AgNPs encapsulated by an amine-functionalized polymer nanocatalyst for CO2 fixation as a carboxylic acid and the oxidation of cyclohexane under ambient conditions

Article abstract of DOI:10.1039/c9nj05865f

Silver nanoparticles (AgNPs) embedded in a porous polystyrene material (AgNPs@m-PS-PC) were synthesized via the polymerization of polystyrene amine and 2-pyridinecarbaldehyde, followed by the reduction of silver nitrate in methanol. The structure and morphology of this porous material were characterized by powder X-ray diffraction, transmission electron microscopy (TEM), scanning electron microscopy, Fourier-transform infrared, ultraviolet-visible, and atomic absorption spectroscopies, and thermogravimetric analysis. TEM showed that the AgNPs were well dispersed in the polymeric matrix, with dimensions of around 4-9 nm. This nanocatalyst showed activity, particularly for the green synthesis of valuable carboxylic acids by the carboxylation reaction of terminal alkynes with carbon dioxide under atmospheric pressure. Additionally, the catalyst displayed efficient catalytic activity for the oxidation of cyclohexane using hydrogen peroxide as the oxidising agent. The AgNPs@m-PS-PC nanocatalyst could be recycled five times and retained reliable efficiency.

Full text of DOI:10.1039/c9nj05865f

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ISSN 1144-2546
PAPER
Chechia Hu, Tzu-Jen Lin et al.
Yellowish and blue luminescent graphene oxide quantum dots
prepared via a microwave-assisted hydrothermal route using
H2O2 and KMnO4 as oxidizing agents
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Received 00th January 20xx,
Accepted 00th January 20xx
AgNPs Encapsulated by Amine-Functionalized Polymer
Nanocatalyst for the CO2 Fixation as Carboxylic Acid and
Oxidation of Cyclohexane under Ambient Conditions
DOI: 10.1039/x0xx0
www.rsc.org/
a
Noor Salam,a,b,# Priyanka Paul,a,c,# Swarbhanu Ghosh , Usha Mandi,d Aslam Khan,e Seikh Mafiz
Alamc,*, Debasis Das b,* and Sk. Manirul Islama,*
Abstract
Silver nanoparticles (NPs) embedded over porous polystyrene (AgNPs@m-PS-PC) material have been synthesized through
the polymerization of polystyrene amine and 2-pyridinecarbaldehyde followed by reduction of silver nitrate in methanol.
The structure and morphology of this porous material were characterized by XRD, TEM, SEM, FTIR spectra, UV-Vis spectra,
AAS and TGA. The transmission electron microscopy has provided that the dispersion of the silver nanoparticles in the
polymeric matrix is well and the dimension of silver nanoparticles are around 4-9 nm. This nanocatalyst shows activity
particularly for green synthesis of valuable carboxylic acids by the carboxylation reaction of terminal alkynes with carbon
dioxide under atmospheric pressure. Additionally, the catalyst was also evaluated as efficiently catalytic activity for the
oxidation of cyclohexane using hydrogen peroxide as oxidising agent. The AgNPs@m-PS-PC nanocatalyst shows excellent
recycled power for five times runs with almost reliable efficiency.
such as converting carbon dioxide into synthesis of fine chemicals
using cheap, abundant environmental friendly and nontoxic
Introduction
Novel metal nanomaterials have potential scientific interest due to
their novel properties and fundamental importance in various
application fields such as catalyst, optoelectronics, drug delivery
and so on.1-5 The catalytic performance of nanomaterial depends on
the size and shape of the nanoparticle and the nature of the
supports used.6-9 So, the development of high-performance
catalytic materials is still a major challenge in synthetic chemistry.
Among noble metal nanoparticles, Silver nanoparticles have
garnered enormous attention in nano research field due to their
exceptional size dependent features in various types of reactions.10-
obtained industrial chemicals. The carboxylation reaction of
terminal alkynes, catalyzed by the transition metals and using CO2,
to synthesize propiolic acids are important in the field of medicinal
chemistry is indeed more advantageous and promising avenues.22
In literature, for this carboxylation reaction, several homogeneous
catalysts of silver salt are reported.23 However, due to prevention
from the recovery of catalyst or separation problems from mixture
of product further application was strictly hampered. Recently few
heterogeneous metal anchored catalytic systems for this reaction
have been reported.24 Thereafter, in our efforts towards
13
Due to their unique nanostructure and properties, surface area,
development environmental favourable processes,
a
few
surface texture, easy aggregation, synthetic methods and reaction
conditions Ag nanoparticles show the highly catalytic performance.
Ag nanoparticles exhibit high catalytic activity for the oxidation of
phenylsilanes to silanols,14 electrochemical oxidation of methanol,15
CO2 fixation,16 oxidation of textile dyes,17 and oxidation of m-
xylene,18 oxidation of cyclohexene19. Furthermore, supported Ag
nanoparticles have unique catalytic behavior in many organic
transformations.20a,b,c
heterogeneous catalyzed the coupling reaction of terminal alkynes
with carbon dioxide used as carbon source for production of
carboxylic acid derivative have been also introduced.25 Notable
these reported metal catalysts may suffer from various problems
like low yield, harsh conditions, or complicated material synthesis.
From the literature survey, only a few works are found related to
the heterogeneous silver nanoparticle based catalysts. For that
reason, the development of robust and highly efficient porous silver
nanocatalyst in the respect of environment favor for CO2 utilization
at room temperature is highly desirable and demand, yet remains
great importance.
The excessive discharge of carbon dioxide for combustion of fossil
fuels in our global has been considered to be a vital issue faced in
the few decades as it is responsible for a series of environmental
and economy troubles due to a series of environmental and
economy problems.21 So, one of the ways to alleviate this problem
is to utilization and transformation of abundant gaseous waste,
Traditionally, the catalytic oxidation of cyclohaxane is also one of
the most promising avenues in recent due to of their potential
applicability of their products in industrial and biological chemistry.
The selective product of cyclohexane into industrial production of
KA oil (the mixture of cyclohexanol and cyclohexanone) serves as
extremely importance as intermediates for the synthesis of
caprolactam and adipic acid for the manufacture of nylon.26 There
are several heterogeneous and homogeneous catalytic systems for
the oxidation of cyclohexane.26 However, either difficulties in
a Department of Chemistry, University of Kalyani, Kalyani, Nadia, 741235, W.B., India
bDepartment of Chemistry, The University of Burdwan, Burdwan, , W.B., India.
c Department of Chemistry, Aliah University, Newtown, Kolkata-700156, W.B., India
dDepartment of Chemistry, Jogamaya Devi College, Kolkata, 700026, W.B., India.
eKing Abdullah Institute for Nanotechnology, King Saud University, Riyadh, 11451, Saudi
Arabia
#
These authors contributed equally.
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reusability and harsh reaction conditions are involved in oxidation
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DOI: 10.1039/C9NJ05865F
of cyclohexane using homogeneous systems, which strictly
28
hampered their further applications.27,
Fortunately,
heterogeneous catalysis can overcome these problems. There are
several reports on metal supported catalyst such as Co, Fe-based
catalysts but which is unsatisfactory in catalytic performance
because of lower yield of desired products or using toxic solvents.29
In this article we have demonstrated a new silver nanoparticle
incorporated onto the surface of micro porous polymer supported
ligand (AgNPs@m-PS-PC). The material shows excellent catalytic
activity towards cyclohexane oxidation and the direct terminal
alkynes carboxylation with help of carbon dioxide as carbon source
under atmospheric pressure.
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Experimental
Scheme 1 Synthesis of the microporous AgNPs@m-PS-PC nanocomposite.
Synthesis of silver nanoparticles grafted microporous polymer-
supported 2-pyridinecarbaldehyde nanocomposite (AgNPs@m-PS-
PC)
Results and discussion
Characterization of Nanomaterial
PXRD Analysis
The microporous AgNPs@m-PS-PC material was synthesized under
in-situ synthesis of silver nanoparticles in polymer framework.
Synthesis of colloidal silver nanoparticles were done by reduction of
40 ml methanolic solution of AgNO3 (100 mg) containing TRIS (0.5 g)
using 1.0 mL of methanolic solution of NaBH4 (0.08%) as reducing
Fig. 1 shows the XRD spectra of m-PS-PC ligand, AgNPs and
AgNPs@m-PS-PC nanocomposite. A broad spectrum appears at 2θo
range of 10-30 clearly reflects the amorphous nature of polymer
matrix.20d,e The XRD pattern of synthesized AgNPs showed four
characteristics sharp peaks at 38.5o, 44.5o, 63.8o and 78.6° could be
attributed to the corresponding diffraction planes of (111), (200),
(220) and (311) respectively which assigned to a face centred cubic
(FCC) structure of metallic silver nanoparticles (JCPDS Card No. 04-
0783)20c. From the XRD of AgNPs@m-PS-PC nanocomposite it is
seen that along with the above mentioned broad peak of polymer
matrix another four distinct sharp diffraction peaks of silver
nanoparticles are found. Thus the sharp intense peaks indicate the
successful formation of single crystalline silver nanoparticles over
surface of the polymer matrix.20a,b,c
agent. Then,
1
g
of prepared polymer-anchored 2-
pyridinecarbaldehyde ligand (m-PS-PC) was taken in synthesized
TRIS-stabilized silver nanocolloidal solution (10 ml) and it was
0
allowed to stay under continuous stirring condition for 2 h at 25 C
temperature (RT) and after complete of reaction mixture of
solution became black which indicates the Ag-NPs decorated over
exterior surface of m-PS-PC matrix. Then centrifugation was help to
collect out black coloured product Ag-NP@m-PS-PC material
followed by water and methanol as washing solvent and dried at
room temperature. It is denoted as AgNPs@m-PS-PC
nanocomposite.
General method of the direct substituted terminal alkynes
carboxylation employing carbon dioxide
For this typical reaction, terminal alkynes (1.0 mmol) were poured
into mixture of Cs2CO3 (1.2 mmol) and AgNPs@m-PS-PC
nanocatalyst (50 mg) in DMF as solvent (3 ml) and then purged by
CO2 balloon and was stirred for 12 h at 70 0C. Upon completion, the
system was allowed to go on at RT. After that resulting mixture was
transferred into 5 ml 2(N) K2CO3 solution and stirred for 30 minutes
and then washed by CH2Cl2.The aqueous layer was allowed to
acidify with conc. HCl to pH=1 and then followed by extraction with
ethyl acetate. At the end of the process, saturated NaCl solution
was used to wash organic layers and then anhydrous Na2SO4 was
utilized to get the free of moisture from product under continuous
filtration. Then it was evaporated to get the desired crude product.
General procedure for oxidation of cyclohexane using H2O2 as
oxidant
To a 50 ml double necked round bottom flask 0.42 g of cyclohexane
(5 mmol), solvent (2 ml) and AgNPs@m-PS-PC material (50 mg)
were added. 0.34 g (10 mmol) of 30% hydrogen peroxide as oxidant
was gradually added as drop wise and reaction mixture was allowed
to stay under stirred condition at 80 °C for 8 h. After reaction,
products were diluted with 1 ml of ethyl acetate and analyzed by
GC-FID chromatography.
Fig.1 PXRD spectra of m-PS-PC ligand, AgNPs and AgNPs@m-PS-PC
nanocomposite.
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UHR-TEM Analysis
supported m-PS-PC material. The electronic absVoirepwtAiortincle Obnalninde
The UHR-TEM analysis of AgNPs@m-PS-PC nanocomposite with between 330-360 nm arises due to n–π* and π–π* transitions of the
DOI: 10.1039/C9NJ05865F
different scales is shown in Fig. 2. This micrograph indicates that the imine system.30 These bands are slightly changed (blue shift) in
silver particles are nanoscopic in nature. It is also observed from the polymer supported silver nanomaterial. The reflectance spectrum
micrographs that the dimension of silver nanoparticles are ca.~ 4-9 of the supported silver nanomaterial shows bands at 430 nm due to
nm and these nanoparticles are uniformly spread at the surface of the surface plasmon resonance of silver.31
the polymeric matrix. EDX spectrum of the silver@PS
nanocomposite is shown in Fig. S1. It clearly indicates the presence
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of Ag particles in the matrix and also confirms successful formation
of AgNPs@m-PS-PC nanocomposite.
Fig.
4 UV spectra of m-PS-PC ligand and AgNPs@m-PS-PC
nanocomposite.
TG analysis
The thermal stability of silver nanocomposite material (AgNPs@m-
PS-PC) was examined by using thermal-gravimetric analysis which
performed at heating rate of 15 °C/min under the N2 flow in
temperature rangee of 33-600 °C shown in Fig. 5. This thermal
analysis data suggested that the ligand degrades at 270-440 °C
whereas the AgNPs@m-PS-PC nanocomposite at 290-470 °C. So,
from Fig. 5, we can conclude that the polymer supported silver
nanocomposite (AgNPs@m-PS-PC) possesses considerably higher
thermal stability compared to the ligand.
Fig. 2 The UHR-TEM images of AgNPs@m-PS-PC nanocomposite at
different magnifications: 500 nm (a), 200 nm (b), 50 nm (c) and 10
nm (d). The SAED pattern of AgNPs@m-PS-PC (e).
SEM analysis
The FE-SEMs were recorded for the amine functionalized ligand and
silver grafted nanomaterial to understand the morphology over the
surface of the materials shown in Fig 3. From the FE-SEM pictures it
is clearly seen that there are difference in morphological between
m-PS-PC ligand and AgNPs@m-PS-PC nanomaterial which suggests
that silver nanoparticle are incorporated into surface of the
polymer matrix. The AAS analysis was done to measure the Ag
content in the AgNPs@m-PS-PC nanocomposite and it was found to
be 0.42 wt%.
Fig. 5 TGA of m-PS-PC ligand and AgNPs@m-PS-PC nanocomposite.
Catalytic activity of AgNPs@m-PS-PC nanocomposite
Now days, designing and developing active silver nanoparticles
grafting porous catalysts have great demand in a wide range of
organic transformation. This porous catalyst can exhibit the
carboxylation of phenyl acetylene under sustainable reaction
conditions. Nanoparticles show significantly high catalytic activity
due to their quantum size effects and extensively studied for the
development of green and clean technology. Propiolic acids have
important application as intermediates in pharmaceutical and fine
chemicals. Thus, we have investigated the catalytic performance of
the porous polystyrene supported silver nanocatalyst (AgNPs@m-
Fig. 3 The FE-SEM images of m-PS-PC ligand (A) and AgNPs@m-PS-
PC nanocomposite (B).
UV-Vis absorbance spectra
UV-Vis reflectance spectrum of the m-PS-PC ligand and AgNPs@m-
PS-PC nanocomposite has been shown in Fig. 4. As noticed from this
spectrum the absorption bands at 310 nm may be assigned to π–π*
transitions of the pyridine and phenyl moieties in the polymer
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PS-PC) in the direct terminal alkynes carboxylation reaction amount of Cs2CO3 to 1.5 mmol, no obvious increase of yield was
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employing carbon dioxide under atmospheric pressure (0.1 MPa). observed. However, the 1.2 mmol was theDsOuI:p1r0e.m10e39b/Cas9eNJf0o5r8t6h5eF
The catalytic activity of our synthesized polymer was then appraised novel reaction under same environment furnished 91% of yield.
for the CO2 fixation with terminal alkynes into various substituted Therefore, after screening of all the parameters it is concluded that
propiolic acids. Firstly at 0.1 MPa of carbon dioxide pressure the the optimized reaction conditions are; Cs2CO3 as base (1.2 mmol),
carboxylation reaction between 1-ethynylbenzene and CO2 was DMF (3ml) as solvent at 70 0C temperature under atmospheric
investigated as a model reaction to optimize various conditions pressure of CO2 for 10 h.
such as solvents, reaction time and temperature for achievement
Table 1. Conditions for optimization of synthesis of phenylpropiolic
the best optimization reaction conditions shown in Table 1 (Scheme
acid under atmospheric CO2 pressure
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2).
Entry
Solvent
(ml)
Base
(mmol)
Temperature
0C )
(
Yield
(%)b
AgNPs@m-PS-PC
HCL
1c
DMF
THF
Cs2CO3
Cs2CO3
Cs2CO3
Cs2CO3
Cs2CO3
Cs2CO3
K2CO3
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70
70
70
---
CO2
Cs2CO3, DMF, 70 °C
2
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52
65
91
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34
67
23
Trace
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45
87
46
89
Scheme 2. Direct C-H carboxylation Reaction of 1-ethynylbenzene
employing CO2 balloon by AgNPs@m-PS-PC.
3
CH3CN
Dioxane
DMSO
DMF
DMF
DMF
DMF
DMF
DMF
DMF
DMF
DMF
DMF
DMF
DMF
4
5
From the solvent screening, it is undoubtedly seen that the
carboxylation reaction was significantly influenced by solvent. The
reaction shows best performance under DMF solvent than others
like CH3CN, THF, 1, 4-dioxane and DMSO under the optimized
conditions because DMF is a weak base which is a better solvent
and increasing the solubility of CO2. Furthermore, the effects of
various bases like K2CO3, Na2CO3 and Cs2CO3 for 10h at 700C
temperature were screened. From this table, we have seen that
Na2CO3 and K2CO3 resulted in rather poor yields. It is seen that
Cs2CO3 was the supreme base for the novel reaction furnished the
excellent yield of the desired propiolic acids due to its ability to
coordinate the terminal alkyne and silver catalyst and generated
silver acetylide intermediate which activated through the
adsorption of CO2 and form the silver carboxylates. With aiding of
cesium carbonate and alkynes, the silver carboxylates are rapidly
converted to cesium carboxylate via the transmetallation process.
At last stage desired carboxylic acid is obtained through the
acidification of formed cesium carboxylate. It is noted that the
temperature plays as crucial rule for excellent yield of desired
product. The effect of reaction temperature was investigated by
changing the temperature from 40 to 80 oC. The reaction should be
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Na2CO3
Cs2CO3
Cs2CO3
----
9
10
12d
13e
14f
15g
16h
17i
18j
Cs2CO3
Cs2CO3
Cs2CO3
Cs2CO3
Cs2CO3
Cs2CO3
aReactions Conditions: CO2 (1 atm), 1-ethynylbenzene (1.0mmol),
base (1.2mmol), Solvent (3 mL), AgNPs@m-PS-PC (30 mg), 10 h. bGC
yield, cWithout catalyst, dWithout base, eReaction was performed by
AgNPs@m-PS-PC (40 mg), Reaction was performed by AgNPs@m-
PS-PC (50 mg). Reaction was performed in presence of Cs2CO3 (1.0
0
carried out at 70 C to achieve the corresponding propiolic acids in
high yield (Table1, entry 6). At below temperature of 70 0C the
lower yield of propiolic acids was achieved due to the lack of
sufficient reactivity. Alternatively, the elevating temperatures did
not facilitate this reaction due to the decarboxylation of propynoate
intermediate and led to also lower yield of desired product. In
addition, it is seen that without catalyst and solvent direct
carboxylation reaction was not proceed. However, further increase
of catalyst amount (40-50 mg) led to an unexpected lower yield (75-
59%), presumably because of the decarboxylative activity of excess
Ag nanoparticle. The influence of reaction duration is found to be
crucial rule for maximum yield in this noted reaction. Therefore,
when reaction is monitored under various reaction duration on the
catalytic transformation it is seen that synthesis of phenylpropiolic
only 5h over AgNPs@m-PS-PC led to good yield of 46%, which
increased to 91% with prolonged reaction of 10 h. Because of
gradual consumption of 1-ethynylbenzene, the reaction became
lethargic, and not as much of increase of yield was obtained upon
performing reaction for 12 h. It is also seen that the amount of
Cs2CO3 showed a profound effect on product yield. When reaction
was subjected under gradually reducing Cs2CO3 amount to 1.0
mmol the yields were also significantly decreased. Increasing the
f
g
h
mmol). Reaction was performed in presence of Cs2CO3(1.5 mmol);
iReaction was performed for 5h; jReaction was performed for 12h.
We have also tested the effect of some other supports for the
terminal carboxylation reaction of terminal alkynes considering
phenyl acetylene as
experiments were carried out with other silver metal based
catalysts as reported in Table S1. Commercially purchased AgNO3
and Ag(OAc) were slightly active for the reaction but the yields (%)
were very low (Table S1, entries 1 and 2) compared to the silver
nanocomposite (Table S1, entry 3). Therefore, it is clear that silver
nanoparticles decorated solid support (AgNPs@m-PS-PC) exhibits
excellent catalytic activity for the synthesis of propiolic acids.
a model substrate (Table S1). Several
We are explored the generality the carboxylation reaction of
various substituted terminal alkynes employing CO2 by porous
AgNPs@m-PS-PC nanocomposite under the optimized conditions
(Table 2). As shown in Table 2, we have obtained good yields from
various functionalized of ethynylbenzene. All of electron-donating
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groups like -CH3, -OMe and –NH2 show slightly less the On the other hand, our observation of the present cVaiteawlyAsrtticlwe Oasnlitnoe
transformation with lower yield than1-ethynylbenzene (Table 2, more employ through another suitable catalytic pathway for
DOI: 10.1039/C9NJ05865F
entries 2-4). But 1, 4-diethynyl benzene gave relatively lower yield cyclohexane oxidation. This type oxidation was performed over
o
than others. From this observation we have concluded that AgNPs@m-PS-PC catalyst with H2O2 in CH3CN at 80 C (Scheme 3).
AgNPs@m-PS-PC nanocomposite gives the excellent catalytic To optimize the reaction condition different types of parameters
performance for CO2 conversion into alkynyl acids.
like solvent, temperature, reaction time, amount of oxidant,
catalyst amount were studied.
Table 2. Synthesis of alkynyl acid derivatives from substituted
terminal alkynes over AgNPs@m-PS-PC a
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Conv.
Yieldd Yielde
Entry
1
Alkyne
Product
(%)b,c
(%)
(%)
94
91
89
Scheme 3. Oxidation of cyclohexane catalyzed by AgNPs@m-PS-PC
nanocomposite.
Solvent plays an important role for conversion and selectivity of
products. Fig. 7 shows the wide range of solvents employed over
the oxidation of cyclohexane in presence of AgNPs@m-PS-PC
catalyst. It was seen that when acetonitrile was used as solvent the
conversion was highest (65%) under the optimized conditions.
Methanol (35%), ethanol (30%), ethylacetate (45%), chloroform
(22%) and n-hexane (40%) produced the desired product with low
conversion of cyclohexane. Furthermore, the rate of the oxidation
reaction has been also influenced by volume of solvent. When
reaction conducted by 2 to 10 ml volume of solvent conversion of
cyclohexane did not improve and gave low conversion.
85
89
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80
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2
3
83
79
76
4
73
69
66
5
aReaction condition: alkyne (1.0 mmol), DMF (3 mL), reaction
temperature (70 °C), Cs2CO3 (1.2 mmol), 10 h, CO2 (1 atm), catalyst
(50 mg; bConversion was determined by GC; cSelectivity of propiolic
acid derivatives >99%. dYield was determined by GC.. eIsolated yield.
Fig. 7 Influence of various solvents on the oxidation of cyclohexane
We have proposed a probable mechanistic pathway, based on some
reported articles25a to synthesize propiolic acids via chemical
fixation of CO2 over terminal alkynes using AgNPs@m-PS-PC (Fig. 6).
using AgNPs@m-PS-PC; Reaction condition: Cyclohexane (5 mmol),
o
Solvent (2 mL), AgNPs@m-PS-PC (50mg), 80 C, H2O2 (10 mmol), 8
h.
This reaction is monitored under different range of temperature (60
°C to 100 °C) on AgNPs@m-PS-PC catalyst keeping the other
parameters constant displayed in Fig. 8. Subsequently best outcome
of result was achieved at 80 oC and maximum conversion
cyclohexane in 65%. On further increase of temperature no such
change of conversion was observed.
Fig.
6 Plausible reaction mechanism for terminal alkyne
carboxylation over AgNPs@m-PS-PC nanocatalyst.
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Fig. 8 Influence of temperature on cyclohexane oxidation; Reaction We have performed the oxidation of cyclohexane in the presence of
condition: Cyclohexane (5 mmol), ACN (2 ml), H2O2 (10 mmol), various catalysts shown in Table 3. When we used AgVNieOw A,rAticgleOO,nlAinge
DOI: 10.1039/C9NJ05865F
3
2
AgNPs@m-PS-PC (50 mg), 8 h.
nanoparticles and polystyrene (PS) as catalysts, it was seen that the
low of conversion observed (entries 1-4). But to our delight, when
the reaction was conducted with AgNPs@m-PS-PC catalysts, then it
showed the conversion in 65% and gave excellent the selectivity of
the desired product (Table 3, entry 5) due to the synergistic effect
of Ag and polystyrene (PS) in AgNPs@m-PS-PC nanocomposite.
Conducting the reaction with AgNPs@m-PS-PC, 59% isolated yield
of cyclohexanone was achieved. Further, it is seen from the table
that, in absence of any catalyst oxidation reaction did not occur
(Table 3, entry 6). Hence, the oxidation of cyclohexane was carried
out using AgNPs@m-PS-PC nanocatalyst.
The effect of oxidant amount was also carried out on the
cyclohexane conversion (Fig. 9). A sharp increase of cyclohexane
conversion was observed under variation of the oxidant amount
from 0.17 g to 0.51 g. But no significant changes in conversion of
cyclohexane when there further increase of the H2O2 amount to
0.68 g. Hence, 0.34 g of H2O2 produced the desired product with
high conversion (65%).
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Table 3. Oxidation of cyclohexane with 30% H2O2 over different
catalystsa
Entry
Catalyst
Conversion
(%)b
Selectivityb (%)
Cyclohexanol Cyclohexanone
1
2
3
AgNO3
Ag2O
16
~9
13
38
45
41
62
55
59
Ag
nanoparticle
Polystyrene
(PS)
AgNPs@m-
PS-PC
4
5
6
Trace
Trace
Trace
65
15
85
Fig. 9 Influence of amount of oxidant on the oxidation of
cyclohexane using AgNPs@m-PS-PC catalyst; Reaction condition:
Cyclohexane (5 mmol), Acetonitrile (2 mL), AgNPs@m-PS-PC (50
mg), 80 oC, 8 h.
Without
catalyst
-
-
-
aReaction condition: Cyclohexane (5 mmol), ACN (2 mL), 80 oC, 8 h,
H2O2 (10 mmol),. bConversion and selectivity were determined by
GC.
The oxidation of cyclohexane was investigated with various amount
of our catalyst shown in Fig. 10. The reaction was conducted with
30, 40, 50 and 60 mg of AgNPs@m-PS-PC catalyst. When reaction
was conducted with 50 mg of catalyst the maximum percentage
conversion was provided due to the higher catalytic sites. No
reaction was further proceeding without catalyst. It revealed that
50 mg of catalyst loading was optimal in this system. It is suggested
that our nanomaterial truly behaves as a heterogeneous catalyst.
Evaluation of catalytic power of AgNPs@m-PS-PC for
Carboxylation reaction of terminal alkynes with other reported
systems
The comparative studies of our catalytic system with some others
are shown in Table 4.16c,32-33 From the Table 4 it is proved that our
AgNPs@m-PS-PC catalyst showed comparatively better catalytic
power towards the direct carboxylation of various alkynes with CO2
compared to the other reported systems.16c, 32-33
Table 4. Alkyne carboxylation reaction employing CO2 balloon with
other reported catalysts
Reaction
Conditions
Yield
(%)
Reactions
Catalysts
Ref.
Phenylacetylene
(1.0
mmol),
DMSO (5 mL),
68
16c
Ag@FeNT
Cs2CO3
(1.5
mmol), 15 h.
Carboxylation
of
terminal
alkynes
Phenylacetylene
(0.22 ml), Cs2CO3
Ag(O2CNMe2) (3.0 mmol), DMF
(10 ml), CO2 (1
Fig. 10 Influence of amount of nanocatalyst on the oxidation of
cyclohexane using AgNPs@m-PS-PC; Reaction condition:
Cyclohexane (5 mmol), ACN (2 ml), 80 oC, H2O2 (10 mmol), 8 h.
60
89
32
33
bar), 24 h.
From the above discussions, we conclude that the optimum
reaction condition for the best conversion and the selectivity of
desired product resulted with 30% H2O2 as oxidant in acetonitrile as
solvent at 80 oC for 8 h using AgNPs@m-PS-PC nanocomposite.
Phenylacetylene
(4.0 mmol), DMF
(20 mL), Cs2CO3
(7.2 mmol), 40
Ag@ZIF-8
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oC, 20 h, CO2 (1.0
atm).
View Article Online
DOI: 10.1039/C9NJ05865F
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Phenylacetylene
(1.0
Cs2CO3
mmol),
(1.2
AgNPs@m-
PS-PC
This
91
mmol), DMF (3
mL), 70 °C, 10 h,
CO2 (1 atm)
study
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Comparison of catalytic activity of AgNPs@m-PS-PC for the
oxidation of cyclohexane with other reported systems
The comparative studies of our catalytic system with some others
are shown in Table 5.34-35 From the Table 5, it is clear that our
AgNPs@m-PS-PC catalyst showed moderately better catalytic
efficiency compared to the other reported systems in the oxidation
reaction.34-35
Fig.11 Recycling efficiency of AgNPs@m-PS-PC nanocatalyst for
synthesis of propiolic acid.
Table 5. Comparison of AgNPs@m-PS-PC for oxidation of
cyclohexane with other reported catalysts
Reaction
Conditions
Conv.
(%)
Reactions
Catalysts
Ref.
Cyclohexane (60
mmol), TBHP (60
mmol),
acetic
Pt/Al2O3
30
63
34
acid (50 mL), 6 h,
70oC.
Cyclohexane(1ml)
, TBHP (2ml), 17 h
Fig. 12 Recycling efficiency of AgNPs@m-PS-PC nanocatalyst for the
oxidation of cyclohexane.
Ag6-GO
35
Oxidation of
cyclohexane
Cyclohexane (5
mmol), H2O2 (10
mmol),
AgNPs@m- Acetonitrile
PS-PC mL), catalyst (50
mg), reaction
(2
This
study
65
temperature 80
oC
Recyclability of AgNPs@m-PS-PC nanocomposite
For a heterogeneous catalyst, it is important to understand its
potential for reuse. The reusability of the AgNPs@m-PS-PC
nanocatalyst was investigated both for synthesis of phenylpropiolic
acid under atmospheric CO2 pressure and the oxidation of
cyclohexane using hydrogen peroxide as oxidant. The activity of the
recovered catalyst did not lead to any significant decline in its
catalytic activity for next five consecutive cycles shown in Fig. 11
and 12. After the completion of the reaction, solid catalyst was
separated by centrifugation from the reaction mixture. The catalyst
was then thoroughly washed with distilled water and and ethyl
acetate for more times, then allow to dry in air and used for
continuation of the next run. The reused AgNPs@m-PS-PC
nanocomposite was characterized by FTIR spectroscopic studies
(Fig. S3) and UHR-TEM analysis (Fig. 13).
Fig. 13 The UHR-TEM images of Reused AgNPs@m-PS-PC
nanocomposite at different magnifications: 500 nm (a), 200 nm (b),
50 nm (c) and 20 nm (d). The SAED pattern of Reused AgNPs@m-
PS-PC (e)
Heterogeneity Test of AgNPs@m-PS-PC catalyst
A hot filtration test has been carried out in the oxidation of
cyclohexane using hydrogen peroxide as oxidant with our
AgNPs@m-PS-PC nanocatalyst to examine whether silver was being
leached out from the solid support to the solution. The solid
catalyst was removed from the reaction mixture after 4 h by
filtration during the hot conditions and the filtrate was allowed to
react for another 4 h under the same reaction conditions. The
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oxidation reaction was completely stopped after the removal of the Science and Technology (DST) New Delhi, India for providing
View Article Online
catalyst, which confirms the true heterogeneity of the catalyst. It support to the University of Kalyani under PURSE program.
DOI: 10.1039/C9NJ05865F
was also noticed that after filtration of the catalyst from the reactor
no evidence for leaching of silver or decomposition of the complex
catalyst was observed. The leaching test was performed for Ag by
atomic absorption spectrometric analysis using the filtrate and it
was found that no Ag ions were present in the filtrate. Thus, from
the hot filtration test it suggested that the AgNPs@m-PS-PC
nanocatalyst is truly heterogeneous in nature and Ag was not being
leached out from the solid support during the oxidation reactions.
To check the heterogeneous nature of AgNPs@m-PS-PC
nanocatalyst, we have performed hot filtration test for the
oxidation reaction of cyclohexane. From this leaching limit studied
by AAS instrument we can conclude that after the first reaction
cycle, leaching of silver was observed in negligible amount in ppm
scale. The AAS analysis recorded that after several reaction runs, a
very negligible quantity of silver was leached out in our experiment
compared to the other reported systems. For further confirmation
we have done ICP-AES analysis of the filtrate and the recovered
nanocatalyst. We did not get any considerable metal trace in the
filtrate and in AgNPs@m-PS-PC catalyst got same metal loading as
that of fresh catalyst (≈0.38 %). All these experimental data clearly
confirmed the heterogeneous nature of the AgNPs@m-PS-PC
nanocomposite together with the catalyst synthesis.
* Author to whom correspondence should be addressed.
Dr. Sk. Manirul Islam, Department of Chemistry, University of
Kalyani, Kalyani, Nadia, 741235, W.B., India. Phone: + 91- 33-2582-
8750, Fax: 91-33-2582-8282, E-mail: manir65@rediffmail.com
Dr. Debasis Das, Department of Chemistry, The University of
Burdwan, Burdwan, 713104, W.B., India. Fax: +91 342 2530452, e-
mail: ddas100in@yahoo.com
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Dr. Seikh Mafiz Alam, Department of Chemistry, Aliah University,
Newtown, Kolkata-700156, West Bengal, India, Phone: +91-
8902214131,
Fax:
+91-33-2986-0252,
E-mail:
mafizchem@gmail.com.
Notes and references
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Conclusions
In conclusion, we have decorated silver nanoparticles AgNPs
embedded over porous polymer AgNPs@m-PS-PC nanocatalyst via
a very simple in situ synthetic method and it acts as effective
catalyst for both for the C-H carboxylation reaction of terminal
alkyne CO2 using to synthesis propiolic acids under atmospheric
pressure and additionally for the oxidation of cyclohexane,
achieving high efficiency in terms of activity, selectivity and stability.
It is demonstrated good catalytic activity, stability and recyclability
during the heterogeneous catalytic process. Therefore, it suggested
that our work achieves valuable and novel composite which have
bright prospects in applications in organic, medicinal, industrial
chemistry and also wide application in CO2 transformation.
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Acknowledgements
SMI acknowledges the Department of Science and Technology,
DST-SERB (project reference no. EMR/2016/004956), New
Delhi, Govt. of India, Board of Research in Nuclear Sciences
(BRNS), Project reference No: 37(2)/14/03/2018-BRNS/37003),
Govt. of India, and Council of Scientific and Industrial and
Research, CSIR (project reference no 02(0284)2016/EMR-II
dated 06/12/2016), New Delhi, Govt. of India for providing
financial support. NS wish to acknowledge the University Grants
Commission, New Delhi for providing D. S Kothari Postdoctoral
Fellowship (Award letter no. F.4-2/2006(BSR)/CH/17-18/0176).PP
also acknowledges to the Aliah University, Kolkata for providing
financial assistance. UM thankful to the Department of Chemistry,
Jogamaya Devi College, Kolkata, W.B., India for support. AK thanks
the Researchers Supporting Project (Grant no. RSP-2019/127), King
Saudi University, Riyadh, Saudi Arabia for financial support. We
acknowledge Department of Science and Technology (DST) and
University Grant Commission (UGC) New Delhi, India for providing
support to the Department of Chemistry, the University of Kalyani
under FIST and SAP program. We are grateful to the Department of
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DOI: 10.1039/C9NJ05865F
Graphical Abstract
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AgNPs Encapsulated by Amine-Functionalized Polymer Nanocatalyst for
the CO2 Fixation as Carboxylic Acid and Oxidation of Cyclohexane under
Ambient Conditions
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a
Noor Salam,a,b,# Priyanka Paul,a,c,# Swarbhanu Ghosh , Usha Mandi,d Aslam Khan,e Seikh
Mafiz Alamc,*, Debasis Das b,* and Sk. Manirul Islama,*
aDepartment of Chemistry, University of Kalyani, Kalyani, Nadia, 741235, W.B., India.
bDepartment of Chemistry, The University of Burdwan, Burdwan, , W.B., India.
c Department of Chemistry, Aliah University, Newtown, Kolkata-700156, W.B., India.
dDepartment of Chemistry, Jogamaya Devi College, Kolkata, 700026, W.B., India.
eKing Abdullah Institute for Nanotechnology, King Saud University, Riyadh, 11451, Saudi Arabia
# Authors contributed equally.
Silver nanoparticles grafted porous polystyrene material has been synthesized for the
production of valuable propiolic acid derivatives via atmospheric CO2 incorporation and oxidation of
cyclohexane under ambient reaction conditions.