Magnetic apple seed starch functionalized with 2,2′-furil as a green host for cobalt nanoparticles: Highly active and reusable catalyst for Mizoroki–Heck and the Suzuki–Miyaura reactions

Article abstract of DOI:10.1002/aoc.5075

From the perspective of green chemistry, in catalytic systems, being low cost and eco-friendly, in addition to high chemical and thermal stability, are requirements of support materials. In this regard, we used apple seed starch as an accessible, nontoxic, and cost-effective support material. In order to take advantage of magnetic separation, the magnetite nanoparticles were chosen as an ideal pair for apple seed starch. Furthermore, during the Schiff base reaction, the magnetic apple seed starch was functionalized with 2,2′-furil along with amine functionality to be used as a bio-support for immobilization of cobalt. The introduction of cobalt had a significant effect on the greenness of the catalyst and reducing its price. FT-IR, TGA, XRD, FE-SEM, TEM, VSM, ninhydrin test, element mapping, AAS, and EDX analysis were applied to characterize the newly prepared catalyst. The effectiveness of this novel Schiff base supported catalyst was evaluated in the Mizoroki–Heck and the Suzuki–Miyaura coupling reactions. High reactivity and selectivity were among the most prominent characteristics of the catalyst as compared to previously reported catalysts. The longevity test and hot filtration showed the ability to use the catalyst at least 5 times and negligible cobalt leaching during the reaction, respectively. This work is the first report on the usage of apple seed starch as a supporting catalyst and 2,2′-furil as a ligand in the catalyst modifications and catalytic activity. Accordingly, this can be the beginning of an attractive way in the design and synthesis of heterogeneous catalysts.

Full text of DOI:10.1002/aoc.5075

Received: 20 February 2019
DOI: 10.1002/aoc.5075
Revised: 20 May 2019
Accepted: 30 May 2019
F U L L P A P E R
Magnetic apple seed starch functionalized with 2,2′‐furil as
a green host for cobalt nanoparticles: Highly active and
reusable catalyst for Mizoroki–Heck and the Suzuki–
Miyaura reactions
Maryam Arghan
| Nadiya Koukabi
| Eskandar Kolvari
Department of Chemistry, Semnan
University, P.O. Box 35195‐363, Semnan,
Iran
From the perspective of green chemistry, in catalytic systems, being low cost
and eco‐friendly, in addition to high chemical and thermal stability, are
requirements of support materials. In this regard, we used apple seed starch
as an accessible, nontoxic, and cost‐effective support material. In order to take
advantage of magnetic separation, the magnetite nanoparticles were chosen as
an ideal pair for apple seed starch. Furthermore, during the Schiff base reac-
tion, the magnetic apple seed starch was functionalized with 2,2′‐furil along
with amine functionality to be used as a bio‐support for immobilization of
cobalt. The introduction of cobalt had a significant effect on the greenness of
the catalyst and reducing its price. FT‐IR, TGA, XRD, FE‐SEM, TEM, VSM,
ninhydrin test, element mapping, AAS, and EDX analysis were applied to char-
acterize the newly prepared catalyst. The effectiveness of this novel Schiff base
supported catalyst was evaluated in the Mizoroki–Heck and the Suzuki–
Miyaura coupling reactions. High reactivity and selectivity were among the
most prominent characteristics of the catalyst as compared to previously
reported catalysts. The longevity test and hot filtration showed the ability to
use the catalyst at least 5 times and negligible cobalt leaching during the reac-
tion, respectively. This work is the first report on the usage of apple seed starch
as a supporting catalyst and 2,2′‐furil as a ligand in the catalyst modifications
and catalytic activity. Accordingly, this can be the beginning of an attractive
way in the design and synthesis of heterogeneous catalysts.
Correspondence
Nadiya Koukabi, Department of
Chemistry, Semnan University, P.O. Box
35195‐363. Semnan, Iran 54058.
Email: n.koukabi@semnan.ac.ir
Funding information
Semnan University
KEYWORDS
apple seed starch, biodegradable support, cobalt nanoparticles, cross coupling reaction, green catalyst,
magnetic bio‐material
1 | INTRODUCTION
considering how to reduce waste and hazardous sub-
stances for more than 30 years. For instance, in synthetic
With mounting concerns over the state of our planet, it is
becoming critically important that we reduce our envi-
ronmental footprint. As ever, science is well ahead of
the curve in that respect. In fact, scientists have been
organic chemistry, much attention has been devoted to
developing a greener and more effective routes for the syn-
thesis of biodegradable catalysts. One of the ways to realize
this goal is to use biocompatible and biodegradable
Appl Organometal Chem. 2019;e5075.
wileyonlinelibrary.com/journal/aoc
© 2019 John Wiley & Sons, Ltd.
1 of 16
https://doi.org/10.1002/aoc.5075

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ARGHAN ET AL.
materials. Biological macromolecular biopolymers are
noteworthy candidates to prospect for supported catalysis
because of their unbeatable attributes, such as being
chemically stable, renewable, and more eco‐friendly
comparisons with commercial materials.[1,2] Polysaccha-
rides are the most abundant and common renewable
biopolymers, which can be used to reduce global depen-
dence on fossil fuels and replace synthetic polymers.[3]
From another point of view, given the increasing con-
sumption of energy and products in the world, one of
the most useful ways is to use waste materials in line
with the principles of green chemistry. For instance,
applying waste materials in catalytic field can be a con-
structive step as far as environment and the economy
are concerned.[4] The wastes can either be used directly
as a catalyst or be converted into active catalysts by mod-
ifying.[5] Of course, it is to be noted that not all supports
are not suitable for use in catalytic applications. Typi-
cally, suitable properties of catalyst support materials
are: (i) environmental friendliness, (ii) high chemical
and thermal durability, (iii) low cost, (iv) inertness
against air and moisture, and (v) ease of chemical modi-
fication. Apple seed, rich in starch, can be introduced as
a very exciting option, as it has all the desired properties
of catalyst support, and it is considered to be biodegrad-
able, and on the other hand, most of the time is disposed
of as waste, and there have been limited reports in the
literature about its use.[6,7] To the best of our knowledge,
there is no published research on the use of apple seed
starch as a catalyst support. Among polysaccharides,
amylum is the most considerable non‐toxic, biodegrad-
able, and biocompatible bio‐polymer.[1] There is a great
quantity of reactive free hydroxyl groups in starch;
therefore, order to prepare efficient catalysts, apple seed
starch can be either directly used for the immobilization
of metal ions through chelate mechanism or easily
modified by esterification, oxidation, hydrolysis, or
etherification. Meanwhile, magnetite nanoparticles with
unique properties such as non‐toxicity, magnetic recover-
ability, and high surface area can be a good pair for the
apple seed starch to provide greener supported catalysts.
In organic chemistry, a large number of reviews have
been published covering Heck–Mizoroki and Suzuki–
Miyaura C–C cross‐coupling reactions as they are the
most fundamental reactions in organic synthesis owing
to their application in the synthesis of natural products,
numerous drugs, biologically active compounds, and
many organic building blocks.[8,9] Principally, palladium
catalysts are used to activate aryl halides for the Heck–
Mizoroki[10] and the Suzuki–Miyaura[11–13] cross‐
coupling reactions. Although palladium catalysts are
uncompetitive in synthetic versatility, they suffer from
disadvantages such as high cost, air sensitivity, and
toxicity of complexes, all of which limit their use in the
industry. Therefore, recently, many studies have been
conducted to replace them with affordable transition
metal catalysts, containing nickel,[14] iron,[15] copper,[16]
and cobalt.[17] Cobalt catalysts are a very good choice
owing to their higher catalytic activities, nontoxicity,
low‐cost, chemical and mechanical stability, and avail-
ability.[18] Accordingly, to improve the Heck–Mizoroki
and the Suzuki–Miyaura cross‐coupling reactions, a
number of important studie have utilized new catalytic
systems based on cobalt.[17,19–25] Development of func-
tional groups on supports such as –SO3H, –COOH, –
NH2, –CONH2, and –OH for immobilization of metallic
nanoparticles is yet another challenge. In this regard,
we are pleased to introduce a new ligand called 2,2′‐furil,
which, to the best of our knowledge, is yet to be consid-
ered as a ligand in the catalyst modifications and cata-
lytic activity in the literature. Regarding our efforts to
develop and expand environmentally benign and effec-
tive heterogeneous catalysts,[26–29] we wish to reveal the
first successful synthesis of magnetic apple seed starch,
and its subsequent modification with 2,2′‐furil, denoted
as MNP@Seed starch@FR. In the last step of the synthe-
sis of the catalyst, cobalt nanoparticles were successfully
supported on MNP‐apple seed starch functionalized with
2,2′‐furil to prepare MNP@Seed starch@FR‐Co as a user‐
friendly, highly stable, and magnetic‐separated catalyst.
The performance of the resultant biocatalyst was tested
through the use of Mizoroki–Heck and the Suzuki–
Miyaura coupling reaction, which revealed excellent
reaction activity, selectivity, turn over frequency (TOF),
and turn over number (TON).
2 | EXPERIMENTAL SECTION
2.1 | General
The chemicals, reagents, and solvents were purchased
from Merck and Sigma‐Aldrich chemical companies and
were employed without further purification. TLC on com-
mercial plates coated with silica gel 60 F254 was applied
for checking the progress of the reactions and the purity
of the products. The FT‐IR spectra were recorded by a
Shimadzu 8400 s spectrometer using KBr pressed powder
discs. The thermogravimetric analysis (TGA) was per-
formed using a Du Pont 2000 thermal analysis apparatus
heated from 25 °C to 1000 °C at ramp 10 °C/min under
air atmosphere. X‐ray diffraction (XRD) analysis
was done on a Siemens D5000 (Siemens AG, Munich,
Germany) using Cu‐Ka radiation of wavelength 1.54 °A.
FE‐SEM–EDX analysis was accomplished using TESCAN
MIRA II digital scanning microscope. The amount of

ARGHAN ET AL.
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cobalt in the catalyst was measured with an Agilent
model 240 AA Shimadzu (USA) flame atomic adsorption
spectrometer. All measurements were done in an
air/acetylene flame, and the Co hollow cathode lamps
were used as the radiation sources. The magnetic
measurement was carried out in a vibrating sample
magnetometer (VSM) (4 inches, Daghigh Meghnatis
KashanCo., Kashan Iran) at room temperature. TEM
images were collected using transmission electron micro-
scope (TEM; Philips EM 208S‐100 KV). Detection of the
prouducts was performed by a gas chromatograph (GC‐
2.2.2 | Preparation of apple seed starch.
Apples were procured from the local supermarket. They
were each cut into four pieces and then the fresh seed
were separated from other tissues with a knife. The
extracted apple seed must be crushed into powder form
before use. So, the fresh apple seed were peeled off and
disintegrated with a mortar and pestle, and then, to
remove the lipid and water, the resulting material washed
three times with ethyl acetate and two times with ace-
tone. A vacuum desiccator was used to dry the powder
and then stored at 4 °C.
17A, Shimadzu, Kyoto, Japan) equipped with
a
splitless/split injector and a flame ionization detector.
Helium (purity 99.999%) was used as the carrier gas at
the constant flow rate of 4 mL min−1. The temperatures
of injector and detector were set at 275 °C and 320 °C,
respectively. The injection port was operated at splitless
mode and with sampling time 1 min. For FID, hydrogen
gas was generated with a hydrogen generator (OPGU‐
2200S, Shimadzu, Kyoto, Japan). A 30 m BP‐10 SGE
fused‐silica capillary column (0.32 mm i.d. and 0.25 μm
film thickness) was applied for separation of PAHs. Oven
temperature program was: started from 60 °C, held for
3 min, increased to 190 °C at 20 °C min−1, held for
0 min, increased to 240 °C at 10 °C min−1 and then held
for 3 min. A 10.0 μL ITO (Fuji, Japan) micro‐syringe
applied for the collection of sedimented organic solvent
and injection into the GC. The NMR spectra obtained
using a Brucker Avance 400 MHz instruments (1H‐
NMR 400 MHz and 13C‐NMR 125 MHz) in pure
dimethyl sulfoxide.
2.2.3 | Preparation of magnetic apple seed
starch (MNP@Seed starch)
0.5 g of Fe3O4 was dispersed in 20 ml of distilled water for
20 min. The prepared apple seed starch (0.5 g) was
completely dissolved in 5 ml of distilled water at 80 °C
and then added to the uniform mixture of Fe3O4. Then,
about 2 to 3 ml of 0.1 M solution of NaOH was added
drop wisely to the mixture. The reaction mixture was
stirred at 60 °C for 2 hours. At the end, the product was
separated by an external magnet, washed with deionized
water and ethanol with, and dried at 50 °C.
2.2.4 | Silylation procedure of magnetic
apple seed starch (MNP@Seed starch‐NH2)
The amination of the surface of the magnetic apple seed
starch was carried out using the method reported in the
literature.[31–37] A mixture of 2 g of MNP@Seed starch
and 5 ml of APTES was stirred in 50 ml of dry toluene
for 48 hours at 100 °C under a nitrogen atmosphere. After
the mentioned time, the NH2 functionalized magnetic
apple seed starch was collected by a magnet, washed with
ethanol and dried in an oven at 60 °.
2.2 | Catalyst preparation
2.2.1 | Synthesis of Fe3O4 nanoparticles
The magnetic (Fe3O4) nanoparticle was synthesized
based on a reported method.[30] 3 mL of FeCl3.6H2O
(2 M dissolved in 2 M HCl) was mixed with 10.33 mL of
ultrapure water. In the next step, 2 mL of Na2SO3 (1 M)
was dropwise added into the prior solution in 1 min
under magnetic stirring. After mixing the solutions, a
complex of SO32−and Fe3+ was formed, changing the
color of the mixture from light yellow to red. After the
color of the solution returned, it was added to 80 mL
NH3·H2O solution (0.85 M) under intense stirring. A
black precipitate was quickly formed, which was allowed
to completely crystallize for another 30 min under mag-
netic stirring. The magnetic nanoparticles were then puri-
fied by a magnetic decantation and washed several times
with deionized water (to pH < 7.5). The precipitates were
dried in a vacuum oven at 60 °C for 12 h.
2.2.5 | Schiff base reaction of MNP@seed
starch‐NH2 (MNP@Seed starch@FR)
MNP@Seed starch‐NH2 (5 g), 2,2′‐furil (5 mmol), and
absolute ethanol (100 mL) were transferred to a round‐
bottomed flask. The reaction mixture was stirred at
60 °C for 24 hours to complete the modification of
MNP@Seed starch‐NH2. The imine bond formation was
followed by FT‐IR. After the Schiff base reaction, the
product was separated, washed completely with ethanol,
and dried overnight at 95 °C.

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ARGHAN ET AL.
3 | RESULTS AND DISCUSSION
2.2.6 | Synthesis of support catalyst for Co
nanoparticles (MNP@Seed starch@FR‐Co)
3.1 | Fabrication and characterization of
MNP@Seed starch@FR‐co
In order to immobilize cobalt nanoparticles on
MNP@Seed starch@FR, 4.2 mmol of Co(OAc)2.4H2O
was dissolved in 10 ml of ethanol, and added to a uniform
mixture of MNP@Seed starch@FR (1 g) in ethanol
(5 mL). The reaction mixture was stirred at 60 °C for
18 hours. The final complex was isolated by a magnet,
washed with ethanol several times, and dried at room
temperature.
As already noted above, apple seed starch has not been
discussed in catalytic applications despite having unique
features. So as to eliminate the void in literature, we
synthesized cobalt supported on magnetic‐apple seed
starch functionalized with a new ligand. The process of
biocatalyst production is summarized in Scheme 1,
comprising the following steps: a) preparation of apple
seed starch, b) synthesis of magnetit nanoparticles, c) for-
mation of magnetic‐apple seed starch as a result of pre-
pared apple seed starch reacting with the synthesized
nano‐Fe3O4,d) preparation of NH2‐functionalized
magnetic‐apple seed starch produced by the reaction
between (3‐aminopropyl)triethoxysilane and MNP@Seed
starch, e) functionalization of MNP@Seed starch‐NH2
with 2,2′‐furil, and f) immobilization of cobalt nanoparti-
cles on the surface of the prepared bio‐support to prepare
a novel green biocatalyst.
2.3 | Studies on the catalytic activity.
2.3.1 | General procedure for Mizoroki–
heck reaction catalyzed by MNP@Seed
starch@FR‐Co
A round‐bottomed flask equipped with a magnetic
stirrer was charged with 1 mmol of aryl halide, 1.5 mmol
of olefin, 4.0 mmol of K3PO4, 0.33 mol% of MNP@Seed
starch@FR‐Co, and a mixture of DMF (1.5 mL) and
H2O (1.5 mL). The reaction continued for an
appropriate time under stirring at 100 °C. After comple-
tion of the reaction as followed by TLC, the catalyst
was magnetically collected and the reaction mixture
was cooled to ambient temperature. The product was
extracted by ethyl acetate and dried with MgSO4. Some
products were characterized by comparing their 1H‐
NMR and 13C‐NMR spectra with those found in the lit-
erature and the results are represented in supporting
information.
AAS analysis determined that the synthesized catalyst
contains approximately 1.1 mmol g−1 Co. FT‐IR, XRD,
TGA, FE‐SEM, VSM, TEM, ninhydrin test, AAS, element
mapping and EDX analysis were used to confirm the
structure of the catalyst and its stability before and after
the catalytic reaction.
3.1.1 | FT‐IR spectra
To investigate the physical structure of the prepared sam-
ples, The FT‐IR spectra of n‐Fe3O4, apple seed starch,
MNP@Seed starch, MNP@Seed starch‐NH2, MNP@Seed
starch@FR, and MNP@Seed starch@FR‐Co were
recorded (Figure 1a–f). The presence of the characteristic
absorption bands at about 557 and 570 cm−1 observed in
magnetic samples are related to the Fe–O vibrations
(Figure 1a, and c‐f). The FT‐IR spectrum of apple seed
starch shows characteristic peaks at 3336, 2952, 1647,
1400, and 700–1400 cm−1 which correspond to stretching
vibration of –OH, stretching vibration of –CH, bending
vibration of O‐H, bending vibration of CH2, and
stretching vibration of C‐O, respectively (Figure 1b). In
Figure 1c, the integration of the characteristic peaks of
the magnetic nanoparticles with apple seed starch repre-
sents the successful synthesis of the magnetic apple seed
starch. In the spectrum of MNP@Seed starch‐NH2, the
bands are observed at 3332 cm−1 (–OH and –NH2
stretching), 2929 and 2850 cm−1 (–CH2 stretching),
1654 cm−1 (N‐H bending), and 1000–1026 cm−1 (Si–OR
and O–Si–O stretching) (Figure 1d). The successful
2.3.2 | General procedure for Suzuki–
Miyaura reaction catalyzed by MNP@Seed
starch@FR‐Co
A mixture of phenyl boronic acid (1.2 mmol), aryl halide
(1 mmol), K2CO3 (3 mmol) and MNP@Seed starch@FR‐
Co (0.11 mol%) was placed in a round bottom flask with
5 ml water:ethanol (1: 1) and stirred at 80 °C for a suit-
able time. TLC allowed following of the reaction progress.
After completion of the reaction, the catalyst was
removed from the reaction medium using a magnet. After
cooling the reaction mixture to ambient temperature, the
product was extracted with ethyl acetate. Then, the
organic layer was washed with water and dried by anhy-
drous MgSO4. Characterization of some products was
1
done by comparing their H‐NMR and 13C‐NMR spectra
with those found in the literature and the results are rep-
resented in supporting information.

ARGHAN ET AL.
5 of 16
SCHEME 1 Preparation of the catalyst
attachment of APTES on the magnetic apple seed starch
indicate that the synthesis of MNP@Seed starch@FR‐Co
was successfully achieved.
[38]
was proven due to these important changes.
In the
spectrum of the MNP@Seed starch@FR, the expected
vibration band of the imine group is observed at
1647 cm−1. Moreover, the appeared peaks at 1473 and
1558 cm−1 can be ascribed to the stretching vibration of
–C=C– of the aromatic ring. Therefore, according to
these observations, the Schiff base reaction of the
MNP@Seed starch‐NH2 with 2,2′‐furil is confirmed. In
the spectrum of the MNP@Seed starch@FR‐Co, the
azomethine band (1647 cm−1) shifts to a lower wave-
length (1635 cm−1) and decreases its peak intensity,
which is due to the to the strong interaction of functional
groups with the Co nanoparticles.[39] The overall results
3.1.2 | X‐ray diffraction spectra
X‐ray diffraction (XRD) analysis was used to obtain evi-
dence for the presence of iron and cobalt. Characteristic
peaks at around 30.5°, 35.9°, 43.5°, 53.9°, 57.2°, and 63°
2θ are clearly visible in all spectrums, which are related
to the inverse cubic spinel structure of Fe3O4.[28] As it is
clear from Figure 2b and c, chemical modification
decreased the intensity of the Fe3O4 peaks but did not
change the phase of magnetit nanoparticles. In Figure 2

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ARGHAN ET AL.
FIGURE 3 TGA curve of (a) apple seed starch, (b) MNP@Seed
starch, (c) MNP@Seed starch@FR, and (d) MNP@Seed
starch@FR‐Co
FIGURE 1 FT‐IR spectra of (a) zn‐Fe3O4, (b) apple seed starch,
(c) MNP@Seed starch, (d) MNP@Seed starch‐NH2, (e)
MNP@Seed starch@FR, and (f) MNP@Seed starch@FR‐Co
decomposition of apple seed starch (Figure 3a, b, c, d).
According to Figure 3b, the amount of grafted apple seed
starch to the magnetic nanoparticle can be estimated. It
appears that the incorporation of apple seed starch in
MNP@Seed starch is about 22%. But, in Figure 3c, the
amount of loss weight at second region increased after
modification of magnetic apple seed starch with APTES
and FR (46%). It demonstrates that the synthesis of
MNP@Seed starch@FR was carried out successfully. A
closer inspection of the TGA curve of MNP@Seed
starch@FR‐Co shows slightly lower thermal stability after
the immobilization of cobalt, which can be due to the
interaction of the cobalt species with the ligands[43] and
the catalytic effect of them in the decomposition of the
organic moieties.[37] Also, compared to the remaining
mass percentage of MNP@Seed starch@FR (~54%)
(Figure 3c), MNP@Seed starch@FR‐Co has higher
undecomposed content (~62%) (Figure 3d). This amount
of difference (~8%) can be attributed to the amount of
loaded Co which is relatively consistent with the result
of AAS analysis. The eminent thermal stability of the
prepared substrate was proved by considering the high
temperature required to remove organic layers from the
MNP surface.
FIGURE
2
XRD pattern of (a) n‐Fe3O4, (b) MNP@Seed
starch@FR, and (c) MNP@Seed starch@FR‐Co
b and c, a broad reflection in the region between 2θ = 15°
and 2θ = 24° is related to the seed starch.[40–42] The XRD
pattern of the MNP@Seed starch@FR‐Co also shows
characteristic diffraction peaks at around 2θ = 29.9°,
39.5°, 55.4°, and 63.5° which correspond to the cubic
phase of cobalt nanoparticles that reveal the crystalline
nature of the cobalt species.[17]
3.1.3 | Thermogravimetric analysis
3.1.4 | Field emission scanning electron
microscopy
The representative TGA curves of apple seed starch,
MNP@Seed starch, MNP@Seed starch@FR, and
MNP@Seed starch@FR‐Co are shown in Figure 3. They
show two key stages decomposition. The first weight loss
zone (under 200 °C) is allocated to the release of molecu-
lar water (Figure 3a, b, c). The second weight loss region
is obtained at 225–570 °C, which corresponds to the
Scanning electron microscopy was used to highlight
and get an insight of the structural changes caused by
the chemical modifications and the morphology of the
apple seed starch, MNP@Seed starch, and MNP@Seed
starch@FR‐Co (Figure 4). As evident from the Figure 4,
structural changes clearly occurred after coating,

ARGHAN ET AL.
7 of 16
FIGURE 4 FE‐SEM images of (a, b) apple seed starch, (c, d) MNP@Seed starch, (e) MNP@Seed starch@FR‐Co, and (f) the particle size
distribution histogram of MNP@Seed starch@FR‐Co
functionalization, and immobilization. What is most
apparent is the change in the size of the nanoparticles fol-
lowing each step. These changes indicate that the catalyst
development process has been successfully completed.
Spherical shape and homogenous distribution are com-
mon in all the images. However, in the SEM image of

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ARGHAN ET AL.
MNP@Seed starch@FR‐Co, there is some aggregation of
the particles that results from the functionalization and
immobilization processes. The particle size distribution
from the FE‐SEM image indicates that the maximum par-
ticle size distributions were in the range of 15–25 nm.
Fe3O4), carbon (related to apple seed starch, APTES, and
FR), silicon (related to APTES), oxygen (related to Fe3O4,
APTES, apple seed starch, and FR), and nitrogen (related
to APTES) are observed. According to the EDX spectrum
of the synthesized catalyst, the presence of the cobalt is
also apparent in addition to other elements in the body
of the catalyst. The amount of Co‐entrapped with the
bio‐support detected by EDX is 7%.
3.1.5 | Energy dispersive X‐ray (EDX)
analysis
The formation of the green cobalt catalyst was further
corroborated through energy dispersive X‐ray studies
(Figure 5). In Figure 5, the peaks of iron (related to
3.1.6 | Energy dispersive X‐ray spectros-
copy (EDS) mapping
EDS element mapping was used to evaluate the spatial
distributions and density of the support material and
cobalt supported onto the MNP@Seed starch@FR
(Figure 6). As shown in Figure 6, Co species distributes
homogeneously as well as C, N, O, Si, and Fe in the
bio‐catalyst. These observations indicate that aggregation
did not occur during coating, functionalization, and
immobilization processes.
3.1.7 | Transmission electron microscopy
Further characterization of the morphology and structure
of the catalyst was performed by transmission electron
microscopy (TEM) (Figure 7). It was easily observed in
Figure 7a, b, c, that the Fe3O4 NPs core is well encapsu-
FIGURE 5 EDX spectra of MNP@Seed starch@FR‐Co
FIGURE 6 EDS element mapping of (a) Fe, (b) Si, (C) C, (d) N, (e) O, and (f) Co

ARGHAN ET AL.
9 of 16
FIGURE 7 TEM images of (a, b, c) MNP@Seed starch, and (d, e, f) MNP@Seed starch@FR‐Co
lated by apple seed starch. The TEM images of
MNP@Seed starch@FR‐Co showed well‐defined spheri-
cal Co particles and good distribution of them in the cat-
alyst, which, have a good agreement with FE‐SEM and
EDS results (Figure 7d, e, f). Very similar morphology
observation has been previously reported.[17] All these
observations indicate that the magnetic apple seed starch
functionalized with 2,2′‐furil is a good host and ligand for
cobalt nanoparticles.
the level of catalyst magnetizations is still adequate to
strongly respond to an external magnet thorough catalyst
recovering.
3.1.9 | Atomic absorption spectroscopy
(AAS) analysis
Finally, atomic absorption spectroscopy was performed to
determine the exact loading of cobalt in the catalyst.
According to the AAS results, a loading at 1.1 mmol.g−1
of Co was calculated in the catalyst, which is in good
agreement with the EDX result.
3.1.8 | Vibrating sample magnetometer
The magnetic properties of bare n‐Fe3O4 and the
MNP@Seed starch@FR‐Co were measured at room tem-
perature through a vibrating sample magnetometer
(VSM) (Figure 8a, b). It can be seen that the Fe3O4
nanoparticles are superparamagnetic with magnetic
saturation (MS) value of about 70. The magnetic satura-
tion value dramatically decreased to 21 emu/g for
MNP@Seed starch@FR‐Co nanocomposites. However,
3.1.10 | Ninhydrin test
Ninhydrin can be used for the determination of the pres-
ence of APTES on the surface of magnetic apple seed
starch, because it can react with a terminal primary
amine and produces a purple‐blue complex (Ruhemann's
purple).[44] Before doing the test, according to the pub-
lished procedure,[45] it was ensured that the un‐reacted
APTES from the surface of MNP@Seed starch‐NH2 was
removed by washing with ethanol. Then, 0.032 g of the
sample was sonicated in 5 mL of ethanolic ninhydrin
solution (0.175 M) for 30 min and continuously refluxed
at 90 °C for 25 min. After the mentioned time, the solu-
tion was cooled to room temperature, centrifuged for
10 min at 6000 rpm, and its optical density determined
at 580 nm with a UV/Vis colorimetric. Therefore, it was
concluded that 3‐aminopropyl groups are covalently
linked with hydroxyl groups in the surface of magnetic
apple seed starch.[31,46]
FIGURE 8 Room temperature magnetization curves of (a) n‐
Fe3O4, (b) MNP@Seed starch@FR‐Co

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ARGHAN ET AL.
3.2 | Application of MNP@Seed
starch@FR‐Co in C‐C coupling reactions
3.2.1 | Optimization of the reaction
parameters for the Suzuki–Miyaura cou-
pling reaction
In order to prove the effectiveness of our green catalyst,
we were interested to study the catalyst's performance
in C─C bond formation via Suzuki–Miyaura cross‐
coupling reaction (Scheme 2) and Mizoroki–Heck cross‐
coupling reaction (Scheme 3).
Before investigation of the catalytic activity of the cata-
lyst, optimizing the parameters that have critical effects
on the result of the reaction, such as temperature,
solvent, base system and amount of the catalyst, are
required. So, the Suzuki–Miyaura cross‐coupling of
iodobenzene (1.0 mmol) with phenyl boronic acid
(1.2 mmol) was considered as a model reaction to opti-
mize reaction conditions.
SCHEME
Miyaura reaction
2
MNP@Seed starch@FR‐Co‐catalysed Suzuki‐
MNP@Seed starch@FR‐Co‐catalysed Mizoroki‐
Effect of the amount of the catalyst
The effect of the catalyst on the reaction was investigated
by testing different amounts of catalyst in the reaction.
As shown in Table 1, the product yield increased gradu-
ally with increasing catalyst amount because of the avail-
ability of more catalytic sites (Table 1, entries 1–4). As
SCHEME
3
Heck reaction
TABLE 1 Optimization of the reaction parameters for the Suzuki–Miyaura reaction
Entry
Amount of catalyst (% mol)
Base
Solvent
Temperature (°C)
Time (h (min))
Yield (%)
1
0.05
0.08
0.11
0.22
‐
K2CO3
K2CO3
K2CO3
K2CO3
K2CO3
K2CO3
K2CO3
K2CO3
Na2CO3
KOH
H2O
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
80
(55)
(50)
(45)
(45)
24
75
80
90
92
‐
2
H2O
3
H2O
4
H2O
5
H2O
6
0.001(g)a
0.001(g)b
0.11c
0.11
0.11
0.11
0.11
0.11
0.11
0.11
0.11
0.11
0.11
0.11
0.11
H2O
24
15
Trace
35
90
55
50
85
90
85
98
70
75
95
85
‐
7
H2O
24
8
H2O
24
9
H2O
(50)
(45)
(45)
(45)
(50)
(45)
(45)
(45)
(45)
(45)
(50)
6
10
11
12
13
14
15
16
17
18
19
20
H2O
NaOH
K3PO4
Et3N
H2O
H2O
H2O
K2CO3
K2CO3
K2CO3
K2CO3
K2CO3
K2CO3
K2CO3
EtOH
H2O:EtOH (1/1)
CH3COOEt
DMF
H2O:EtOH (1/1)
H2O:EtOH (1/1)
H2O:EtOH (1/1)
60
R.T
aReaction was carried out the presence of Fe3O4NPs.
bReaction was carried out in the presence of MNP@Seed starch@FR.
cReaction was carried out in the presence of Co(OAc)2.4H2O.

ARGHAN ET AL.
11 of 16
shown in Table 1, 0.11 mol% is sufficient to obtain a sat-
isfactory efficiency. In the following, in order to prove
the vital role of the catalyst in the Suzuki–Miyaura cou-
pling reaction, the reaction was also performed in the
absence of the catalyst, in the presence of Fe3O4 NPs,
MNP@Seed starch@FR, and Co(OAc)2.4H2O, which, as
can be seen, did not produce good results (Table 1,
entries 5–8).
temperatures (Table 1, entries 15, 18–20). With respect to
the reaction yields and times, 80 °C was chosen as the
optimum temperature.
3.2.2 | Catalytic performance of the
MNP@Seed starch@FR–Co on several sub-
strates for the Suzuki–Miyaura reaction
In order to investigate the generality of this new green
catalyst and extend the scope of its application in the
Suzuki–Miyaura reaction, several aryl halides (aryl
iodides, aryl bromides, and aryl chlorides) reacted with
phenyl boronic acid (Scheme 2). The findings are shown
in Table 2. The order of the leaving group ability of hal-
ogens is as follows: I > Br > Cl, thus, the results obtained
from Table 2 are logical, and the coupling reactions with
aryl iodides are faster than aryl bromide and aryl chlo-
ride, and aryl chloride needs more time and the reaction
efficiency is lower. The structure of some products was
checked using their high‐field 1H‐NMR and 13C‐NMR
spectra. Furthermore, turnover numbers (TON) and
turnover frequency (TOF) are listed for all products in
Table 2.
Effect of base
Since the basic role of base in Suzuki reaction cannot be
denied, it should be sought to find the best option as a
base for use in the reaction. For this regard, the model
reaction was carried out in the presence of several bases
and, according to the results, K2CO3 was the best choice
(Table 1, entries 3, 9–13).
Effect of solvent
Solvents can control chemical reactions thermodynami-
cally and kinetically. Therefore, the choice of a suitable
high‐performance solvent is important. For this purpose,
the reaction progress was tested in the presence of differ-
ent solvents (Table 1, entries 3, 14–17). The results
showed that the reaction was carried out with higher effi-
ciency and shorter time in the presence of a mixture of
EtOH and H2O in 1:1 ratio.
3.2.3 | Optimization of the reaction condi-
tions for the Mizoroki–heck reaction
Effect of temperature
Temperature is another parameter that influences the
reaction, so it was decided to set the reaction at different
Having obtained satisfactory results from the use of this
new catalyst in Suzuki–Miyaura reaction, we were
a
TABLE 2 Suzuki–Miyaura coupling reactions of aryl halides with PhB(OH)2
Entry
Aryl halide
Product
Time (min)b
Yield (%)c
TON
TOF
1
45
95
863
1150
2
3
4
5
6
7
45
60
70
45
50
3 h
88
91
86
93
92
60
800
827
781
845
836
545
1066
827
673
1126
1007
181
aReaction condition: aryl halide (1.0 mmol), phenyl boronic acid (1.2 mmol), K2CO3 (3 mmol), catalyst (0.11% mol), and EtOH:H2O (1:1) (5 mL), at 80 °C.
bDetected by TLC.
cIsolated yield.
TON: (turnover number, yield of product/per mol of Co).
TOF: (turn over frequency, TON/time of reaction (hour)).

12 of 16
ARGHAN ET AL.
stimulated to examine the effectiveness of the synthesized
catalyst in the Mizoroki–Heck reaction. First of all,
because of the need of performing the reaction in the best
of conditions, the reaction between iodobenzene and
methyl acrylate was considered as a model reaction to
optimize the parameters (temperature, amount of cata-
lyst, solvent, and base).
Co(OAc)2.4H2O, which did not yield satisfactory results
(Table 3, entries 5–8). The best result was obtained in
the presence of 0.33 mol% of the catalyst.
Effect of base
Regarding the vital role of base in preventing the forma-
tion of homo‐coupling product and neutralizing hydro-
gen halides,[28] carrying out the reaction in the presence
of a suitable base is important. In this regard, after
performing the reaction in the presence of different bases,
K3PO4 was selected as the most suitable base (Table 3,
entries 3, 9–13).
Effect of amount of catalyst
In order to find the optimal amount of catalyst, the car-
rying out of the model reaction was investigated in the
presence of different amounts of the synthesized catalyst
(Table 3, entries 1–4). On the other hand, to prove the
activity and specific role of the catalyst, the reaction
was performed in the absence of the catalyst, in the
presence of Fe3O4 NPs, MNP@Seed starch@FR, and
Effect of solvent
After analyzing the effect of different solvents on the
result of the reaction, the best conditions were found with
TABLE 3 Optimization of the reaction conditions for the Mizoroki–Heck reaction
Amount of
Entry
catalyst (% mol)
Base
Solvent
Temperature (°C)
Time (h (min))
Yield (%)
1
0.11
0.22
0.33
0.44
‐
K2CO3
K2CO3
K2CO3
K2CO3
K2CO3
K2CO3
K2CO3
K2CO3
Na2CO3
KOH
H2O
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
120
80
(75)
(70)
(65)
(60)
24
55
70
75
75
‐
2
H2O
3
H2O
4
H2O
5
H2O
6
0.003(g)a
0.003(g)b
0.33c
0.33
0.33
0.33
0.33
0.33
0.33
0.33
0.33
0.33
0.33
0.33
0.33
0.33
H2O
24
10
Trace
30
70
70
65
80
70
70
87
60
55
92
94
80
‐
7
H2O
24
8
H2O
24
9
H2O
(65)
(65)
(65)
(60)
(65)
(65)
(60)
(80)
(80)
(55)
(55)
(65)
6
10
11
12
13
14
15
16
17
18
19
20
21
H2O
NaOH
K3PO4
Et3N
H2O
H2O
H2O
K3PO4
K3PO4
K3PO4
K3PO4
K3PO4
K3PO4
K3PO4
K3PO4
EtOH
DMF
DMSO
PEG
H2O:DMF (1/1)
H2O:DMF (1/1)
H2O:DMF (1/1)
H2O:DMF (1/1)
R.T
aReaction was performed in the presence of Fe3O4 NPs.
bReaction was performed in the presence of MNP@Seed starch@FR.
cReaction was performed in the presence of Co(OAc)2.4H2O.

ARGHAN ET AL.
13 of 16
a mixture of DMF and H2O in 1:1 ratio as solvent (Table 3,
entries 12, 14–18).
to synergistic good effects of cobalt nanoparticles with
ligand which grafted on MNP and good dispersion of
cobalt nanoparticles. The identification of the structure
of some compounds was carried out using their 1H‐
NMR and 13C‐NMR spectra and according to the results
it was found that all products were produced in the form
of E‐isomers. The calculated TON and TOF values for all
products are given in Table 4.
Effect of temperature
In order to complete the optimization process, the reac-
tion was followed at various temperatures, which showed
an optimal temperature of 100 °C (Table 3, entries 18–21).
3.2.4 | Catalytic performance of the
MNP@Seed starch@FR–Co on several sub-
strates for the Mizoroki–Heck reaction
3.3 | Comparison of MNP@Seed
starch@FR‐Co results with those obtained
by other workers for the Mizoroki–Heck
The generality and scope of this new bio‐catalyst in the
Mizoroki–Heck reaction was studied using a variety of
aryl halides with various olefins under the optimized
reaction conditions (Scheme 3). The results are depicted
in Table 4. Considering the first step of the Mizoroki–
Heck reaction (oxidative addition), it will be concluded
that the coupling reaction with aryl iodide is faster than
aryl bromide and aryl chloride. If we look at Table 4,
the results are evidence of this fact. Although aryl chlo-
ride reacted for a long time and with low efficiency, but,
it should be taken into account that many reported cobalt
catalytic systems showed no activity with aryl chloride
substrates in the Mizoroki–Heck reaction.[25,47,48] The
high performance of this bio‐catalyst can be attributed
In order to further examine the efficiency of the present
catalytic method in the coupling reaction of methyl acry-
late with iodobenzene, we compared the performance of
the MNP@Seed starch@FR‐Co with some of the pub-
lished heterogeneous (Co, Fe, and Ni) catalysts
(Table 5). Some clear advantages of the present catalytic
system over other supported catalyst systems are: lower
temperature, shorter reaction time, greener media, high
product yield, use of safe metal, minimization of metal
contamination, easy magnetic separation capability, high
recyclability, no need to use additional equipment like
microwave oven, using low weight percentage of the cat-
alyst, and low cost.
TABLE 4 Mizoroki–Heck coupling reactions of aryl halides with olefinsa
Entry
Aryl halide
Olefin
Product
Time (min)b
Yield (%)c
TON
TOF
1
55
92
278
305
2
3
90
55
85
85
257
257
171
282
4
100
87
263
164
5
6
7
4 h
55
30
90
85
90
22
272
242
298
172
85
aReaction condition: aryl halide (1.0 mmol), olefin (1.5 mmol), K3PO4 (4.0 mmol), catalyst (0.33% mol), DMF:H2O (1:1) (3 mL), at 100 °C.
bDetected by TLC.
cIsolated yield.
TON: (turnover number, yield of product/per mol of Pd).
TOF: (turn over frequency, TON/time of reaction (hour)).

14 of 16
ARGHAN ET AL.
TABLE 5 Comparison of results for MNP@Seed starch@FR‐Co with those for other catalysts in the coupling of iodobenzene with methyl
acrylate
Entry
Catalyst
Solvent
Temperature (°C)
Time (h)
Yield (%)
Ref.
[49]
1
Co–NHC@MWCNTsa
PEG
80
5
85
85
88
53
85
73
56
98
87
97
90
92
[15]
[17]
[17]
[23]
[22]
[24]
[47]
[25]
[50]
[51]
2
SiO2‐Fe (acac)
PEG
130
80
1.5
1
3
Co‐MS@MNPs/CSb
Co@MNPs/CS
PEG
4
PEG
80
1
5
Nano Co
NMP
140
130
150
130
100
100
120
100
16
16
24
12
3
6
Co hollow nanospheres
Co/Al2O3
NMP
7
NMP
8
Co‐B
water/DMF (5/5)
Toluene
DMF
9
Co‐IL@MWCNTsc
Ni (II)–DABCO@SiO2
Nano Co
10
11
12
3
NMP
8
MNP@Seed starch@FR‐Co
water/DMF (1:1)
0.91
This work
aMulti walled carbon nanotubes supported N‐heterocyclic carbene–cobalt (ΙΙ).
bCobalt immobilized on MNPs‐chitosan functionalized with methyl salicylate (Co‐MS@MNPs/CS).
cCobalt nanoparticles supported on ionic liquid‐functionalized multiwall carbon nanotubes.
3.4 | Reusability of MNP@Seed
starch@FR‐Co
From an economic, industrial, and environmental point
of view, catalyst recyclability is among the most impor-
tant features. Therefore, catalyst recycling was tested
through conducting the Suzuki–Miyaura reaction of
iodobenzene with phenyl boronic acid at the optimized
reaction conditions. At the end of each cycle, the cata-
lyst was magnetically separated, washed thoroughly
with ethanol and distilled water, and dried in an oven
at 60 °C. As shown in Figure 9, the catalyst was able
to be reused up to 5 times without a significant reduc-
tion in efficiency. No changes were observed in the
nature and morphology, and negligible Co‐leaching
and consistent composition of the catalyst, after 5 time
reuse, were fixed using FE‐SEM and EDX (Figure 10)
analysis, respectively.
FIGURE 9 Recyclability in the Suzuki–Miyaura reaction of
iodobenzene with phenyl boronic acid under the optimized
reaction conditions
separated from the reaction medium using a magnet,
after which, the reaction proceeded under the same
optimal conditions without adding any fresh catalyst for
2 hours. The reaction progress was controlled by TLC.
As expected, no further coupling reaction occurred,
indicating that there was no leaching phenomenon here.
The heterogeneous nature of the catalyst has been
proven by the result,[17,28] and it can be concluded that
the attachment of cobalt to the MNP@Seed starch@FR
surface is strong.
3.5 | Leaching
In supported metal catalysts, a major problem preventing
the separation and reuse of the catalyst is the leaching
of metal ions. In order to prove the heterogeneity of
the catalyst, the reaction between iodobenzene and
phenyl boronic acid was accomplished under optimal
conditions. At half the reaction time, the catalyst was

ARGHAN ET AL.
15 of 16
FIGURE 10 (a) FE‐SEM images, and (b) EDX spectra of the recovered MNP@Seed starch@FR‐Co nanocomposite
ORCID
4 | CONCLUSIONS
Maryam Arghan https://orcid.org/0000-0003-1447-1615
Nadiya Koukabi https://orcid.org/0000-0002-7358-783X
Eskandar Kolvari https://orcid.org/0000-0003-0484-5273
The present work is the first to report the use of apple seed
starch as a supporting catalyst and its attachment to mag-
netic nanoparticles. As far as the authors are concerned,
the present work is also the first to apply 2,2′‐furil as a
ligand in the catalyst modifications and catalytic activity.
The magnetic apple seed starch‐Schiff base support acted
as a suitable host for cobalt nanoparticles to synthesize
MNP@Seed starch@FR‐Co as a novel, highly efficient,
inexpensive, low‐toxicity, user‐friendly, highly stable, and
magnetic‐separated catalyst. The catalytic performance of
the resultant biocatalyst was investigated in Mizoroki–
Heck and Suzuki–Miyaura reactions. This novel green cat-
alyst showed high selectivity and reactivity in the reactions
and minimized the time and the energy required for the
Suzuki and Heck reactions in comparison with other
previoualy reported cobalt‐catalyzed cross‐coupling reac-
tions. Subsequently, desirable reusability for at least 5
times was achieved with negligible cobalt leaching during
the reaction. It is noteworthy that, demonstration of the
combination of cobalt and organic ligands is very rare, so
this phosphine and palladium‐free catalyst can be intro-
duced as a high effective and recyclable catalyst which
can be used in reactions which require a metal catalysis,
such as hydroacylation, functionalization of C − H bonds,
Fischer–Tropsch synthesis, and Diels–Alder reaction. The
extent of the use of this new biocatalyst will be taken into
consideration in our laboratory.
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