C, H and N) were obtained from a Perkin-Elmer 240 analyzer.
Fourier-transform infrared spectra (FT-IR) were performed on a Nicolet Impact 410 FT-IR
spectrometer in the 4000-400 cm–1 range using KBr pellets. All gas sorption measurements were
acquired on a surface area analyser ASAP 2020. The catalytic yields were calculated and
performed on a Thermo Fisher Trace ISQ GC/MS. 1H NMR spectra in ppm were collected on a
Bruker AV 400 spectrometer.
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Synthesis of 3,3',5,5'-tetrabromo-[1,1'-biphenyl]-4,4'-diamine. A sample of benzidine (1.0 g,
2.0 mmol) was dissolved in 30 mL of glacial acetic acid at room temperature. Bromine (1.2 mL)
was added slowly with rapid stirring and then the mixture was continually stirred for 4 h. The
brown precipitate was filtered off, washed with water several times, and dried in vacuum (yield:
83%). 1H NMR (400 MHz, CDCl3) 5.31 (s, 4H), 7.53 (s, 4H).
Synthesis of 4'',6'-diamino-5',5''-bis(4-carboxyphenyl)-[1,1':3',1'':3'',1'''-quaterphenyl]-
4,4'''-dicarboxylic acid (H4DCBA). First, 3,3',5,5'-tetrabromo-[1,1'-biphenyl]-4,4'-diamine
(1.98 g, 4 mmol), methyl 4-boronobenzoate (3.14 g, 19.2 mmol), Pd(PPh3)4 (0.30 g, 0.26 mmol)
and K3PO4 (3.82 g, 18.0 mmol) were placed in a 500 mL two-necked round bottom flask under a
N2 atmosphere. The flask was further charged with a 200 mL of dry 1,4-dioxane, and the
contents were heated for 48 h. After the mixture was cooled to room temperature, the solvent
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was removed, water was added. The water phase was washed with CH2Cl2. The mixed organic
phases were dried with MgSO4. After the solvent was removed, the crude product was purified
by column chromatography with CH2Cl2 as the eluent. Then, the above obtained dimethyl 4'',6'-
diamino-5',5''-bis(4-(methoxycarbonyl)phenyl)-[1,1':3',1'':3'',1'''-quarterphenyl]-4,4'''-
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dicarboxylate (2.0 g, 2.8 mmol) was dissolved in 50 mL MeOH, 50 mL 2 M NaOH aqueous
solution was added. The mixture was stirred at 50 ℃ overnight. The organic phase was removed,
the aqueous phase was acidified with diluted hydrochloric acid to give yellow precipitate, which
1
was filtered and washed with water several times. H NMR (400 MHz, CDCl3): 4.46 (s, 4H),
7.46 (s, 4H), 7.69 (d, 8H), 8.03 (d, 8H). Selected FT-IR data (KBr pellet, cm–1, see Figure S1 in
the Supporting Information): 3417 (br), 2928 (br), 2364 (s), 1694 (s), 1610 (s), 1537 (s), 1451
(s), 1396 (s), 1236 (s), 1176 (s), 1107 (s), 1015 (s), 867 (s), 782 (s), 711 (s), 538 (s), 411 (s).
Synthesis of [Tb6(μ3-OH)8·(2-FBA)2·(H2O)6·(DCBA)2]·10DMF·4H2O (Tb-DCBA).
A
mixture of Tb(NO3)3•6H2O (16 mg, 0.035 mmol), H4DCBA (10 mg, 0.015 mmol), N,N-
dimethylformamide (DMF, 2.0 mL), H2O (0.5 mL), and 2-fluorobenzoic acid (2-FBA, 140 mg)
was sealed into
a 23.0 mL Teflon-lined autoclave. The mixture was heated at 115 °C for 4 days
and then allowed to cool to room temperature to obtain the brown block crystals with the yield of
67% (based on ligand). Element analysis (%) Calc. for C124H154O48N14F2Tb6: C, 41.4; H, 4.3; N,
5.4; Found: C, 41.6; H, 4.1; N, 5.5 Selected FT-IR data (KBr pellet, cm–1, see Figure S1 in the
Supporting Information): 3431 (br), 1600 (s), 1534 (s), 1401 (s), 1269 (s), 1090 (s), 1018 (s), 866
(s), 786 (s), 716 (s), 625 (s), 547 (s), 424 (s).
Gas Sorption Measurement. The as-synthesized samples were soaked in dry methanol for 6 h,
which was slowly activated to obtain activated Tb-DCBA by using the supercritical CO2
approach. Gas adsorption and desorption measurements for activated samples were collected on
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a surface area analyser ASAP 2020. The Brunauer-Emmett-Teller (BET) surface area and pore
size distribution were both analyzed and calculated by the N2 isothermal adsorption curve at 77
K in a liquid N2 bath.
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Catalyze Knoevenagel Condensation Reaction. Generally, aldehyde (1.0 mmol) and
malononitril (1.1 mmol) were dissolved in 4 mL of CH2Cl2 in a round-bottom flask. Activated
Tb-DCBA (10 wt%) was added in the reaction system and slowly stirred at room temperature.
The reaction process can be constantly monitored by TLC, illustrating that this catalytic reaction
was almost completed after 6 h. Then, the reaction system was filtered and washed with fresh
CH2Cl2 for three times to recollect Tb-DCBA for the continuous catalytic reaction.
Single Crystal X-ray Analysis. Crystallographic data of Tb-DCBA were taken on SuperNova
CCD-based diffractometer with graphite Cu-Kα radiation (λ = 1.54184 Å) using -ω scan
technique at 110 K. Multi-scan absorption corrections were applied with the SADABS
program.47 The crystal structure was determined by direct methods with SHELXT 6 and refined
with full-matrix least-squares technique using SHELXL-201548,49 through OLEX2 interface
program50. All non-H atoms were located successfully and refined by anisotropic thermal
parameters. It was unsuccessful to locate and model the highly disordered guest DMF and H2O
molecules in the porous structure. Therefore, the SQUEEZE routine as a part of the PLATON
software package51,52 was used to calculate the disorder areas and remove the diffraction
contribution to afford a set of solvent free diffraction intensity. Solvent molecules were not
included in the crystal data. The chemical formula of as-synthesized Tb-DCBA was determined
based on the results of elemental analysis and TGA. Crystal data of as-synthesized Tb-DCBA
are summarized in Table 1 and the selected bond lengths and bond angles are listed in Table S1.
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Table 1 Crystallographic data and structure refinement for Tb-DCBA
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Compound
Empirical formula
Formula weight
Crystal system
Space group
a (Å)
Tb-DCBA
C46H32O17N2Tb3
1361.53
Hexagonal
P6/mmm
41.9264(18)
41.9264(18)
14.9781(7)
90.00
90.00
120.00
22801
6
0.598
6.941
8510
3954.0
0.0556
1.102
0.0509, 0.1745
0.0633, 0.1844
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b (Å)
c (Å)
α (º)
β (º)
γ (º)
V (Å3)
Z
ρ calc g cm–3
μ (mm-1)
Nref
F(000)
R(int)
Goodness-of-fit on F2
R1, wR2 [I > 2σ(I)]
R1, wR2 (all data)
RESULTS AND DISCUSSION
Structural Description.
Single-crystal X-ray diffraction analysis shows that Tb-DCBA crystallizes in hexagonal crystal
system and the P6/mmm space group. As shown in Figure S2 in the Supporting Information, Tb-
DCBA contains a quarter independent Tb1 atom, a half independent Tb2 atom, one quarter fully
deprotonated DCBA4– linker, a half μ3-O(4)H, one second μ3-O(7)H, one quarter 2-FBA linker, a
half terminal H2O(5) molecule, and one fourth coordinated H2O(6). A Tb6 hexanuclear cluster
was founded in Tb-DCBA, which is similar with some reported RE hexanuclears in MOFs
(Figure 1a).32,33 Each hexanuclear cluster can connect with eight –COOH groups from eight fully
deprotonated DCBA4– linkers; meanwhile, the square planar DCBA4– linker can link with four
hexanuclear clusters by adopting only one coordination mode as 8-1: 1: 1: 1: 1: 1: 1: 1
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(Figure 1b). More interestingly, the –NH2 group is uncoordinated and free in Tb-DCBA. All
hexanuclear clusters and DCBA4– linkers are further connected with each other to generate a 3D
skeleton with smaller microporous triangular channel (~1.2 nm) and larger mesoporous
hexagonal channel (~3.3 nm). Figure 1c obviously shows that Tb-DCBA is a rare micro- and
mesoporous MOF likely several reported MOFs. It's worth noting that the free –NH2 group is
exposed on the porous surface to create a porous environment with abound Lewis basic sites (see
Figure S3 in the Supporting Information). The infrequent micro- and mesoporous MOF can be
considered and investigated as a heterogeneous catalyst for catalyzing Knoevenagel
condensation reaction.
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Figure 1. Tb6 hexanuclear cluster (a) and square planar DCBA4– linker (b); and (c) viewing of a
3D micro- and mesoporous structure along c axis (C, gray; O, red; N, blue; Tb, green).
TGA, PXRD, and Gas Sorption.
The TGA result of as-synthesized Tb-DCBA clearly exhibits that an apparent weight loss of
~25.06% before 200 °C, which is mainly attributed to losing guest and coordinated solvents in
porous structure. The weight loss is well consistent with the calculated value of ~25.29 % (see
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Figure S4 in the Supporting Information). The whole structure further starts collapse when the
heating temperature reaches up to 420 °C. The purity of bulk as-synthesized samples can be
confirmed by PXRD at room temperature. As displayed in Figure S5 in the Supporting
Information, the diffraction peaks of solvent-formed Tb-DCBA are well consistent with those of
simulated data to prove the purity of these as-synthesized crystals. The fresh Tb-DCBA was
soaked in dry methanol for 6 h and then slowly activated to obtain activated samples by using the
supercritical CO2 approach. The PXRD profile of activated sample can well retain the diffraction
peaks of original samples to prove its high crystallinity and stability after desolvating solvents
(see Figure S6 in the Supporting Information). The N2 adsorption isotherm of activated sample
was measured at 77 K under 1 atm to in depth explore the internal porous context. The BET
surface area is calculated to be ~1902 m2 g–1; meanwhile, the corresponding pore size
distribution can be obtained by the density functional theory (DFT) method in Figure 2. These
results obviously indicate that Tb-DCBA is a rare hierarchically micro- and mesoporous MOF
with high surface area.
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Figure 2. N2 sorption isotherm at 77 K of activated samples and the corresponding pore size
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distribution by the DFT method.
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Catalytic Property.
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Benefiting of a great deal of –NH2 group in this hierarchically micro- and mesoporous Tb-DCBA,
it may be implemented in a potential application in catalyzing Knoevenagel condensation
reaction as an excellent heterogeneous catalyst. In a typical catalytic reaction, aldehyde (1.0
mmol) and malononitril (1.1 mmol) were both dissolved in 4 mL of CH2Cl2 in a round-bottom
flask, which was further added activated Tb-DCBA (10 wt%) and slowly stirred at room
temperature. The reaction process can be constantly monitored by TLC, illustrating that this
catalytic reaction was almost completed after 6 h. The catalytic yield is able to obtain well and
truly by using the GC method and use diphenyl in the reaction system as an internal standard. As
revealed in entry 1 of Table 2, benzaldehyde was firstly implemented as reaction substrate to
react with malononitril in the presence of Tb-DCBA, which almost can completely react after 6 h
with the high yield of >99%. The result is comparable to that of PCN-12453, Cz-MOF54, UPC-
102-Zr55, and PCP-156, which evidently shows that Tb-DCBA is a potential heterogeneous
catalyst for the C-C coupling Knoevenagel condensation reaction, which encourages us to
expand various aldehydes containing different functional substituent groups for this reaction.
The corresponding yields of targeted products remarkably decrease from >99% for benzaldehyde
to 89% for 4-fluorobenzaldehyde (entry 2), 87% for 4-methylbenzaldehyde (entry 3), 67% for 4-
nitrobenzaldehyde (entry 4), 19% for 4-biphenylcarboxaldehyde (entry 5), and 17% for 4-
phenoxybenzaldehyde (entry 6), respectively. The relative lower yields of these aldehydes with
large molecule sizes are prevailingly attributed to that the large sizes will directly slow down the
diffusion rate of reactants and substrates, which is similar with some reported MOFs.49-52 The
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control test was measured to catalyze benzaldehyde and malononitril without Tb-DCBA as
catalysis. It is not found any product in the catalytic system to prove the necessary of Tb-DCBA
for this reaction (entry 7). In addition, if Tb-DCBA was filtered from the reaction system of
benzaldehyde and malononitril, the catalytic reaction will be terminated immediately to further
illustrate that Tb-DCBA is an outstanding heterogeneous catalyst for this reaction (see Figure S7
in the Supporting Information).
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Table 2. The Knoevenagel condensation reaction.a
CN
O
+
NC
CN
CN
R
R
Entry
1
R
–
Catalyst
Product
Yield(%)b
CN
H–
Tb-DCBA
Tb-DCBA
Tb-DCBA
Tb-DCBA
>99
CN
CN
4-F–
2
3
4
5
89
CN
F
CN
4-Me–
87
CN
Me
CN
4-NO2–
67
CN
O2N
CN
4-Ph–
Tb-DCBA
Tb-DCBA
19
17
CN
CN
6
4-PhO–
CN
O
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CN
CN
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8
H–
H–
none
<1
CN
CN
>99
Tb-DCBA
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a Reaction conditions: aldehyde (1.0 mmol), Tb-DCBA (10 wt%), malononitril (1.1 mmol), CH2Cl2 (4 mL) at
room temperature. b Calculated by GC with diphenyl as internal standard.
The repeatability is a significantly critical factor for heterogeneous catalysts in the practical
application. After each Knoevenagel condensation reaction of benzaldehyde and malononitril,
Tb-DCBA can be directly collected by centrifugation at 8000 r min–1 for 2 min and regenerated
by washing with fresh CH2Cl2 for several times. The recycled Tb-DCBA can well keep the
catalytic performance even after reusing four times, which has high catalytic yield of >99%
(entry 8 and Figure 3a). On the other hand, all PXRD profiles of Tb-DCBA after recycling
several times are matched well with that of pristine crystals exhibiting that Tb-DCBA can keep
well structure during the catalytic process (Figure 3b). Meanwhile, the FT-IR spectra of recycled
samples are consistent well with the original spectrum to further prove the stability of reused Tb-
DCBA (see Figure S8 in the Supporting Information).
Figure 3. (a) Reusability and (b) PXRD profiles of reused Tb-DCBA.
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Referring to the early similar research work,57-63 the assumptive mechanism of catalytic
reaction mainly consists several parts in Figure 4. The full catalytic process can be firstly
activated the O atom of aldehyde by interacting with –NH2 as the Lewis basic acid catalytic site
on the linker. An amide intermediate state is generated by removing a H2O molecular.
Subsequently, malononitril can be quickly interacted with the amide intermediate to form the
targeted product. Finally, the catalytic center of Lewis basic site (–NH2) can be regenerated for
the next catalytic reaction. Nonetheless, the catalytic mechanistic for this Knoevenagel
condensation reaction still far surpasses than our scope to accurately understand the authentic
catalytic mechanism, which require more investigations in the future work and more advanced
characterization techniques.
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Figure 4. Assumptive catalytic mechanism of Knoevenagel condensation reaction by Tb-DCBA.
CONCLUSION
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In conclusion, a 3D hierarchically micro- and mesoporous MOF based on Tb6 clusters has been
successfully designed and synthesized, which has lots of Lewis basic site (–NH2) on the porous
surface. The resultant sample can highly efficient catalyze Knoevenagel condensation reaction
and also has preferred recyclability. We really hope that this work can create an interesting and
useful method to prepare such mesoporous MOFs in terms of special catalytic application areas.
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ASSOCIATED CONTENT
Supporting Information
The FT-IR, PXRD, TGA, crystal structure and crystal data (CIF) were provided in the supporting
information. The crystallographic data was deposited in the Cambridge Crystallographic Data
Centre (CCDC) as CCDC No. 1970448. This material is available free charge via the Internet at
http://pubs.acs.org.
AUTHOR INFORMATION
Corresponding Author
*E-mail: hehongminghz@163.com or hxxyhhm@tjnu.edu.cn (H. He.)
ORCID
Hongming He: 0000-0001-5535-8825
Notes
The authors declare no competing financial interest.
ACKNOWLEDGMENT
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We are grateful to the financial support from Education Department of Henan Province
(19A150047) and National Natural Science Foundation of China (21801187).
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Design and Assembly of a Hierarchically Micro- and Mesoporous MOF as a
Highly Efficient Heterogeneous Catalyst for Knoevenagel Condensation
Reaction
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Kun Cai,†,‖ Wenjun Tan,†,‖ Nian Zhao§ and Hongming He*,‡
This work presents a hierarchically micro- and mesoporous MOF with preferable stability as a
potential excellent heterogeneous catalysis for Knoevenagel condensation reaction with excellent
recyclability.
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