Iron oxide nanoparticles modified with carbon quantum nanodots for the stabilization of palladium nanoparticles: An efficient catalyst for the Suzuki reaction in aqueous media under mild conditions

Article abstract of DOI:10.1002/cctc.201500925

Magnetic Fe₃O₄ nanoparticles (NPs) functionalized with carbon dots (C-dots) that contain carboxylic acid and hydroxyl groups were synthesized successfully and used for the reduction of Pd^II and the formation of Pd NPs. The new material was characterized by SEM, TEM, energy-dispersive spectroscopy, solid UV spectroscopy, vibrating sample magnetometry, XRD, and X-ray photoelectron spectroscopy and was used as a very efficient catalyst in the Suzuki-Miyaura cross-coupling reaction of aryl bromides and chlorides with arylboronic acids in aqueous media. Design of experiments indicates that the use of 0.22 mol % of Pd, K₂CO₃ as the base, and aqueous ethanol are the best reaction conditions. The reactions of aryl bromides take place at room temperature, and aryl chlorides react at 80 °C. The easily synthesized and air-stable catalyst Pd@C-dots@Fe₃O₄ NPs could be separated from the reaction mixture by using an external magnet and reused in eight consecutive runs with no significant loss of catalytic activity. Dot to dot: Pd supported on Fe₃O₄ nanoparticles modified with carbon quantum nanodots is shown to be an efficient catalyst for Suzuki coupling reactions.

Full text of DOI:10.1002/cctc.201500925

DOI: 10.1002/cctc.201500925
Full Papers
Iron Oxide Nanoparticles Modified with Carbon Quantum
Nanodots for the Stabilization of Palladium Nanoparticles:
An Efficient Catalyst for the Suzuki Reaction in Aqueous
Media under Mild Conditions
[
a]
[a]
[a]
Mohammad Gholinejad,* Mohammad Seyedhamzeh, Mehran Razeghi,
[b]
[a]
Carmen Najera,* and Mohsen Kompany-Zareh
Magnetic Fe O nanoparticles (NPs) functionalized with carbon
media. Design of experiments indicates that the use of
0.22 mol% of Pd, K CO as the base, and aqueous ethanol are
3
4
dots (C-dots) that contain carboxylic acid and hydroxyl groups
were synthesized successfully and used for the reduction of
2
3
the best reaction conditions. The reactions of aryl bromides
take place at room temperature, and aryl chlorides react at
808C. The easily synthesized and air-stable catalyst Pd@C-
dots@Fe O NPs could be separated from the reaction mixture
II
Pd and the formation of Pd NPs. The new material was charac-
terized by SEM, TEM, energy-dispersive spectroscopy, solid UV
spectroscopy, vibrating sample magnetometry, XRD, and X-ray
photoelectron spectroscopy and was used as a very efficient
catalyst in the Suzuki–Miyaura cross-coupling reaction of aryl
bromides and chlorides with arylboronic acids in aqueous
3
4
by using an external magnet and reused in eight consecutive
runs with no significant loss of catalytic activity.
Introduction
Pd-catalyzed cross-coupling reactions are very important and
properties. They are green, nontoxic, abundant, and inexpen-
sive materials. In addition, C-dots have unique properties such
as photostability and fluorescence emission, and for these rea-
sons have been considered in different applications such as
powerful strategies for the formation of CÀC and CÀhetero-
[
1]
atom bonds. As a result of the toxicity and high price of Pd,
in recent years, interest has grown in the organization and use
[2]
of recoverable heterogeneous Pd catalysts. For this purpose,
biosensing, bioimaging, light emitting diodes, fluorescent ink,
[3]
[4]
[9,10]
different solid materials such as modified silicas, polymers,
and photocatalysis.
Different methods such as laser abla-
[5]
[6]
[7]
mesoporous materials, ionic liquids, and natural supports
tion, pyrolysis, wet oxidation, ultrasound- and microwave-as-
sisted synthesis, hydrothermal synthesis, and electrochemical
have been designated as supports for the heterogenization of
Pd catalysts. Even with significant achievements in this area,
the separation and efficient recovery of the heterogeneous cat-
alyst from the reaction medium by conventional methods such
as filtration or centrifugation is not always an easy assignment.
One of the best methods to solve this problem is the use of
magnetic nanoparticles (NPs) of Fe O as a very convenient
[
8,9]
etching have been developed for the synthesis of C-dots.
The carboxylic and hydroxyl moieties of the C-dots confer ex-
cellent water solubility as well as biocompatibility and give
them promise as an excellent support for catalyst stabilization.
However, compared to other carbon structures such as carbon
[
11]
nanotubes and graphene, less attention has been paid to
the use of C-dots as solid supports for catalysis design. Recent-
ly, C-dots-reduced Pd NPs have been reported as an efficient
3
4
[8]
support for heterogenization of Pd catalysts. Very simple iso-
lation and recovery, high surface area, and low toxicity are the
key advantages of magnetic-NP-supported catalysts.
[
12]
catalyst in Suzuki and Heck coupling reactions in water.
Recently, carbon quantum nanodots (C-dots) have been de-
scribed as a new class of carbon structures with interesting
However, to the best of our knowledge, there are no reports
that deal with the modification of Fe O NPs using C-dots and
3
4
its application for stabilization of Pd NPs. In continuation of
our interest into magnetically separable heterogeneous Pd cat-
[
a] Dr. M. Gholinejad, M. Seyedhamzeh, M. Razeghi, Prof. M. Kompany-Zareh
Department of Chemistry, Institute for Advanced Studies in Basic Sciences
[13]
alysts, herein, we wish to report for the first time the synthe-
(
IASBS)
sis and characterization of Pd NPs supported on magnetite
NPs modified with C-dots and its application as a sustainable
catalyst in the Suzuki–Miyaura cross-coupling reaction in aque-
ous media.
P. O. Box 45195-1159, Gavazang, Zanjan 45137-6731 (Iran)
E-mail: gholinejad@iasbs.ac.ir
[
b] Prof. C. Najera
Departamento de Química Orgµnica and Centro de Innovación en Química
Avanzada (ORFEO-CINQA), Universidad de Alicante
Apdo. 99, E-03080-Alicante (Spain)
E-mail: cnajera@ua.es
Supporting Information for this article is available on the WWW under
http://dx.doi.org/10.1002/cctc.201500925.
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Results and Discussion
Fe O NPs were prepared in a coprecipitation step based on
3
4
[
14]
the procedure of Massart using FeCl ·6H O and FeCl ·4H O.
3
2
2
2
C-dots were prepared following a procedure described previ-
ously using a mixture of citric acid and urea that was trans-
[
15a]
ferred to a Teflon autoclave and heated at 1608C for 6 h.
The obtained C-dots were treated with Fe O NPs at 608C for
3
4
2
4 h to afford C-dots@Fe O NPs. The final Pd@C-dots@Fe O
3 4 3 4
3 4
Figure 2. XRD pattern of Pd@C-dots@Fe O .
catalyst was obtained simply by dissolving PdCl in water by
2
sonication and the addition of C-dots@Fe O , also dissolved in
3
4
water by sonication, and heating at 608C for 1 day. The load-
ing of Pd in the obtained material was determined by induc-
À1
tively coupled plasma (ICP) analysis to be 0.27 mmolg . Ther-
mogravimetric analysis (TGA) of the prepared material showed
two major weights loses between 25 and 7008C. The first
weight loss, which occurs between 25 and 1008C, is related to
water and physically adsorbed solvents. The second weight
loss, which occurred between 100 and 7008C, may be related
to the C-dots on the Fe O NPs (Figure 1).
3
4
2 3 4
Figure 3. DR UV/Vis spectra of PdCl and Pd@C-dots@Fe O .
3 4
Figure 1. TGA profile of Pd@C-dots@Fe O .
3 4
Figure 4. XPS spectrum of Pd@C-dots@Fe O in the Pd3d region.
FTIR spectroscopy provided further confirmation that the
surface of the magnetic NPs was modified by C-dots (Figure 1,
tively. These results indicate that most of the Pd is present in
the reduced form, which confirms the capability of
II
0
[19]
Supporting information). The absorption bands at n˜ =3000–
C-dots@Fe O in the efficient reduction of Pd to Pd NPs.
3 4
À1
3
500 cm are assigned to the stretching vibrations of OH and
Moreover, the presence of carbon in the structure of Pd@C-
dots@Fe O confirmed by XPS analysis by the appearance of
À1
NH groups, and a peak at n˜ =1622 cm can be assigned to
2
3
4
the C=O band.
peaks related to C1s at BE=283.87 eV for graphitic or aliphatic
carbon, BE=286.13 eV for oxygenated carbon, and BE=
XRD analysis of the prepared material showed the formation
0
[15]
of Pd NPs on the C-dot@Fe O surface by the appearance of
287.75 eV for nitrous forms of carbon (Figure 5).
3
4
[16]
Bragg’s reflections related to Fe O NPs at 2q=30.17, 35.46,
3
4
[
17]
4
3.38, 53.69, 57.23, and 62.778 and those related to Pd NPs
at 2q=40.1, 46.7, and 68.18 (Figure 2).
II
0
The reduction of Pd to Pd was also confirmed by diffuse re-
flectance UV/Vis (DR UV/Vis) spectroscopy from the disappear-
ance of the peak related to PdCl at l=280 nm in the spec-
2
[18]
trum of Pd@C-dots@Fe O (Figure 3).
3
4
However, to obtain exact information about the oxidation
state of Pd species, X-ray photoelectron spectroscopy (XPS)
was performed (Figure 4). Results showed the presence of an
intense doublet at a binding energy (BE) of 335.6 and 340.8 eV
0
II
related to Pd and peaks at BE=338 and 343 eV related to Pd ,
which correspond to the Pd3d5/2 and Pd3d3/2 peaks, respec-
3 4
Figure 5. XPS spectrum of Pd@C-dots@Fe O in the C1s region.
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SEM images of the Pd@C-dots@Fe O showed the formation
3
4
of uniform spherical particles (Figure 6), and the energy-disper-
sive spectrum (EDS) obtained from SEM confirmed the pres-
ence of Pd, Fe, and C species in the structure of the material
(
Figure 7). Furthermore, TEM images of the material at different
magnifications showed the nanostructure character of the pre-
pared material of an average size of 20 nm and showed the
presence of carbon shells in the structure (Figure 8).
Figure 9. Magnetization values.
absence of a hysteresis loop in both samples confirmed the su-
perparamagnetic properties and the ease of separation of the
material from the reaction mixture.
The catalytic activity of the prepared Pd@C-dots@Fe O was
3
4
evaluated in the Suzuki–Miyaura coupling reaction of aryl bro-
mides and chlorides. To find the optimized reaction conditions,
[
20]
design of experiments (DoE) for the reaction of 4-bromoani-
sol and phenylboronic acid as a model reaction was pursued.
A five-level, three-factor central composite design to study of
the effect of the parameters on coupling reaction was created
(
Table S1). The three independent variables (factors) are the
solvent type (X ), base type (X ), and the amount of catalyst
Figure 6. SEM image of Pd@C-dots@Fe
3
O
4.
1
2
(
X3). The regression coefficients obtained from the mathemati-
cal linear second-order model [Eq. (1), Supporting Information]
are given in Table S2. From the results of Table S2, a second-
order mathematical model [Eq. (2)] was generated. After we
substituted regression coefficients into Equation (1), a new
equation that involved Y (reaction yield), X , X , and X was ob-
1
2
3
tained.
Y ¼ 89:8515þ7:2724 X þ2:3165 X þ2:3764 X
1
2
3
2
þ6:6250 X X À0:3750 X X À1:1250 X X À29:9348 X
ð2Þ
1
2
1
3
2
3
1
3 4
Figure 7. EDS spectrum of Pd@C-dots@Fe O obtained from SEM.
2
2
À28:6974 X À1:1202 X
2
3
We used statistical analysis of variance (ANOVA) significance
and fitness of the model as well as the effects of significant in-
dividual terms and their interactions to study the chosen re-
sponses (Tables S2 and S3).
Usually, the parameters with p<0.05 are considered as sig-
2
nificant parameters, and a correlation factor R >0.85 is desired
for the mathematical model to be considered as a good ap-
proximation of the reaction. The type of solvent, quadratic
term of the solvent, quadratic term of the base, and solvent–
base interaction term were significant model terms (Table S2).
The results show that the effect of the type of solvent is de-
pendent on the type of base applied in the reaction. In addi-
tion, the effects of catalyst and the quadratic term of catalyst–
base and catalyst–solvent interactions were insignificant. The
insignificant effect of catalysis does not mean that catalysis has
no effect on the reaction rate. It means that a change in con-
centration of the catalyst has no significant effect compared to
that of the type of solvent and applied base. Insignificant
terms can be removed from the model manually to improve
the regression model and optimization results [Eq. (3)].
3 4
Figure 8. TEM image of Pd@C-dots@Fe O at different magnifications.
The superparamagnetic character of Pd@C-dots@Fe O and
3
4
Fe O NPs was also studied. Results showed that the decrease
3
4
in the magnetization value of the Pd@C-dots@Fe O
3
À1
4
À1
(
50 emug ) in comparison with that of Fe O NPs (64 emug )
3 4
confirms the modification of Fe O NPs with C-dots (Figure 9).
3
4
Zero coercivity, remanence on the magnetization loop, and the
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Y ¼ 89:8515þ7:2724 X þ16:6250 X X À0:3750 X X
4-OMe, and 4-Me, as well as electron-withdrawing groups,
1
1
2
1
3
ð3Þ
2
2
such as 4-NO , 4-Cl, 4-CN, 4-CHO, and 2-CHO, with phenylbor-
2
À1:1250 X X À29:9348 X À28:6974 X
2
3
1
2
onic acid proceeded satisfactorily, and the corresponding cou-
pling products were obtained in high to excellent yields
(Table 1, entries 1–11). Moreover, reactions of unsubstituted
aryl bromides, such as bromobenzene, bromobiphenyl, and 1-
bromonaphthalene, proceed efficiently and afford the corre-
sponding products (Table 1, entries 1, 12 and 13). The reaction
of 5-bromopyrimidine as a heterocyclic aryl bromide with phe-
nylboronic acid gave the coupling product in 98% isolated
yield (Table 1, entry 2). Substituted aryl chlorides are less ex-
pensive than aryl bromides and more accessible for Pd-cata-
lyzed cross-coupling reactions. However, the reactions of aryl
chlorides under the optimized reaction conditions at room
temperature were sluggish, therefore, the reaction tempera-
ture was increased to 808C. Under these reaction conditions,
the Suzuki–Miyaura reaction was efficient, and the desired
cross-coupling products were obtained in high to excellent
yields (Table 1, entries 18–22).
We used Equation (3) to plot a 3D graph of the second-
order Suzuki coupling reaction (Figure 10). The yield of the re-
action increased in the middle of the diagram (dark red),
which indicates the use of EtOH/H O as the solvent and K CO
2
2
3
as the base. Furthermore, a contour plot diagram obtained
from the 3D graph confirmed that the best reaction yield
could be obtained using EtOH/H O as the solvent and K CO
2
2
3
as the base (Figure 11).
To show the importance of the C-dots in the activation and
stabilization of Pd NPs, a similar catalyst without C-dots was
synthesized. Pd absorbed physically on Fe O NPs was tested
3
4
in the model reaction under the optimized reaction conditions.
However, the results showed that reaction achieved only 14%
GC yield in 24 h. This result confirms the key role of C-dots for
the reduction and formation of reactive Pd NPs in the catalyst
structure.
Figure 10. 3D graph of the second-order reaction to model the Suzuki cou-
pling.
One of the main advantages of magnetite-NPs-supported
catalysts is the easy separation and recycling of the catalyst. To
study the recycling properties of this catalyst, the reaction of
5
-bromopyrimidine with phenylboronic acid under the opti-
mized reaction conditions was selected. The results showed
that the catalyst is recyclable in eight consecutive runs just by
decantation with a magnetic bar with no significant loss of cat-
alytic activity (Figure 12).
Figure 11. Contour plot diagram obtained from the 3D graph.
Notably, 3D graphs and their corresponding contour plots
for the base with respect to the amount of catalyst and also
the solvent with respect to the catalyst amount indicated that
Figure 12. Recycling experiments for the cross-coupling of 5-bromopyrimi-
dine and phenylboronic acid.
the use of 0.22 mol% of Pd, EtOH/H O as the solvent, and
2
K CO as the base are the best reaction conditions. The model
2
3
reaction under the optimized reaction conditions was also
studied without the catalyst, but only 3% conversion to the
product was observed. Under the optimized reaction condi-
tions, the reactions of structurally different aryl bromides and
chlorides with different arylboronic acids were studied in the
presence of the catalyst (Table 1). The results indicate that aryl
bromides that contain electron-donating groups, such as 4-OH,
The leaching of Pd into the reaction solution after eight runs
was determined by ICP analysis to be 1.26%, which indicates
the stability of the catalyst during the reaction. In addition,
SEM (Figure 13) and TEM (Figure 14) images of the catalyst
after the third run showed that the nanostructure of the cata-
lyst was preserved.
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[
a]
Table 1. Scope of the Suzuki–Miyaura reaction.
1
2
[b]
Entry
1
Ar X
Ar B(OH)
2
t [h]
T [8C]
Product
Yield [%]
98
PhB(OH)
PhB(OH)
2
2
30
2
2
1
30
100
3
4
5
6
7
8
9
PhB(OH)
PhB(OH)
2
2
24
12
24
24
24
24
1
30
30
30
30
30
30
30
98
93
92
93
97
87
97
PhB(OH)
PhB(OH)
2
2
PhB(OH)
PhB(OH)
2
2
1
0
24
30
88
1
1
PhB(OH)
PhB(OH)
2
2
1
30
30
88
95
1
1
1
2
3
4
24
PhB(OH)
2
18
12
30
30
93
91
15
5
30
93
1
1
6
7
PhB(OH)
2
24
2
30
30
95
96
1
1
2
2
2
8
9
0
1
2
PhB(OH)
PhB(OH)
PhB(OH)
2
2
2
36
36
36
36
36
80
80
60
80
80
70
47
66
71
88
PhB(OH)
2
[
2 3
a] Reaction conditions: aryl halide (1 mmol), arylboronic acid (1.5 mmol), K CO (1.5 mmol), solvent (2 mL), catalyst (0.22 mol% Pd). [b] Isolated yield.
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bar in eight consecutive runs with no significant loss of catalyt-
ic activity and its structure and the superparamagnetic proper-
ties were retained.
Experimental Section
[14]
Synthesis of magnetic NPs
FeCl ·6H O (11.0 g) and FeCl ·4H O (4.0 g) were dissolved in deion-
3
2
2
2
ized water (250 mL) and the mixture was stirred using a mechanical
stirrer under an Ar atmosphere. To the resulting mixture, aqueous
ammonia (25%, 40 mL) was added slowly over 20 min, and the
mixture was stirred at 808C for 4 h. A black precipitate of Fe O
3
4
was collected by using an external magnet and washed with de-
ionized water (3”20 mL) and ethanol (3”20 mL) and finally dried
under vacuum.
Figure 13. SEM image of the catalyst after the third run.
Synthesis of carbon-dots-modified Fe O
3
4
Citric acid (1 g) and urea (0.5 g) were dissolved in distilled water
25 mL), and the mixture was transferred to a Teflon autoclave and
(
heated at 1608C for 6 h. Then, the reactor was cooled to RT, and
the obtained material was centrifuged at 10000 rpm for 10 min to
remove larger particles. Fe O NPs (0.5 g) were sonicated in water
3
4
(
5 mL) for 15 min. Then, the C-dots suspension (0.7 mL) was added
to the flask that contained the magnetic particles, and this mixture
was stirred mechanically for 24 h at 608C. The resulting carbon-
dots-modified Fe O was subjected to magnetic separation and the
3
4
obtained material was washed with deionized water (3”10 mL)
and ethanol (3”10 mL) and dried under vacuum.
Synthesis of Pd@C-dots@Fe O
3
4
Figure 14. TEM image of reused catalyst after the third run.
C-dots@Fe O (500 mg) was sonicated in water (10 mL) for 30 min
3
4
at RT. In another flask, PdCl (60 mg) was sonicated and dissolved
2
Furthermore, a study of the magnetization of the recycled
catalyst after the third run (Figure 9) confirmed the preserva-
tion of the superparamagnetic properties of the catalyst
during the reaction.
in water (5 mL). Then, the solution of PdCl was added to the flask
that contained C-dots@Fe O , and the mixture was mechanically
3 4
stirred for 24 h at 608C under reflux. Then, the solid was separated
magnetically, washed with water (3”20 mL) and ethanol (3”
2
2
0 mL), and dried in an oven at 608C. The loading of Pd on the ob-
tained material was determined by ICP analysis to be
À1
Conclusions
0.275 mmolg .
We have introduced a new magnetically separable Pd catalyst,
in which magnetic Fe O was modified by carbon dots as
General procedure for the Suzuki–Miyaura reaction
3
4
a green and abundant material to support Pd nanoparticles
NPs). The new material can reduce PdCl to Pd NPs without
Aryl halide (1 mmol), arylboronic acid (1.5 mmol), K CO (1.5 mmol),
2
3
(
2
catalyst (8 mg that contained 0.22 mol% Pd) and water/ethanol
(1:1, 2 mL) were added to a 5 mL flask, and the mixture was stirred
mechanically at RT or 808C (depending on the aryl halide). The pro-
gresses of the reactions were monitored by GC. After completion
of the reaction, the crude product was extracted using ethyl ace-
tate. The pure products were obtained by column chromatography
on silica using the hexane and ethyl acetate as eluent.
the use of another reducing agent. The obtained catalyst was
characterized successfully by different techniques, such as
energy-dispersive spectroscopy, TEM, thermogravimetric analy-
sis, FTIR spectroscopy, vibrating sample magnetometry, atomic
absorption spectroscopy, and solid UV/Vis spectroscopy, and
has been applied successfully as an efficient catalyst for the
Suzuki–Miyaura cross-coupling reaction in aqueous media
(
aqueous ethanol). The exact amount of required catalyst and Acknowledgements
type of solvent and base were determined using design of ex-
periments. The reactions of aryl bromides were performed at
room temperature, and that of aryl chlorides at 808C. Compa-
The authors are grateful to the Institute for Advanced Studies in
Basic Sciences (IASBS) and the Iran National Science Foundation
(INSF-Grant number of 94010666) for support of this work. C.N. is
grateful to the Spanish Ministerio de Economia y Competitividad
(MINECO) (projects CTQ2013-43446-P and CTQ2014-51912-REDC),
rative studies with physically absorbed Pd on Fe O4 NPs
3
showed a very low catalytic efficiency with respect to Pd@C-
dots@Fe O The catalyst was recycled easily using a magnetic
3
4.
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FEDER, the Generalitat Valenciana (PROMETEOII/2014/017), and
the University of Alicante for financial support.
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Received: August 18, 2015
Published online on November 13, 2015
ChemCatChem 2016, 8, 441 – 447
www.chemcatchem.org
447
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