Mechanically fabricated Metal–organic framework/resin composite nanoparticles for efficient basic catalysis

Article abstract of DOI:10.1002/aoc.4788

Zeolitic imidazolate framework-8 (ZIF-8) was successfully composited with an anionic basic resin 201?×?7 (717-resin) to provide a novel ZIF-8/717-resin composite. Its catalytic activity toward the Knoevenagel condensation reaction was evaluated. Results s

Full text of DOI:10.1002/aoc.4788

Received: 9 October 2018
DOI: 10.1002/aoc.4788
Revised: 1 December 2018
Accepted: 16 December 2018
F U L L P A P E R
Mechanically fabricated Metal–organic framework/resin
composite nanoparticles for efficient basic catalysis
Zhi‐Hui Zhang1
Jin‐Long Wang1 | Qun Chen1 | Liang Wang1
| Bing‐Bing Qian1 | Pan‐Pan Sheng1 | Sen Yang1 | Xian‐Feng Huang1,2
|
| Ming‐Yang He1
1 Jiangsu Key Laboratory of Advanced
Zeolitic imidazolate framework‐8 (ZIF‐8) was successfully composited with an
anionic basic resin 201 × 7 (717‐resin) to provide a novel ZIF‐8/717‐resin com-
posite. Its catalytic activity toward the Knoevenagel condensation reaction was
evaluated. Results showed that ZIF‐8/717‐resin composite could efficiently cat-
alyze this reaction, affording the corresponding products in good to excellent
yields. Good functional group tolerance, mild reaction conditions, good
stability and reusability of the catalyst are the major features of present
protocol.
Catalytic Materials & Technology,
Advanced Catalysis and Green
Manufacturing Collaborative Innovation
Center, Changzhou University, Changzhou
213164, People's Republic of China
2 School of Pharmaceutical Engineering
and Life Science, Changzhou University,
Changzhou 213164, People's Republic of
China
Correspondence
Liang Wang and Ming‐Yang He, Jiangsu
Key Laboratory of Advanced Catalytic
Materials & Technology, Advanced
Catalysis and Green Manufacturing
Collaborative Innovation Center,
Changzhou University, Changzhou,
213164, People's Republic of China.
Email: liangwang@cczu.edu.cn;
hemingyangjpu@yahoo.com
KEYWORDS
composite, Knoevenagel condensation, mechanical fabrication, metal–organic frameworks,
synergistic catalysis
Funding information
Jiangsu Key Laboratory of Advanced Cata-
lytic Materials and Technology, Grant/
Award Number: BM2012110; National Nat-
ural Science Foundation of China, Grant/
Award Numbers: 11775037 and 21676030
1 | INTRODUCTION
particular materials gives rise to multifunctional compos-
ites adopting favorable properties that superior to the
Metal–organic frameworks (MOFs) are promising porous
materials for diverse applications due to their adjustable
of apertures and versatile framework functionalities,[1–6]
which lead to potential applications in gas separation
and storage, sensing, and catalysis.[7–13] Among them,
zeolitic imidazole frameworks (ZIFs) represent a series
of MOFs composed by the coordination interaction of
metal ions with the nitrogen atoms from imidazole or
its derivatives.[14,15] Although ZIFs take advantages of
ordered crystalline pores and high stability as zeo-
lites,[14,16] the deliberate combination of ZIFs and
original individual components.[17,18]
ZIF‐8, bearing a zeolitic sodality (SOD) topology, is
one of the most classic ZIFs materials.[14] Owing to its
unique cages with a pore diameter of 1.16 nm and an
aperture of 0.34 nm, ZIF‐8 is readily to accommodate
multiple nanoparticles within cages for heterogeneous
catalysis. ZIF‐8 itself has both nitrogen basic sites and
ZnII Lewis acidic sites and has been extensively used to
construct versatile nanoparticle composites with metal
or metal oxides, silica, organic polymers, quantum dots
(QDs) and graphene toward diversiform structures for
Appl Organometal Chem. 2019;e4788.
wileyonlinelibrary.com/journal/aoc
© 2019 John Wiley & Sons, Ltd.
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https://doi.org/10.1002/aoc.4788

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ZHANG ET AL.
desired properties.[19] Through compositing with proper
species, the active sites on ZIF‐8 enable the activation of
substrates to facilitate different type organic transforma-
tions such as the Knoevenagel condensation,[20–22] CO2
cycloaddition of epoxides,[23,24] conjugate‐addition reac-
tion,[25] and so on.
with few ZIF‐8 particles in the macropores of the resin
and used for selective solid‐phase extraction.[39] However,
to the best of our knowledge, the composition of ZIFs
with crosslinking resins has not been documented so
far. Notably, since anion‐exchange resins have amine
groups, they are typical catalysts for heterogeneous
base‐catalyzed model reactions including Knoevenagel
condensation.[40–42] We anticipated that the combination
of ZIF‐8 with an anion‐exchange basic resin may afford
a bifunctional catalyst, which may serve as an efficient
heterogeneous catalyst for Knoevenagel reactions. More-
over, the hydrophobility of ZIF‐8 can be adjusted by
introduction of a hydrophilic resin, which may enhance
its catalytic activity in polar solvents.
Herein, we report the mechanical synthesis of a novel
composite from ZIF‐8 and an anionic 201 × 7 resin (717‐
resin) containing basic divinylbenzene‐styrene copolymer
trimethylammonio groups and hydroxyl ions (Figure S1).
Multiple characterizations clearly showed that the 717‐
resin was successfully composited with ZIF‐8. The cata-
lytic activity of ZIF‐8/717‐resin was also evaluated using
Knoevenagel condensation reaction as the model reac-
tion. High activity was observed under mild reaction con-
ditions. Moreover, the ZIF‐8/717‐resin catalyst could be
easily isolated from the reaction mixture by simple filtra-
tion and reused without significant loss in its activity.
The Knoevenagel condensation is one of the most use-
ful organic reactions, which has been widely utilized for
the synthesis of valuable α,β‐unsaturated carbonyl com-
pounds..[26–28] Conventionally, this reaction is catalyzed
in the presence of either an acid or a base catalyst follow-
ing a SN1 path of nucleophilic addition–elimination.
Recently, the utilization of heterogeneous catalysts have
received increasing attention. For example, supported
amines catalysts have been successfully developed and
employed in the Knoevenagel condensation.[29–31] These
catalysts not only exhibited good activities but also could
be readily recovered and reused after simple filtration.
Recently, MOFs especially ZIFs catalysts have also
been found as efficient catalysts for the Knoevenagel con-
densation.[21,22,32–34] Phan and co‐workers[22] reported that
pristine ZIF‐8 could efficiently promote the condensation
of benzaldehyde and malononitrile at room temperature,
albeit in an environment unfriendly solvent (toluene).
Whereas methanol turned out to be an ineffective solvent
due to the hydrophobility of the ZIF‐8 catalyst. ZIF‐8 nano-
particles has also been reported as an efficient and reusable
catalyst for the Knoevenagel synthesis of cyanoacrylates
and 3‐cyanocoumarins.[33] The introduction of hydroxy
groups to the substrates led to reasonable yields of cyanoac-
rylates in the polar ethanol solvent. Recently, a bimetallic
Zn@ZIF‐67 catalyst performed excellent catalytic activities
for the Knoevenagel condensation between p‐Br‐benzal-
dehyde and malononitrile.[32] Although leading to a quan-
titative conversion, MeOH sovent was observed to be less
reactive than toluene and DMSO. Obviously, heteroge-
neous catalyzed Knoevenagel reactions are very sensitive
to the solvent polarities, and further studies need to be car-
ried out to elucidate the effect of solvents and modify the
ZIF‐8 catalyst by changing its hydrophobility.
2 | EXPERIMENTAL
2.1 | Synthesis of ZIF‐8
The synthesis procedure was proceeded according to our
previous reports.[43] Briefly, zinc nitrate hexahydrate [Zn
(NO3)2·6H2O (2.76 g, 9.30 mmol)] was dissolved in
18 ml deionized water with sonication. 2‐Methylimi-
dazole (6.60 g, 80.38 mmol) was dissolved in 120 ml
deionized water with sonication. Then the two solutions
were mixed in a 250 ml round‐bottom flask under
mechanical stirring at room temperature for 6 hr. The
obtained product was collected by centrifugation and
washed with deionized water and methanol for three
times. Finally, the obtained product was vacuum‐dried
at 80 °C for 24 hr.
In another aspect, ion‐exchange resins, most of them
known as hydrophilic for they having hydrophilic groups,
have been extensively employed as catalysts or support
due to their good stability, high adsorption capacity,
cost‐economy, facile recoverability and rapid kinet-
ics.[35,36] Recent literature showed that MOF could be
composited with ion‐exchange resins.[37] Such composites
are more stable with enhanced catalytic activity in some
cases. For example, the classic MOF‐5 was introduced to
strengthen a cycloaliphatic epoxy resin.[37] A Fe‐MOF
namely MIL‐53 (Fe) was modified by ionic resins to
improve its photocatalytic performance.[38] Very recently,
a ZIF‐8 modified macroporous D101‐resin was prepared
2.2 | Synthesis of ZIF‐8/717‐resin
composites
717‐Resin spheres (hydroxide or chloride‐type) were suc-
cessively washed with methanol, followed by vacuum‐
drying at 50 °C before the synthesis of ZIF‐8/717‐resin.
ZIF‐8 (100 mg) and 717‐resin were mixed in a mortar
and grinded into powder in different mass ratios (1:1

ZHANG ET AL.
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and 1:2). During grinding, the appropriate amount of
dichloromethane (DCM) was added to the mixture to
enable the mixing homogeneity. The mixed powder was
suspended in 15 ml DCM and stirred at room tempera-
ture for 7 days. After completion of the reaction, the solid
was collected by rotary evaporation to remove DCM sol-
vent. The solid was subsequently refluxed in tetrahydro-
furan (THF) overnight and the filtered solid was washed
with ethanol. Finally, the obtained product was dried at
80 °C in vacuum for 4 hr. The yields of ZIF‐8/717‐resin
composites are 92% and 87% on the basis of the ZIF‐8
moiety for the ZIF‐8 and hydroxide‐type 717‐resin mass
ratios of 1:1 and 1:2, respectively.
2.3 | Catalytic studies
FIGURE 1 PXRD diagrams of ZIF‐8 and ZIF‐8/717‐resin
Catalytic activity of ZIF‐8/717‐resin for the Knoevenagel
reaction was carried out using benzaldehyde and
malononitrile as the model substrates. Initially, ZIF‐8/
717‐resin was added to a methanol solution (8 ml) of
benzaldehyde under magnetically stirring for 5 min. A
solution of malononitrile in methanol was then added,
and the resulting mixture was further stirred at room
temperature for 6 hr. Aliquots of the reaction mixture
were withdrawn at different time intervals to monitor
the reaction conversion. Before the GC–MS examination,
aliquots were quenched by acetone and filtered through a
short silica gel pad. After the reaction, the ZIF‐8/717‐
resin catalyst was separated from the reaction mixture
by simple centrifugation, washed by methanol and
DCM several times, dried under vacuum at 80 °C for
6 hr, and reused if necessary.
the composition of 717‐resin and ZIF‐8, Energy‐
dispersive X‐ray spectroscopy (EDS) was conducted on
the chloride‐type ZIF‐8/717‐resin samples. EDS mapping
indicates the successful composition of ZIF‐8 and 717‐
resin by the observation of well‐dispersed chlorine
(Figure 2e and 2f). Different ratios of the starting ZIF‐8
and 717‐resin lead to different weight percentages of
ZIF‐8 in ZIF‐8/717‐resin (ca. 68%/59% for ZIF‐8/717‐
resin = 1:1/1:2 according to EDS element analysis
(Table S1 and Figure S2). On the contrary, a previously
reported D101‐resin @ZIF‐8 was prepared using in‐situ
generation of ZIF‐8 particles within the pores of the
D101‐resin, resulting in a relatively low loading amount
of ZIF‐8 (0.43 wt % of Zn2+).[39] Increasing the ratio of
starting 717‐resin cannot effectively enhance the percent-
age of 717‐resin in the composite product. So the ZIF‐8/
717‐resin = 1:1 composite sample was chosen for the fur-
ther investigation.
3 | RESULTS AND DISCUSSION
The as‐synthesized ZIF‐8/717‐resin was then character-
ized using a variety of techniques. Firstly, the powder X‐
ray diffraction (PXRD) diagrams (Figure 1) verify the
highly crystalline feature of the ZIF‐8/717‐resin as its par-
ent ZIF‐8 materials. In this work, mechanical stirring of
ZIF‐8 and 717‐resin in DCM leads to a well composited
ZIF‐8/717‐resin, which is significantly different from the
morphology of the pristine and crushed 717‐resin
(Figure 2a and 2b). The scanning electron microscope
(SEM) micrograph (Figure 2c) shows that the crystal size
of composites in irregular profile are ranging from 100 to
300 nm with somewhat aggregation, which is signifi-
cantly different with the as‐synthesized ZIF‐8 nanoparti-
cles that in well‐shaped cubic crystals.[43] As expected,
the transmission electron microscope (TEM) observation
clearly reveals that the small aggregations reside on big-
ger crystalline composites (Figure 2d). To further confirm
Furthermore, the loading ratio of 717‐resin in ZIF‐8/
717‐resin = 1:1 sample is confirmed to be around
32 wt% of the composite based on thermogravimetric
(TG) analysis. TG curve (Figure 3a) of ZIF‐8/717‐resin
shows little weight loss from room temperature to
200 °C, demonstrating the release of water for 717‐resin
during composition. Due to the presence of ZIF‐8, the
thermal stability of the composite at 200–400 °C was sig-
nificantly improved in comparison with 717‐resin. It is
also found a sharp weight loss step at the temperature
range of 400 to 700 °C, representing the thermal decom-
position of the ZIF‐8/717‐resin at this temperature range.
The satisfactory thermal stability ensures the applicability
of ZIF‐8/717‐resin in a wide temperature range. Fourier
transform Infrared (FT‐IR) spectra of ZIF‐8/717‐resin
exhibited a combination feature of ZIF‐8 and 717‐resin
(Figure 3b). The similar characteristic bands for ZIF‐8

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ZHANG ET AL.
FIGURE 2 (a) Photos of the pristine 717‐resin and ZIF‐8/717‐resin. (b) A SEM image of the crushed 717‐resin. (c) and (d) SEM and TEM
images of the as‐synthesized ZIF‐8/717‐resin. (e) and (f) A SEM image and the EDS mapping of the ZIF‐8/717‐resin tablet
and ZIF‐8/717‐resin samples within the ranges of 1300–
1500 cm−1 and 1100–1200 cm−1 could be assigned to the
stretching and the plane vibration of the imidazole skele-
ton, respectively.[32] In comparison with respective spec-
tra of ZIF‐8 and 717‐resin, the absence of absorption
bands at approximately 2300 cm−1 of ZIF‐8/717‐resin
may due to the effective composition, which has also
been found in a composite that is ZIF‐8 coatings on a pol-
yimide substrate.[44]
composites. Both of the two kinds of nanoparticles
reveals reversible type I isotherms that indicates excellent
N2 uptake at relatively low pressures (P/P0 < 0.1), featur-
ing typical microporous materials. By using the adsorp-
tion data points in the range of P/P0 = 0.01–0.10, The
surface areas of 1774 m2/g (Langmuir model) and
1108 m2/g [Brunauer–Emmett–Teller (BET) model] for
ZIF‐8 nanoparticles were obtained with a micropore vol-
ume of 0.523 cm3/g. The corresponding values are lower
than the reported ones of pristine ZIF‐8[45] and fast‐
formed ZIF‐8 nanoparticles,[33] which may be due to the
lower quality of the crystalline products. For the ZIF‐8/
In addition, the nitrogen‐sorption isotherm measure-
ments (Figure 4) were carried out to compare the porosity
of original ZIF‐8 nanoparticles and ZIF‐8/717‐resin

ZHANG ET AL.
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FIGURE 3 (a) TG curves of the ZIF‐8/717‐resin. (b) FT‐IR spectra of the ZIF‐8/717‐resin
FIGURE 4 N2 adsorption/desorption isotherms (a) and the pore size distributions (b) of ZIF‐8 and ZIF‐8/717‐resin nanocrystals
717‐resin composite, the Langmuir and BET surface area
are 1083 and 728 m2/g, respectively, and the values are
lower than that of ZIF‐8 nanoparticles, which is attrib-
uted to the successful composition of 717‐resin (ca.
32%). Therefore, the crystallization of ZIF‐8 components
has strong tendency to form microspores without 717‐
resin blocking during the composition. The total pore
volume of micropores for ZIF‐8/717‐resin is about
0.358 cm3/g, and the stacking mesopores and macropores
are not detected in this case, which is different with the
aggregates of ZIF‐8 nanocrystals.[46]
Due to fully exposing of large external surfaces, fast
mass transfer within ZIFs heterogeneous catalysts is eas-
ily accessed even by large molecules. As a prototypical
ZIF material, ZIF‐8 has been verified as an efficient het-
erogeneous catalyst for the C‐C bond formation reac-
tion.[22] But its hydrophobility influence the catalytic
activity in polar solvents, such as methanol, ethanol and
water. Our strategy of the composition is based on the
combination of ZIF‐8 that adopts unsaturated Lewis
acidic sites and 717‐resin that possesses strong basic sites,
which may have strong affinity to various substrates with
good tolerance to different sizes and substituents. So the
catalytic activity of ZIF‐8/717‐resin catalyst was firstly
assessed in the Knoevenagel condensation of benzalde-
hyde (1a) and malononitrile (2) to form benzylidene
malononitrile (3a) as the target product (Scheme 1).
The initial reaction was carried out using 5 mol %
(based on Zn) ZIF‐8/717‐resin catalyst (40 mg) relative
to benzaldehyde in methanol at room temperature. A
moderate yield (64%) of desired product 3a was obtained
after 2 hr (Table 1, entry 1). As the reaction time
increased, the reaction conversion rate increased, and
the yield reached up to 97% after 6 hr (Table 1, entry 4).
Taking the aforementioned results into account, we
decided to investigate the effect of catalyst concentration
on the reaction yield. The catalyst concentration, with
respect to zinc content in the ZIF‐8/717‐resin, was
SCHEME 1 Knoevenagel condensation
of benzaldehyde (1a) and malononitrile (2)

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ZHANG ET AL.
TABLE 1 Optimization of reaction conditionsa
In addition, the molar ratios of two substrates signifi-
cantly affected the yields (entries 16–18). Only slight
increase in the yield was observed when increasing the sub-
strate 2 to 3 equivalents (97% yield), while decreasing the
substrate 2 to 1 equivalent led to a moderate yield (70%).
Thus, the optimum reaction conditions were determined
as following: aldehyde 1a (3.8 mmol), 2 (2 equivalents),
methanol as the solvent, room temperature, and 6 hr.
The scope and generality of the Knoevenagel conden-
sation was then explored under the optimized reaction
conditions (Table 2). In most cases, both malonitrile (2)
and ethyl cyanoacetate (4) condensed with aromatic alde-
hydes smoothly to afford the corresponding products (5)
in excellent yields. A series of functional groups including
nitro, halogen, hydroxyl, methoxyl, methyl, and methyl-
thio were well tolerated. Generally, benzaldehyde deriva-
tives containing electron‐withdrawing groups were more
active than those with electron‐donating groups since
nucleophilic addition was the rate‐determination step in
such condensation reactions. Interestingly, the ZIF‐8/
717‐resin catalyst exhibited high activity for benzalde-
hyde derivatives bearing either electron‐withdrawing or
electron‐donating substituents, indicating the high cata-
lytic activity of the bifunctional composite catalyst. The
positions of the substituted groups have trivial influence
on the yields of regioisomeric isomers (3b, 3c, 3i~3 k;
5b, 5c, 5i~5 k). However, when the aryl aldehydes were
replaced by aliphatic aldehydes, the yields dropped dra-
matically (3 l, 3 m, and 5 m). Especially for 5 l, several
tries to obtain the pure products were failed. The reduced
yields might be attributed to the presence of alkyl that
weakens the conjugation effect, arisen from the original
benzene ring and aldehyde carbonyl.
1a/2
Cat.
Time Yield
(h)
Entry (molar ratio) (mg) Solvent
(%)b
1
1/2
1/2
1/2
1/2
1/2
1/2
1/2
1/2
1/2
1/2
1/2
1/2
1/2
1/2
1/2
1/1
1/3
1/4
1/2
1/2
40
40
40
40
20
30
40
40
40
40
40
40
40
40c
40d
40
40
40
40e
40f
methanol
methanol
methanol
methanol
methanol
methanol
ethanol
2
4
5
6
6
6
6
6
6
6
6
6
6
6
6
6
6
6
6
6
64
86
94
97
77
94
89
73
94
90
39
30
19
32
51
70
97
93
95
85
2
3
4
5
6
7
8
dichloromethane
DMF
9
10
11
12
13
14
15
16
17
18
19
20
toluene
acetonitrile
dioxane
ethyl acetate
methanol
methanol
methanol
methanol
methanol
methanol
methanol
aReaction conditions: ZIF‐8/717‐resin catalyst (specific amounts) and 1a
(0.4 ml, 3.8 mmol) was dissolved in 8 ml solvent in a round‐bottom flask
under stirring for 5 min at room temperature. 2 (specific amount) was dis-
solved in 5 ml solvent. Then the solution was decanted into the flask and
stirred for specific time.
bGC yields.
cZIF‐8 as the catalyst.
Another feature of heterogeneous catalysts is the facile
separation and sustained reusability. Therefore, the recov-
erability and reusability was investigated using the model
reaction listed in Table 1. After the reaction, the catalyst
was separated by simple centrifugation and then washed
with mixed solvents of anhydrous methanol and DCM to
remove possible physisorbed reagents. The recovered cata-
lyst was then dried under vacuum overnight. It was found
that the ZIF‐8/717‐resin catalyst could be recovered and
reused without a significant loss in its catalytic activity
over five successive runs (Figure 5). Meanwhile, hot‐
filtration experiment was performed using the model reac-
tion to testify the reaction a heterogeneous or homoge-
neous process. The reaction mixture was filtrated to
remove the catalyst after one hour and the filtrate was kept
stirring under the same condition. The completely termi-
nation of the reaction upon the removal of ZIF‐8/717‐resin
was confirmed by GC and ICP analysis.
d717‐resin as the catalyst.
eZIF‐8/717‐resin = 1:2 sample as the catalyst.
fThe ZIF‐8:717‐resin (1:1) mixture as the catalyst.
studied in the range of 20–40 mg. As expected, higher
quantity of catalyst led to increased yields of product 3a
(Table 1, entries 4–6). The solvent also played an impor-
tant role on this transformation. Conducting the reactions
in other solvents such as ethanol, dichloromethane
(DCM), N,N‐dimethylformamide (DMF) and toluene pro-
vided the desired product 3a in good to excellent yield
(73–94%, entries 7–10). However, much lower yields were
obtained by preforming the reactions in acetonitrile, 1,4‐
dioxane or ethyl acetate (entries 11–13). Notably, the cat-
alytic performance of ZIF‐8/717‐resin composite is much
better than those of ZIF‐8 or 717 resin (entry 14 and 15).
Methanol was found to be more effective than toluene
that used in the same Knoevenagel condensation accord-
ing to previous reports.[22,44]
To evaluate the catalytic activities, some controlled
experiments were performed (Table 1, entry 14, 15, 19

ZHANG ET AL.
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TABLE 2 Reaction scope
3c, 98%
5c, 95%
3d, 98%
5d, 98%
3b, 98%
5b, 96%
3f, 93%
5f, 95%
3e, 84%
5e, 93%
3g, 94%
5g, 95%
3i, 98%
5i, 95%
3j, 97%
5j, 96%
3h, 92%
5h, 94%
3k, 94%
5k, 93%
3m, 39%
5m, 43%
3l, 41%
5l, trace
FIGURE 5 (a) PXRD patterns of reused ZIF‐8/717‐resin with a SEM image of the catalyst after 5 runs. (b) Recycling study
and 20). Results showed that when the reaction was per-
formed in the presence of ZIF‐8 or 717‐resin, only 32%
and 51% yields were obtained, respectively. For the ZIF‐
8:717‐resin (1:1) mixture as the catalyst, the yield of the
product is 85%, which is a little lower than that of ZIF‐
8/717‐resin = 1:2 sample as the catalyst. On the contrary,
nearly quantitative yield (97%, Table 1, entry 4) was
obtained in the presence of the 1:1 ZIF‐8/717‐resin
composite, indicating that the composite had synergistic
catalytic effect.
methanol was found to be an ineffective solvent for
the catalysis because of the hydrophobility of the ZIF‐8
catalyst. In this work, the catalytic activity in methanol
of ZIF‐8 catalyst was significantly enhanced by
compositing with hydrophilic 717‐resin. As for the cata-
lytic mechanism, the composite catalyst is an amphi-
pathic catalyst that could form possible hydrogen‐
bonding interactions to the polar methanol solvent.
Additionally, both the basic catalytic centers of 717‐resin
and the acidic centers (Zn2+) of ZIF‐8 promoted the
nucleophilic addition–elimination SN1 path of the
Knoevenagel condensation.
In previous Knoevenagel condensation reaction that
performed by using ZIF‐8 or functionalized ZIF‐8,[47]

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ZHANG ET AL.
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4 | CONCLUSION
In summary, a new type of ZIF‐8/717‐resin composite
material was successfully prepared with highly crystalline
and comparable loading amounts of both materials. The
compositions of this composite were identified and quan-
tified through a variety of methods especially EDS, IR,
and TG analyses. The catalytic performance of ZIF‐8/
717‐resin was probed using Knoevenagel reaction with
an extended scope of benzaldehyde derivatives substrates
in an eco‐friendly alcohol solution instead of toluene.
Highly conversions were achieved under the ambient
without inert atmospheres, and the ZIF‐8/717‐resin cata-
lyst could be easily reused without significant degrada-
tion in 5 runs in the catalytic activity.
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We gratefully acknowledge the financial supports from
the National Natural Science Foundation of China
(Grant 11775037 and 21676030), and the Jiangsu Key
Laboratory of Advanced Catalytic Materials and Tech-
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