Mechanically Strong Heterogeneous Catalysts via Immobilization of Powderous Catalysts to Porous Plastic Tablets

Article abstract of DOI:10.1002/cjoc.202100280

Main observation and conclusion: We describe a practical and general protocol for immobilization of heterogeneous catalysts to mechanically robust porous ultra-high molecular weight polyethylene tablets using inter-facial Lifshitz-van der Waals Interactions. Diverse types of powderous catalysts, including Cu, Pd/C, Pd/Al₂O₃, Pt/C, and Rh/C have been immobilized successfully. The immobilized catalysts are mechanistically robust towards stirring in solutions, and they worked well in diverse synthetic reactions. The immobilized catalyst tablets are easy to handle and reused. Moreover, the metal leaching of immobilized catalysts was reduced significantly.

Full text of DOI:10.1002/cjoc.202100280

Chinese Journal
of Chemistry
CJC
中 国 化 学 - An International Journal
Accepted Article
Title: Mechanically Strong Heterogeneous Catalysts via Immobilization of
Powderous Catalysts to Porous Plastic Tablets
Authors: Tingting Li, and Bo Xu*
This manuscript has been accepted and appears as an Accepted Article online.
This work may now be cited as: Chin. J. Chem. 2021, 39, 10.1002/cjoc.202100323.
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published online in Early View: http://dx.doi.org/10.1002/cjoc.202100323.
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Xu Bo (Orcid ID: 0000-0001-8702-1872)
Cite this paper: Chin. J. Chem. 2021, 39, XXX—XXX. DOI: 10.1002/cjoc.202100XXX
Mechanically Strong Heterogeneous Catalysts via Immobilization
of Powderous Catalysts to Porous Plastic Tablets
Tingting Li, and Bo Xu*
Key Laboratory of Science and Technology of Eco-Textiles, Ministry of Education, College of Chemistry, Chemical Engineering and Biotech-
nology, Donghua University, Shanghai 201620, China
Keywords
Heterogeneous catalysts | Solution-phase chemistry | Immobilization | Porous plastic tablets | Metal leaching
Main observation and conclusion
We describe a practical and general protocol for immobilization of heterogeneous catalysts to mechanically robust porous ultra-high
molecular weight polyethylene tablets using inter-facial Lifshitz-van der Waals Interactions. Diverse types of powderous catalysts, in-
cluding Cu, Pd/C, Pd/Al2O3, Pt/C, and Rh/C have been immobilized successfully. The immobilized catalysts are mechanistically robust
towards stirring in solutions, and they worked well in diverse synthetic reactions. The immobilized catalyst tablets are easy to handle
and reused. Moreover, the metal leaching of immobilized catalysts was reduced significantly.
Comprehensive Graphic Content
Catalyst
particles
Sintering
weight
a
Stir in
Ultrahigh molecular
powder
suspension
polyethylene
Waals Interactions
der
Lifshitz-van
Filtration
General
Mechanically
immobilization
protocol
strong
Recyclable
metal
Much
reduced
leaching
tablet
Catalyst-loaded
*E-mail: bo.xu@dhu.edu.cn
View HTML Article
Supporting Information
Chin. J. Chem. 2021, 39, XXX－XXX
© 2021 SIOC, CAS, Shanghai, & WILEY-VCH GmbH
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through the copyediting, typesetting, pagination and proofreading process which may lead to
differences between this version and the Version of Record. Please cite this article as doi:
10.1002/cjoc.202100280
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First author et al.
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is smaller than the pores in the tablets, the catalyst particles
will be absorbed by the porous tablet via interfacial Lifshitz-
van der Waals interactions.[5] Also, the whole porous tablet has
a 'maze’-like structure, and catalyst particles are not easy to
escape the ‘maze' (Figure 1b). We found this immobilization
method is general, and diverse catalysts as micro- or nanopar-
ticles, including Cu, Pd/C, Pd/Al2O3, Pt/C, and Rh/C, could be
immobilized successfully (Figure 1c).
Background and Originality Content
Heterogeneous catalysis is critical in the production of
chemicals.[1] Heterogeneous catalysts usually are prepared by
the deposition of nanosized active catalysts (usually precious
metals) to porous inorganic supports such as TiO2, Al2O3, and
molecular sieves (Figure 1a). Although heterogeneous catalysts
are highly successful in gas phase reactions, they are not ideal
for solution-phase reactions. Although many inorganic catalyst
supports such as Al2O3 have very high hardness, when becom-
ing porous, they tend to be fragile and are not mechanically
stable to withstand the constant stirring and collision in solu-
tions. As a result, for solution-phase chemistry, heterogeneous
catalysts (e.g., Pd/C, Pt/Al2O3) were supplied as fine powders
or will be broken to fine powders when stirring in solution. This
leads to many problems like the difficulty of catalyst recovery
by filtration, leaching of heavy metals, and hazardous opera-
tions in the handling of fine catalyst particles. Metal leaching
is especially problematic for the production of pharmaceuti-
cals.
In recent years, there are significant processes and develop-
ments on polymer-supported catalysts.[2] Polymer-supported
catalysts have the advantages of the easy workup of the reac-
tion by filtration of the solid-catalysts, low residual metal levels
in the final crude product, recyclability of the solid-supported
catalysts. The most common polymer backbone is crosslinked
polystyrene (PS), and the active catalysts are bonded to the PS
backbone through covalent or coordination bonds. Moreover,
many polystyrene and other polymers supported catalysts
have been commercialized.[3] Although organic polymers such
as PS are generally less fragile, they are often still not mechan-
ically robust enough for a long time stirring. Also, because the
active catalyst was bonded to the polymer backbone cova-
lently, this type of supported catalysts are generally expensive
to prepare. As a result, inorganic supports such as activated
carbon and TiO2 based on heterogeneous still play a significant
role in the industry.
Filtration
als
yst-loaded tablet
ver broken by stirring
@Tab
Rh/C@Tab
Figure 1. Immobilization of powderous catalysts to porous plastic tablets.
Results and Discussion
Our strategy to address this problem is using an inert poly-
mer with high plasticity (plastics) as catalyst supports (Figure
Among conventional engineering plastics, ultra-high-molec-
ular-weight polyethylene (UHMWPE) has the best corrosion,
abrasion, wear, and impact resistance. UHMWPE has much
better abrasion wear resistance and impact strength than most
tough materials, including steel, polycarbonate, ABS.[6] We en-
vision catalyst support made from UHMWPE will be mechani-
cally robust toward stirring in solution-phase reactions. We use
inexpensive and commercially available UHMWPE powders
1b). Plastics are much softer than inorganic supports such as
TiO2, but they are much more resistant to collision due to their
high plasticity. We use powder sintering (a process of compact-
ing and forming a solid mass of material by heat or pressure
without melting it to the point of complete liquefaction)[4] to
generate a porous structure. More specifically, we sintered
wear- and impact-resistant ultra-high molecular weight poly-
ethylene powders to a convenient shape such as a tablet (Fig-
ure 1b). The tablet has a porous and open-cell structure that
allows the fast mass transfer. Moreover, because the tablets
are made from wear- and impact-resistant material, they may
not break in a long time stirring.
(molecular weight > 1500000, ca 30-80 µm in diameter) to pre-
pare porous tablets via powder sintering.[7] The porous plastic
generated from the sintering of plastic powders has been
widely used in industries to make filtration devices.[7] So the
porous tablets could be prepared in large quantities. UHMWPE
is also highly chemical inert and exhibits virtually no water ab-
sorption, and it is not soluble in most organic solvents.
Although many other shapes could be made, we chose a tablet
for catalyst immobilization because tablets are both conven-
ient to manufacture and also to handle. We prepared tablets
Our catalyst immobilization process is straightforward. The
powderous catalysts as micro- or nanopowders are suspended
in a suitable inert solvent (e.g., ethanol) in the presence of po-
rous plastic tablets. After stirring, if the particle size of catalysts
Key Laboratory of Science and Technology of Eco-Textiles, Ministry
of Education, College of Chemistry, Chemical Engineering and Bio-
technology, Donghua University, Shanghai 201620, China
E-mail: bo.xu@dhu.edu.cn
Chin. J. Chem. 2018, template© 2018 SIOC, CAS, Shanghai,
&
WILEY-VCH Verlag GmbH
&
Co. KGaA,
Weinheim

Running title
Chin. J. Chem.
in 7.1 mm and 5.1 mm diameters with the thickness at 4 mm particle is simplified as a sphere and the surface of porous tab-
and 2.5 mm respectively (Figure 1b). The obtained porous ul- lets is simplified as a flat slab).[5] This indicated that interfacial
tra-high molecular weight polyethylene tablets could be cut by Lifshitz-van der Waals interactions could function via a much
sharp knife but they almost never break during stirring.
The catalyst immobilization process is shown in Figure 2
longer distance. As a result, catalyst particles could be drawn
to the surface of porous tablets effectively.
.
First, the powderous catalysts such as micron-size copper
powders (ca 0.5 m in diameters) and Pd/Al2O3 (ca 1-5 m in
µ
µ
diameters) are suspended in ethanol, then porous tablets
were added. To our delight, after stirring for 4.0 h, both copper
and Pd/Al2O3 were easily trapped or encapsulated by porous
tablets, and the solution becomes clear (Figure 2). The obser-
vation that the solution becomes clear indicates that the vast
majority of catalysts have been loaded to tablets. We found
that this is a general method to bond the reactive catalysts to
the porous tablets as long as the particle size of the catalyst is
LW = - /12πd2
A
d
Figure 3. Lifshitz-van der Waals interactions between a sphere and a flat slab
(d = distance).
Our proof of concept application is the immobilization of
commercially available and widely used Pd/C (10 wt/wt% Pd
content) and Pd/Al2O3 (5 wt/wt% Pd content). Both commer-
cial Pd/C and Pd/Al2O3 are supplied as very fine powders,
which causes many problems during weighing, transferring,
and filtrating. Our immobilization protocol could solve these
problems. The catalyst loaded tablets are mechanically robust
for stirring. Pd/C@Tab-based reactions had a similar kinetic
profile (only slightly slower) compared to reactions conducted
using catalysts in powders in the hydrogenation of nitro-com-
pound (Figure 4a). Pd/C@Tab could be recycled and reused for
6 times without significant loss of reactivity (Figure 4b). When
powderous Pd/C was used, 13 ppm of palladium (determined
by ICP-AES) remained in the reaction mixture after filtration by
smaller than the pores in the tablets (ca 10-25
µm, see Figure
2
d). The immobilized catalysts (named as Cu@Tab and
Pd/Al2O3@Tab) (See Supporting Information for more details)
were much easier to recover by filtration. As a comparison, af-
ter an ethanol suspension containing the powderous catalyst
(Pd/Al2O3) was filtered through a filter paper, the filtrate still
contains a considerable amount of catalyst particles, as indi-
cated by the Tyndall effect (the illumination with a green laser).
However, when the solution containing immobilized catalyst
tablets was illuminated with a laser light directly without fil-
tration, the Tyndall effect is very weak (Figure 2c). We also in-
vestigated the microscopic images of blank tablets and tablets
immobilized with catalysts. As shown in Figure 2d, the blank
tablet has pores ranged from 10-100 μm in diameters. The
SEM images of the cross-section of Cu@Tab (Figure 2e) and
Pd/Al2O3@Tab (Figure 2f) clear indicated that the surface of
porous tablets was covered with catalyst particles (Cu and
Pd/Al2O3).
a filtration paper[8]
(Figure 4c). Our immobilization method can
reduce palladium leaching significantly. As shown in Figure 4c,
the palladium leaches in the reaction mixture of each cycle
were all below 0.15 ppm. Similarly, Pd/Al2O3@Tab based reac-
tions also had a similar kinetic profile (slightly slower) com-
pared to reactions conducted using catalysts in powders (Fig-
ure 4d).
Pd/Al2O3
a)
Micron Cu
c)
b)
Pd/Al2O3
Pd catalyst
H
2 (1
atm) EtOH
,
NO2
NH2
a)
b)
Filtered with
filterpaper
Pd/Al2O3@Tab
Before stirring
Afterstirring
Before stirring
Afterstirring
d)
f)
e)
d)
30 µm
100 µm
5 µm
Pd leaching of
powderous Pd/C: 13 ppm
Figure 2. Immobilization of powderous catalysts to porous plastic tablets. a)
Immobilization of micro-size copper powders. b) Immobilization of commer-
cial Pd/Al2O3. c) Tyndall effects of immobilized and un-immobilized catalysts.
d) SEM image of the cross-section of a blank tablet. d) SEM image of the
cross-section of Cu@Tab; f) SEM image of the cross-section of Pd/Al2O3@Tab.
It should be noted that the porous tablets have no adsorp-
tion capacity for small molecule compounds (e.g., ferrocene)
and macromolecular compounds (e.g., polyimide) soluble in
solutions. However, the tablets could adsorb the suspended
nano or microparticles in liquids. The immobilized catalyst par-
ticles appeared to be in a monolayer according to the SEM
images (Figure 2). We propose that the porous support absorbs
the catalyst particles via interfacial Lifshitz-van der Waals in-
teractions (van der Waals forces between bodies) (Figure 3).[5]
In contrast to van der Waals forces between two molecular
(proportional to 1/d6, d = distance), the interfacial Lifshitz-van
der Waals force is approximately proportional to 1/d2 (derived
from a simplified system-a sphere and a flat slab, the catalyst
Figure 4. Pd catalyzed hydrogenation of nitro-compound. Pd loading (1%),
please see SI for the preparation of Pd/C@Tab. The conversions were deter-
mined by GC). a) Kinetic profile comparison between Pd/C powder and
Pd/C@Tab. b) Recycling experiments of Pd/C@Tab. c) Leaching of catalysts
in cycling experiments. d) Kinetic profile comparison between Pd/Al2O3 pow-
der and Pd/Al2O3@Tab.
Because the hydrogenation reactions[9] are one of the most
used reactions in industry, encouraged by the success in the
hydrogenation of nitro-compound, we explored the applicabil-
ity of our immobilized catalyst in diverse hydrogenation reac-
tions. As shown in Table 1, our immobilized catalyst worked
very well for the hydrogenation reaction of alkenes and al-
kynes (Table 1, entries 1–4), nitro-compounds (Table 1, entry 5),
imines (Table 1, entry 6), organo-azides (Table 1, entries 7–12),
Chin. J. Chem. 2021, 39, XXX－XXX
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First author et al.
Report
aldehydes and ketones (Table 1, entries 13–16). Good yields of
corresponding reduction products were all obtained. It is
worth mentioning that the selectivity of catalyst is retained by
immobilizing powderous catalysts to tablets. For example, our
Pd/C@Tab exhibited high activity in the selective hydrogena-
tion of (E)-chalcone to produce dihydrochalcone with high se-
lectivity (Table 1, entry 1). We then explored the applicability
of our immobilized catalyst in deprotection reactions (Table 2),
and high isolated yields of deprotection products were
obtained without exception. In a controlled experiment, the
Pd/C@Tab was taken out of the reaction solution 2 hours after
the reaction started. The reaction stopped at 38% even if it
kept stirred for another 2 h. That indicates that the real catalyst
is tablet supported palladium and not Pd leached to the solu-
tion.
a Reaction conditions: substrate (0.18 mmol), Pd/C@Tab (1 tablet, 1 mol%),
EtOH (2 mL), rt, in H2 atmosphere (balloon). All yields are isolated yields.
Table 2. Pd/C@Tab catalyzed deprotection. a
Entry
Substrate
Product
Yield (%)
98
O
O
H
N
O
H
N
O
OH
O
O
OH
O
HN
Ph
O
NH2
1
O
O
Ph
O
HO
OH
O
OH
O
HN
O
HN
O
2
93
O
O
O
Table 1. Pd/C@Tab catalyzed hydrogenation. a
O
Entry
1
Substrate
Product
Time(h)
2
Yield(%)
86
OH
Cbz
OH
O
3
4
85
90
HN
NH2
O
O
Ph
Ph
Cbz
O
NH
Cbz
O
S
O
O
S
O
HO
OH
2
3
4
3
85
75
96
96
83
84
94
92
95
84
95
80
88
87
63
O
NH2
HO
HO
HO
O
O
O
O
OH
O
OH
O
HN
N
5
84
O
N
HN
N
HN
O
H2N
S
S
4
8
O2N
N
O
N
O
a
Reaction conditions: substrate (0.10 mmol), Pd/C@ tab (3 tablets, 5.4
mol%), EtOH (2 mL), rt, 4h, in H2 atmosphere (balloon). All yields are isolated
yields.
5
6
N
H
N
H
NH2
NO2
N
H
N
Our immobilization protocol appeared to be very general. As
shown in Figure 5, we investigated Cu@Tab, Rh/C@Tab, and
Pt/C@Tab catalyzed reactions. We first investigated the cop-
per-catalyzed borylation reaction[10] (Figure 5a). Cu@Tab could
be reused 8 times without significant loss of reactivity, and the
copper leaches in each cycle were all below 1 ppm except the
first time. The relative higher leaching of copper in the first cy-
cle could be rationalized by the loss of copper absorbed in the
surface part of tablets. Besides, Cu@Tab worked well in more
variety of copper-catalyzed reactions such as Sonogashira type
coupling, tandem borylation-Suzuki reactions, and C-O bond
formations (Figure 5b)[10-11]. Next, we investigated Pt/C@Tab
(Figure 5c), and Rh/C@Tab catalyzed reactions (Figure 5e),[12]
they both worked well in reusability and metal leaching. In
both cases, the leaching of metal was well below 0.2 ppm. We
also explored several additional reactions catalyzed by
Rh/C@Tab and Pt/C@Tab (Figure 5d and f), good yields of
products were always obtained.[13]
6
12
6
N3
NH2
O
S
O
7
O
S
O
8
2
N3
NH2
O
NH2
O
N3
S
S
O
O
9
2
O
O
N
H
H
N
O
S N3
O
O
S NH2
O
10
11
12
13
14
15
16
2
O
O
O
S
O
O
S
O
2
HN
HN
N3
NH2
O
S
O
O
S
O
N3
NH2
2
It should be noted that our immobilization protocol makes
the reuse of micro- and nanocatalyst much easy and metal
leaching could be minimized. For example, in copper-catalyze
OH
OH
4
CHO
CHO
borylation reaction, micro copper powders (0.5 µm) and nano
OH
OH
4
copper powders (50 nm) were used. However, the small size of
copper powders makes it difficult for a conventional filter to
filter off, and a considerable amount of copper particles will
pass through during filtration. As a result, metal leaching will
be high, and the catalysts are difficult to be reused.
OH
O2N
CHO
6
H2N
O
OH
3
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Running title
Chin. J. Chem.
CH ONa
3
Cu@Tab,
EtOH,
B(pin)
+
Ph
B
Ph
2(pin)2
rt, 6h
PPh K CO
,
Cu@Tab,
3
2
3
+
I
Ph
Ph
DMF, 135o 12 h
C,
82%
5
4
3
2
1
0
100
80
60
40
20
Ph
I
, CH3ONa
Cu@Tab, Pd(PPh3)4
+
+
Ph
B
2(pin)2
NaOH, Dioxane/EtOH
NC
60 o 18 h
NC
79%
C,
O
OH
O
Cs CO
Cu@Tab,
2
3
+
O
0
1
DMF, 110o 12 h
2
3
4
5
6
7
8
C,
1
2
3
4
5
6
7
8
I
Cycles
Cycles
96%
O
O
O
O
Na CO
Pt/C@Tab,
2
3
Na CO
Pt/C@Tab,
2
3
iPrOH/H Ar, Reflux, 24h
2O,
86%
F
i-PrOH/H
Ar, Reflux, 24h
2O,
F
O
Na CO
Pt/C@Tab,
2
3
1.0
0.8
0.6
0.4
0.2
0.0
F
83%
O
iPrOH/H
Ar, Reflux, 24h
2O,
100
80
60
40
20
O
)
O
O
B
O
O
B
O
B
O
Ar
Pt/C@Tab,
toluene, 70o 12h
+
Ph
B
C,
O
91%
0
1
H
Pt/C@Tab,
2
1
2
3
4
Cycles
5
6
7
2
6
7
3 Cy4cles5
130o 12h
N
H
N
O,
C,
1-pentanol/H2
75%
H
CH CN
3
,
Rh/C@Tab,
2
CH
NH2
3(CH2)9
CH
NHCH2CH3
3(CH2)9
rt, 24h
MeOH,
1.0
100
80
60
40
20
N
)
0.8
0.6
0.4
0.2
0.0
N
Rh/C@Tab
TFA
+
N
N
88%
0
1
1
2
3
4
5
6
7
2
3
4
5
6
7
Cycles
Cycles
Figure 5. More applications of immobilized catalysts. a) Recycling and leaching experiments of Cu@Tab (0.25 mg/Tab). b) Additional applications of Cu@Tab. c)
Recycling and leaching experiments of Pt/C@Tab (0.90 mg Pt per tablet). d) Additional applications of Pt/C@Tab. e) Recycling and leaching experiments of
Rh/C@Tab (1.0 mg/tab). f) Additional applications of Rh/C@Tab. The conversions were determined by GC–MS. The reaction yields in b), d) and f) are all isolated
yields.
(balloon). Then the substrate (0.18 mmol) in EtOH (2 mL) was
Conclusions
added by syringe. The reaction was stirred at room temperature
and monitored by TLC or GC-MS. After the reaction was completed,
the Pd/C tablet was removed and washed with DCM three times.
The combined solution was concentrated in vacuo to give the
crude hydrogenated product.
In summary, we have developed a practical immobilization
protocol for the encapsulation of powderous catalysts to po-
rous plastic tablets. Our immobilization method is general,
and it could be applied to diverse heterogeneous catalysts
such as Pd/C, Pd/Al2O3, copper, Pt/C, and Rh/C catalysts. The
immobilized catalysts are easy to handle and reuse. Moreover,
the metal leaching of treated catalysts was reduced signifi-
cantly. More applications for heterogeneous catalyst immobi-
lization and larger-scale applications are under investigation
in our laboratory.
Supporting Information
The supporting information for this article is available on the
WWW under https://doi.org/10.1002/cjoc.2021xxxxx.
Acknowledgment
Experimental
We are grateful to the National Science Foundation of China
(NSFC-21871046). TL was also thankful to “the Fundamental Re-
search Funds for the Central Universities and Graduate Student In-
novation Fund of Donghua University”.
General immobilization process. Heterogeneous catalysts (300
mg) were suspended in ethanol (50 mL) and crushed with a high-
speed disperser. Then 30 PE tablets were added. The mixture was
stirred with a magnetic stir bar for 1-24 hours. The porous polyeth-
ylene tablet supported catalysts were took out from the suspen-
sion and stirred in clean ethanol (50 mL) for 12 h to wash off the
excess catalysts on the surface. In this way, the load of the catalyst
was the maximum value.
References
[1] (a) Kudaibergenov, S. E.; Tatykhanova, G. S.; Selenova, B. S. Polymer
Protected and Gel Immobilized Gold and Silver Nanoparticles in
Catalysis. J. Inorg. Organomet. Polym. Mater. 2016, 26, 1198-1211; (b)
Navalón, S.; García, H. Nanoparticles for Catalysis. Nanomaterials
2016, 6, 1-3.
Ggeneral procedure for the Pd/C tablet (Pd/C@Tab) catalyzed
hydrogenation. An oven-dried Schlenk tube was charged with
Pd/C@Tab (1 tablet, 1.8 µmol Pd, 1 mol %) and H2 atmosphere
Chin. J. Chem. 2021, 39, XXX－XXX
©2021 SIOC, CAS, Shanghai, & WILEY-VCH GmbH
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First author et al.
Report
[2] (a) Benaglia, M.; Puglisi, A.; Cozzi, F. Polymer-Supported Organic
Catalysts. Chem. Rev. 2003, 103, 3401-3430; (b) Nasrollahzadeh, M.;
Sajjadi, M.; Shokouhimehr, M.; Varma, R. S. Recent Developments in
Palladium (Nano)catalysts Supported on Polymers for Selective and
Sustainable Oxidation Processes. Coord. Chem. Rev. 2019, 397, 54-75;
(c) Bi, J.; Chen, J.; Dong, Y.; Guo, W.; Zhu, D.; Li, T. Polymer-supported
Palladium (II) Containing N2O2: An Efficient and Robust
Heterogeneous Catalyst for C-C Coupling Reactions. J. Polym. Sci., Part
A: Polym. Chem. 2018, 56, 2344-2353; (d) Liang, W.; Zhang, T.; Liu, Y.;
Huang, Y.; Liu, Z.; Liu, Y.; Yang, B.; Zhou, X.; Zhang, J.
Polydimethylsiloxane Sponge-Supported Nanometer Gold: Highly
Efficient Recyclable Catalyst for Cross-Dehydrogenative Coupling in
Water. ChemSusChem 2018, 11, 3586-3590; (e) Anjali, J. K.; Sreekumar,
K. Heterogeneous High-Loading Hyperbranched Polyglycidol with
Peripheral NHC-Pd Complex: Synthesis and Application as Catalyst in
Suzuki Coupling Reaction. Catal. Lett. 2019, 149, 1952-1964; (f)
Kuwahara, Y.; Kango, H.; Yamashita, H. Pd Nanoparticles and
Aminopolymers Confined in Hollow Silica Spheres as Efficient and
Reusable Heterogeneous Catalysts for Semihydrogenation of Alkynes.
ACS Catal. 2019, 9, 1993-2006; (g) Liang, Z.; Chen, J.; Chen, X.; Zhang,
K.; Lv, J.; Zhao, H.; Zhang, G.; Xie, C.; Zong, L.; Jia, X. Porous Organic
a Porous Medium: Mechanisms for Particle Filtration and Retardation
during Downward Transport. Water Resour. Res. 2006, 42.
[6] https://www.braskem.com.br/Portal/Principal/arquivos/HRP_15-
016_v02_UTEC_Brochure_iPad.pdf
[7] Alderson, K. L.; Webber, R. S.; Evans, K. E. Novel Variations in the
Microstructure of Auxetic Ultra-high Molecular Weight Polyethylene.
Part 2: Mechanical Properties. Polym. Eng. Sci. 2000, 40, 1906-1914.
[8] Pleated cellulose disc filters (0.03 mm thickness) were used.
[9] (a) Hart, A.; Omajali, J. B.; Murray, A. J.; Macaskie, L. E.; Greaves, M.;
Wood, J. Comparison of the Effects of Dispersed Noble Metal (Pd)
Biomass Supported Catalysts with Typical Hydrogenation (Pd/C,
Pd/Al2O3) and Hydrotreatment Catalysts (Como/Al2O3) for In-situ
Heavy Oil Upgrading with Toe-to-heel Air Injection (THAI). Fuel 2016,
180, 367-376; (b) Mitra, J.; Zhou, X.; Rauchfuss, T. Pd/C-catalyzed
Reactions of HMF: Decarbonylation, Hydrogenation, and
Hydrogenolysis. Green Chem. 2015, 17, 307-313; (c) Pietrobon, L.;
Ronchin, L.; Sadraoui, C.; Pontello, R.; Tosetto, C.; Vavasori, A. Pd/C
Catalyzed Selective Hydrogenation of Nitrobenzene to Cyclohexanone
Oxime in the Presence of NH2OH·HCl: Influence of the Operative
Variables and Insights on the Reaction Mechanism. Appl. Catal. A Gen.
2020, 598, 117570; (d) Shafaghat, H.; Lee, I.-G.; Jae, J.; Jung, S.-C.; Park,
Y.-K. Pd/C Catalyzed Transfer Hydrogenation of Pyrolysis Oil Using 2-
Propanol as Hydrogen Source. Chem. Eng. J. 2019, 377, 119986.
[10] Liu, S.; Zeng, X.; Xu, B. (E)-Alkene Synthesis via Nano-
Copper/Homogeneous Palladium Co-Catalysis and Selectivity
Amplification. Asian J. Org. Chem. 2017, 6, 507-511.
Polymer Supported Rhodium as
A Heterogeneous Catalyst for
Hydroformylation of Alkynes to α,β-Unsaturated Aldehydes. Chem.
Commun. 2019, 55, 13721-13724; (h) Miyamura, H.; Tobita, F.; Suzuki,
A.; Kobayashi, S. Direct Synthesis of Hydroquinones from Quinones
through Sequential and Continuous-Flow Hydrogenation-
Derivatization Using Heterogeneous Au-Pt Nanoparticles as Catalysts.
Angew. Chem., Int. Ed. 2019, 58, 9220-9224; (i) Nasrollahzadeh, M.;
Motahharifar, N.; Ghorbannezhad, F.; Soheili Bidgoli, N. S.; Baran, T.;
Varma, R. S. Recent Advances in Polymer Supported Palladium
Complexes as (Nano)catalysts for Sonogashira Coupling Reaction. Mol.
Catal. 2020, 480, 110645; (j) Ren, C.; Zhu, X.; Zhao, N.; Shen, Y.; Chen,
L.; Liu, S.; Li, Z. Polystyrene Beads Supported Phosphazene Superbase
as Recyclable Organocatalyst for Ring-opening Polymerization of δ-
Valerolactone. Eur. Polym. J. 2019, 119, 130-135; (k) Renuka, M. K.;
Gayathri, V. Oxidation of Benzyl Alcohols by Polymer Supported V(IV)
Complex Using O2. Catal. Lett. 2019, 149, 1266-1276; (l) Valentini, F.;
Mahmoudi, H.; Bivona, L. A.; Piermatti, O.; Bagherzadeh, M.; Fusaro,
L.; Aprile, C.; Marrocchi, A.; Vaccaro, L. Polymer-Supported Bis-1,2,4-
triazolium Ionic Tag Framework for an Efficient Pd(0) Catalytic System
in Biomass Derived γ-Valerolactone. ACS Sustainable Chem. Eng. 2019,
7, 6939-6946; (m) Verheyen, T.; Santillo, N.; Marinelli, D.; Petricci, E.;
De Borggraeve, W. M.; Vaccaro, L.; Smet, M. An Effective and Reusable
Hyperbranched Polymer Immobilized Rhodium-Catalyst for the
Hydroformylation of Olefins. ACS Appl. Polym. Mater. 2019, 1, 1496-
1504; (n) Yu, X.; Yang, Z.; Zhang, F.; Liu, Z.; Yang, P.; Zhang, H.; Yu, B.;
Zhao, Y.; Liu, Z. A Rose Bengal-functionalized Porous Organic Polymer
for Carboxylative Cyclization of Propargyl Alcohols with CO2. Chem.
Commun. 2019, 55, 12475-12478; (o) Zhang, C.; Qiu, Y.; Bo, S.; Wang,
F.; Wang, Y.; Liu, L.; Zhou, Y.; Niu, H.; Dong, H.; Satoh, T. Recyclable
Helical Poly(phenylacetylene)-supported Catalyst for Asymmetric
Aldol Reaction in Aqueous Media. J. Polym. Sci., Part A: Polym. Chem.
2019, 57, 1024-1031.
[11] (a) Oka, H.; Kitai, K.; Suzuki, T.; Obora, Y. N,N-Dimethylformamide-
Stabilized Copper Nanoparticles as
A Catalyst Precursor for
Sonogashira–Hagihara Cross Coupling. RSC Adv. 2017, 7, 22869-22874;
(b) Puthiaraj, P.; Ahn, W.-S. Synthesis Of Copper Nanoparticles
Supported on a Microporous Covalent Triazine Polymer: An Efficient
and Reusable Catalyst for O-arylation Reaction. Catal. Sci. Technol.
2016, 6, 1701-1709.
[12] (a) Khan, A.; Asiri, A. M.; Kosa, S. A.; Garcia, H.; Grirrane, A. Catalytic
Stereoselective Addition to Alkynes. Borylation or Silylation Promoted
By Magnesia-Supported Iron Oxide And Cis-Diboronation or
Silaboration by Supported Platinum Nanoparticles. J. Catal. 2015, 329,
401-412; (b) Ikawa, T.; Fujita, Y.; Mizusaki, T.; Betsuin, S.; Takamatsu,
H.; Maegawa, T.; Monguchi, Y.; Sajiki, H. Selective N-Alkylation of
Amines Using Nitriles under Hydrogenation Conditions: Facile
Synthesis of Secondary and Tertiary Amines. Org. Biomol. Chem. 2012,
10, 293-304.
[13] (a) Sawama, Y.; Yabe, Y.; Shigetsura, M.; Yamada, T.; Nagata, S.;
Fujiwara, Y.; Maegawa, T.; Monguchi, Y.; Sajiki, H. Platinum on Carbon-
Catalyzed Hydrodefluorination of Fluoroarenes using Isopropyl
Alcohol-Water-Sodium Carbonate Combination. Adv. Synth. Catal.
2012, 354, 777-782; (b) Xue, X.; Zeng, M.; Wang, Y. Highly Active and
Recyclable Pt Nanocatalyst for Hydrogenation of Quinolines and
Isoquinolines. Appl. Catal. A Gen. 2018, 560, 37-41; (c) Matsumoto,
K.; Yoshida, M.; Shindo, M. Heterogeneous Rhodium-Catalyzed
Aerobic Oxidative Dehydrogenative Cross-Coupling: Nonsymmetrical
Biaryl Amines. Angew. Chem., Int. Ed. 2016, 55, 5272-5276.
[3] https://www.sigmaaldrich.com/content/dam/sigma-
aldrich/docs/Aldrich/Brochure/al_chemfile_v5_n11.pdf
(The following will be filled in by the editorial staff)
[4] Webber, R. S.; Alderson, K. L.; Evans, K. E. A Novel Fabrication Route
for Auxetic Polyethylene, Part 2: Mechanical Properties. Polym. Eng.
Sci. 2008, 48, 1351-1358.
Manuscript received: XXXX, 2021
Manuscript revised: XXXX, 2021
[5] (a) Van Oss, C. J.; Chaudhury, M. K.; Good, R. J. Interfacial Lifshitz-van
der Waals and Polar Interactions in Macroscopic Systems. Chem. Rev.
1988, 88, 927-941; (b) Bhattacharjee, S.; Sharma, A. Interaction
Energy of Particles in Porous Media:ꢀ New Deryaguin Type
Approximation. Langmuir 1996, 12, 5498-5500; (c) Yoon, J. S.;
Germaine, J. T.; Culligan, P. J. Visualization of Particle Behavior within
Manuscript accepted: XXXX, 2021
Accepted manuscript online: XXXX, 2021
Version of record online: XXXX, 2021
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© 2021 SIOC, CAS, Shanghai, & WILEY-VCH GmbH
Chin. J. Chem. 2021, 39, XXX－XXX

Running title
Chin. J. Chem.
Entry for the Table of Contents
Mechanically Strong Heterogeneous Catalysts via Immobilization of Powderous Catalysts to Porous Plastic Tablets
Tingting Li, and Bo Xu*
Chin. J. Chem. 2021, 39, XXX—XXX. DOI: 10.1002/cjoc.202100XXX
Sinteredporous plastic tablets as catalyst carriers
Examples of catalyst-loadedtablets
Pd/C@Tab
Pd/Al2O3@Tab
Cu@Tab
Pt/C@Tab
Rh/C@Tab
• General immobilization protocol
• Mechanicallystrong
• Recyclable
• Much reduced metal leaching
Chin. J. Chem. 2021, 39, XXX－XXX
©2021 SIOC, CAS, Shanghai, & WILEY-VCH GmbH
www.cjc.wiley-vch.de