In situ biosynthesis of palladium nanoparticles on Artemisia abrotanum extract-modified graphene oxide and its catalytic activity for Suzuki coupling reactions

Article abstract of DOI:10.1016/j.poly.2019.02.053

We progressed the catalytic activity of Pd NPs coated on Artemisia abrotanum extract-modified graphene (Pd NPs/RGO) for the Suzuki coupling reactions. Pd NPs/RGO nanocatalyst was fabricated via modifying the surface of graphene oxide (GO) with A. abrotanum extract as a reducing and stabilizing agent with no addition of any toxic agent to in situ reduction and immobilizing Pd nanoparticles. Sundry methods like FTIR, UV–Vis, ICP-AES, XRD, FE-SEM, WDX, TEM and EDX have been used for explaining the structure and morphology of the Pd NPs/RGO nanocatalyst. The outcomes indicate that the Pd (0) nanoparticles are completely spread on the functionalized GO surface. Pd NPs/RGO showed excellent catalytic performance as a recyclable nanocatalyst in Suzuki-Miyaura reactions with high yields. Moreover, the recycled nanocatalyst showed no considerable loss in its activity.

Full text of DOI:10.1016/j.poly.2019.02.053

Accepted Manuscript
In situ biosynthesis of palladium nanoparticles on Artemisia abrotanum extract-
modified graphene oxide and its catalytic activity for Suzuki coupling reactions
Mirmehdi Hashemi Salehi, Mohammad Yousefi, Malak Hekmati
PII:
S0277-5387(19)30154-8
https://doi.org/10.1016/j.poly.2019.02.053
POLY 13797
DOI:
Reference:
Polyhedron
To appear in:
Received Date:
Revised Date:
Accepted Date:
23 January 2019
25 February 2019
27 February 2019
Please cite this article as: M.H. Salehi, M. Yousefi, M. Hekmati, In situ biosynthesis of palladium nanoparticles on
Artemisia abrotanum extract-modified graphene oxide and its catalytic activity for Suzuki coupling reactions,
Polyhedron (2019), doi: https://doi.org/10.1016/j.poly.2019.02.053
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In situ biosynthesis of palladium nanoparticles on Artemisia abrotanum extract-
modified graphene oxide and its catalytic activity for Suzuki coupling reactions
Mirmehdi Hashemi Salehi,a Mohammad Yousefi,*,a Malak Hekmatib
aDepartment of Chemistry, Yadegar-e-Imam Khomeini (RAH), Shahr-e-Rey Branch, Islamic Azad University,
Tehran, Iran
bDepartment of Organic Chemistry, Faculty of Pharmaceutical Chemistry, Pharmaceutical Sciences Branch,
Islamic Azad University, Tehran, Iran
E-mail myousefi50@hotmail.com
Abstract. We progressed the catalytic activity of Pd NPs coated on Artemisia abrotanum extract-
modified graphene (Pd NPs/RGO) for the Suzuki coupling reactions. Pd NPs/RGO nanocatalyst
was fabricated via modifying the surface of graphene oxide (GO) with Artemisia abrotanum
extract as a reducing and stabilizing agent with no addition of any toxic agent to in-situ reduction
and immobilizing Pd nanoparticles. Sundry methods like FTIR, UV-Vis, ICP-AES, XRD, FE-
SEM, WDX, TEM and EDX have been used for explaining the structure and morphology of the
Pd NPs/RGO nanocatalyst. The outcomes indicate that the Pd (0) nanoparticles are completely
spread on the functionalized GO surface. Pd NPs/RGO showed excellent catalytic performance as
a recyclable nanocatalyst in Suzuki-Miyaura reactions with high yields. Moreover, the recycled
nanocatalyst showed no considerable loss in its activity.
Keywords: Green synthesis, Graphene, Pd nanoparticles, Suzuki
1. Introduction
C-C bond creation, which is an important procedure in organic chemistry and accessible using a
wide range of transition metal catalysts, has been extensively used to prepare pharmacological,
natural products and materials. In this regard, the palladium-catalyzed Suzuki coupling reactions
are one of the most effective approaches to create C-C bonds [1-7]. Though other reactions like
Negishi coupling, Stille coupling and so on are also accessible for this purpose, the palladium-
catalyzed Suzuki coupling reactions has recently been the first choice, particularly yields biphenyl
and its derivatives. The main advantages of Suzuki coupling reactions comparing to other C-C
coupling reactions are the mild reaction conditions, bearing a variety of functional groups, simple
to get the different commercially substrates and harmless byproducts
Metal and graphene nanoparticles (NPs) display two main kind of components in the contemporary
nanotechnology [8]. Owing to their unique structural features and interesting properties, noble
metal NPs and graphene have been extensively taken into account for numerous applications, like
electronic device [9-11], energy conversion and storage [12,13], sensing [14,15], catalytic [16,17],
and several others [18-20]. In catalytic research, graphene is mostly used as a support due to its
high surface area (computed value, 2630 m2g-1) and flexible surface features [21].
Artemisia abrotanum L. (Fig. 1) has traditionally been utilized for pharmaceutical purpose in
treating certain diseases, like upper airway disorders [22]. The polyphenols and flavonoids that are
contained within A. abrotanum L. represents that this herbal extract have potential to be used in a
wide range of applications.
1

Figure 1. Image of the Artemisia abrotanum.
In terms of multiple features of graphene stated above, we herein introduce a simple green
synthetic method to Pd NPs -graphene hybrid with Artemisia abrotanum leaves extract as both
reductant and stabilizer. Firstly, extract can effectively reduce GO and adsorb on the reduced GO
surface. Next, the adsorbed Artemisia abrotanum leaves biomolecules can additionally in situ
reduce Pd ions to Pd NPs and causes their stabilization. Because the concentrations and distribution
of the surface adsorbed Artemisia abrotanum leaves biomolecules are predetermined, well
dispersed Pd NPs could be in situ prepared on the surface of Artemisia abrotanum leaves extract
modified graphene. Moreover, it was used in Suzuki-Miyaura cross-coupling reactions (Scheme
1).
2. Experimental
2.1. Preparation of Artemisia abrotanum extract
10 g of dried Artemisia abrotanum was powdered and heated along with 100 mL of sterile distilled
water at temperature of 80οC for 30 minutes, next it was cooled down to ambient temperature. The
mixture was centrifuged at 4000 rpm, supernatant isolated via filtration, and finally kept in the
ο
refrigerator at temperature of 4 C to be utilized as a reductant and stabilizer agent in following
experiments.
2.2. The Pd NPs/RGO green synthesis using Artemisia abrotanum extract
Finally, the Pd NPs/RGO was synthesized using Artemisia abrotanum aqueous extract. In order to
synthesize the Pd NPs/RGO, the above extract into synthesized GO (100 mg) was added from
natural graphite powder with a modified Hummers method and sonicated for 20 min. Then, the
reaction mixture was refluxed by agitating for 2 h. The mixture color changed from light brown to
black, presenting the reduction of graphene oxide (GO), which was stable. The RGO was separated
via centrifugation, after cooling to ambient temperature. Following rinsing, 30 mL of 0.3 M
Na2PdCl4 under agitation was poured dropwise into the mixture at temperature of 100 ºC for 24 h.
The final Pd NPs/RGO was isolated by centrifugation, and washed 3 steps with DI H2O, next used
for assessment and the catalysis research. The Pd amount in Pd NPs/RGO was 0.18 mmol/g which
measured by ICP-AES.
2

2.3. General procedure for Suzuki-Miyaura reactions
1.0 mmol of aryl halide, 3 mL H2O-EtOH (1:1, v/v), phenyl boronic acid (1.0 mmol), K2CO3 (2
mmol) and Pd NPs/RGO (20 mg, 0.1 mol %) were poured into the reaction system. The resulted
mixture was stirred at 50 ºC for required times in Table 2. At the end of the reaction (controlled
with TLC), 5 mL ethanol was added, and the catalyst was separated via centrifugation. Additional
purification was attained using column chromatography [eluent: hexane: ethylacetate (4:1)].
3. Results and Discussion
In current study, Pd NPs/RGO was synthesized over one stage via Pd2+ ions and GO reduction
with the extract of Artemisia abrotanum as a stabilizer and reductant agent. Artemisia abrotanum
extract as a useful and cost-effective option displays an ecofriendly and interesting synthetic way
to prepare the Pd NPs without using toxic ingredients.
RGO
Graphene oxide
H2O, reflux
Artemisia abrotanum extract-modified
graphene
Na2PdCl4
R
B(OH2)2
X
H2O-EtOH
K2CO3
RGO
= Pd NPs
R
Scheme 1. Green synthesis of Pd NPs/RGO and its performance in the Suzuki coupling
reactions.
The synthesized Pd NPs/RGO nanocomposite was examined using UV–vis spectroscopy. The UV
spectrum of GO (Fig. 2) specifies a maximum absorption peak at λmax 235 nm relating with the
π→π* transition of the aromatic C-C bonds and a weak shoulder can be found at 300 nm
3

corresponding to the n→π* transitions of C=O bonds. The UV–vis spectrum corresponding to
green RGO prepared using the Artemisia abrotanum leaves extract displays a new peak and a red
shift of specific peak at 235 nm to 272 nm shows the completion of the reaction and synthesis of
the RGO. Then, the effective in situ reduced Pd ions to Pd NPs on the RGO surface is proved with
TEM image (Fig. 3).
Fig. 2. UV–vis spectra of the GO and RGO by Artemisia abrotanum leaves extract.
Based on the TEM analysis (Fig. 3), it can be found that Pd NPs evenly dispersed on the modified
graphene surface. The outcomes represented that the extract of Artemisia abrotanum leaves has a
main role to increase the Pd NPs dispersibility. Furthermore, according to TEM image, the RGO
are covered with a thin layer of biomolecules, which could be responsible for reducing and
stabilizing the observed Pd NPs.
4

Fig. 3. TEM image of Pd NPs/RGO.
The GO and Pd NPs/RGO morphology were assessed using FE-SEM as can be observed in Figures
4a,b. Fig. 4b shows the FE-SEM image of Pd NPs/RGO with large Pd NPs quantities are dispersed
on the extract-modified RGO surfaces comparing to GO.
5

Fig. 4. (a) FESEM image of GO, and (b) Pd NPs/RGO.
Energy-dispersive X-ray spectroscopy is an analytical method applied for the elemental analysis
of the newly prepared Pd NPs/RGO catalyst. EDX spectra (Fig. 5) corresponding to Pd NPs/RGO
catalyst demonstrates divers characteristic signals relating with C, N, O and Pd atoms which
confirm the connection of extract bimolecular and Pd on the GO surface. Elemental mapping for
Pd NPs/RGO catalyst was performed for understanding the distribution of elements in the Pd
NPs/RGO catalyst as represented in Fig. 6. According to elemental mapping data, the distribution
of all elements were performed uniformly.
6

Fig. 5. EDX spectrum of Pd NPs/RGO catalyst.
Fig. 6. Elemental mapping of Pd NPs/RGO catalyst.
The XRD pattern corresponding to the Pd NPs/RGO is represented in Fig. 7. XRD analysis indicate
diffraction peak at 2θ of 23.5º (002) corresponding to the RGO. Moreover, it indicates main
diffraction peaks at 39.9º, 46.4º, 67.5º (2θ), which can be assigned to (111), (200), and (220) planes
of the fcc Pd.
7

Fig. 7. XRD pattern of Pd NPs/RGO.
Catalytic activity of the prepared Pd NPs/RGO nanocatalyst was also assessed via Suzuki-Miyaura
coupling reaction of aryl halides with phenyl boronic acid. To carry out a primary evaluation on
the reaction, Suzuki coupling reaction of phenyl boronic acid with 4-methylbromobenzene was
chosen as a model. So that, the values of reaction factors of solvent, base, temperature and catalyst
concentration could be studied. The optimal conditions are represented in Table 1. As it could be
expected, no desired product was considerable in the absence of the catalyst (Table 1, entry 11).
Though, introduction of the catalyst to the reaction medium quickly improved formation of the
product in excellent yields. The reactions were performed in H2O/EtOH (1:1) as the optimal
solvent. Amongst the studied bases, K2CO3 was the best base. Moreover, the effect of catalyst
concentration was showed by using divers amounts of the catalyst in the range of 0.05 mol% to
0.2 mol% (Table 1, entries 7,8 and 9). Based on the results, the maximum yield can be achieved
by using 20 mg of the catalyst (0.1 mol%) (Table 1, entry 8). Furthermore, the optimal reaction
temperature was identified to be 50 °C (entry 8 versus entries 12, 13 and 14). At temperature of
25 °C, lower yield of the target product was inspected while product yield was not increased by
enhancing the temperature to 100 °C, explicitly.
Table 1. The optimized condition for the Suzuki reaction of 4-methylbromobenzene with phenyl
boronic acid.a
Br
various conditions
CH3
+
H3C
B(OH)2
Entry Pd (mol%)
Solvent
DMF
Base
K2CO3
T (°C) Time (h) Yield (%)
80 70
1
0.1
4
8

2
3
4
5
6
7
8
9
10
11
12
13
14
0.1
0.1
0.1
0.1
0.1
0.05
0.1
0.2
0.1
0.0
0.1
0.1
0.1
Toluene
EtOH
H2O
K2CO3
K2CO3
K2CO3
60
60
50
50
90
50
50
50
50
50
25
60
100
2
3
6
3
3
3
2
2
12
12
10
2
60
70
35
60
70
75
95
95
Trace
0.0
65
95
95
EtOH/H2Ob NaOAc
EtOH/H2Ob
Et3N
EtOH/H2Ob K2CO3
EtOH/H2Ob K2CO3
EtOH/H2Ob K2CO3
EtOH/H2Ob No base
EtOH/H2Ob K2CO3
EtOH/H2Ob K2CO3
EtOH/H2Ob K2CO3
EtOH/H2Ob K2CO3
2
aReaction conditions: 4-methylbromobenzene (1.0 mmol), phenyl boronic acid (1.0 mmol), catalyst, base (2 mmol)
and solvent (3 mL).
b3 mL (1:1)
Following optimizing the reaction conditions, the performance of Pd NPs/RGO nanocatalyst was
examined for Suzuki coupling reaction of several aryl halides with phenyl boronic acid and
outcomes are presented in Table 2. The experimental technique is easy and appropriate, and is able
to tolerate a wide range of functional groups. Pd NPs/RGO nanocatalyst was applied in Suzuki
reaction for aryl iodides with both electron withdrawing and electron donating substituents (Table
2, entries 1, 4, 7, 10, 12, 14). The outcomes demonstrate that all aryl bromides resulted in good to
high yields regardless of their substituents electronic features by changing the reaction duration
(Table 2, entries 2, 5, 8, 11, 13, 15). In general, bromo-arenes and iodo-arenes compounds except
chloro-arenes reacted effectively with phenyl boronic acid resulting cross-coupling products in
good to high yield. Though, reaction of chloro-arenes with phenyl boronic acid resulted in cross-
coupling products in low yield (Table 2, entries 3, 6, 9).
Table 2. Catalytic performance of Pd NPs/RGO catalyst in Suzuki reactions.a
Entry RC6H4X
R
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
X
I
Br
Cl
I
Br
Cl
I
Br
Cl
I
Time (h) Yield (%)b
1
2
H
H
0.5
1.0
24
95
95
55
95
95
50
96
92
45
90
90
85
80
90
88
3
H
4
5
6
7
8
9
10
11
12
13
14
15
4-CH3
4-CH3
4-CH3
4-COCH3
4-COCH3
4-COCH3
4-CH3O
4-CH3O
4-NH2
4-NH2
4-OH
1.0
2.0
24
1.5
3.0
24
1.0
3.0
2.0
4.0
2.0
4.0
Br
I
Br
I
4-OH
Br
9

aReaction conditions: 1.0 mmol aryl halides, 1.0 mmol phenyl boronic acid, 2.0 mmol K2CO3, 3 mL of H2O/EtOH
(1:1), and 0.1 mol% Pd NPs/RGO catalyst at 50 ºC.
The catalyst reproducibility [23], we studied efficiency of Pd NPs/RGO catalyst in Suzuki
coupling of model reaction. At the end of each catalytic reaction, Pd NPs/RGO catalyst was
recycled, reformed, and recovered directly for the subsequent run. The reproducibility experiment
indicates that Pd NPs/RGO catalyst could be recovered in eight successive cycles for Suzuki
reactions (Fig. 8). Following the reusability experiments, we still recorded excellent reaction
performances for Suzuki reaction (85%). Furthermore, TEM of Pd NPs/RGO catalyst were
performed following the recycle test to indicate the constancy of the catalyst (Fig. 9). We observed
that Pd NPs/RGO image of the recycled Pd NPs/RGO catalyst was nearly similar to the fresh Pd
NPs/RGO catalyst. These analyses result in a good sign for the excellent constancy of Pd NPs/RGO
catalyst. Moreover, leaching test of Pd NPs/RGO catalyst was carried out following the reusability
studies. ICP-AES outcomes indicated the leaching of palladium ions from Pd NPs/RGO catalyst
was insignificant.
Fig. 8. The recycling of the Pd NPs/RGO.
Fig. 9. TEM image of reused catalyst after the 7th run.
10

Table 3 shows the results of comparing catalytic activity of Pd NPs/RGO catalyst with divers
studied catalysts in the coupling reaction between iodobenzene and bromobenzene with phenyl
boronic acid. As observed in Table 3, Pd NPs/RGO catalyst has better catalytic performance
comparing to other catalysts and also it results in a higher reaction yield with shorter reaction time
under mild condition.
Table 3. Comparison of Pd NPs/RGO catalyst with different reported catalysts in Suzuki-Miyaura
coupling reaction between iodobenzene and bromobenzene with phenyl bronic acid.
Entry Catalyst (mol%)
Conditions
X
Time (h)
Yield (%)
Refs.
1
2
3
4
5
6
7
8
Bis(oxamato)palladate(II) complex (5)
I, Br
2.0
78, 65
98, 90
95, 88
77.7
[24]
[25]
[26]
[27]
[28]
[29]
[30]
this work
Et3N, n‐Bu4NBr, 120 °C
K3PO4.3H2O, H2O, TBAB, 40 °C I, Br
5.0, 6.0
5.0, 5.5
24
NHC‐Pd(II) complex (0.2)
SiO2‐pA‐Cyan‐Cys‐Pd (0.5)
Pd3(dba) (1)
Pd–BOX (2)
γ ‐Fe2O3‐acetamidine‐Pd (0.12)
K2CO3, H2O, 100 °C
K3PO4, THF, 80 °C
K2CO3, DMF, 70 °C
Et3N, DMF, 100 °C
I, Br
Br
I
I, Br
I, Br
I, Br
6.0
100
0.5, 0.5
0.5, 0.7
0.5, 1.0
96, 96
95, 90
95, 95
Pd‐isatin Schiff base‐γ‐Fe2O3 (0.5, 1.5) Et3N, Solvent‐free, 100 °C
Pd NPs/RGO (0.1)
K2CO3, H2O-EtOH, 50 °C
4. Conclusions
In current research, a new and effective reusable Pd catalyst supported on Artemisia abrotanum
extract-modified GO was suggested for the first time. Next, structure characterization of Pd
NPs/RGO catalyst was performed with numerous analytical tools. Then, the catalytic behavior of
Pd NPs/RGO catalyst was studied in Suzuki coupling reactions. The catalytic activity research
showed that Pd NPs/RGO catalyst have good activity towards catalytic reactions under mild
reaction conditions. Furthermore, the catalyst showed excellent performance for eight runs in
Suzuki-Miyaura reaction. Briefly, of the results of current study showed that GO modified by herb
extract is a proper alternative support material for catalytic reactions.
Acknowledgments. We are thankful to Department of Chemistry, Shahr-e-Rey Branch, Islamic
Azad University, Tehran, Iran, for partial support of this work.
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In situ biosynthesis of palladium nanoparticles on Artemisia abrotanum extract-
modified graphene and their catalytic activity for Suzuki coupling reactions
Mirmehdi Hashemi Salehi, Mohammad Yousefi,* Malak Hekmati
13

RGO
Graphene oxide
H2O, reflux
Artemisia abrotanum extract-modified
graphene
Na2PdCl4
R
B(OH2)2
X
RGO
Suzuki
= Pd NPs
R
In situ biosynthesis of palladium nanoparticles on Artemisia abrotanum extract-
modified graphene and their catalytic activity for Suzuki coupling reactions
Mirmehdi Hashemi Salehi, Mohammad Yousefi,* Malak Hekmati
14

RGO
Graphene oxide
H2O, reflux
Artemisia abrotanum extract-modified
graphene
Na2PdCl4
R
B(OH2)2
X
RGO
Suzuki
= Pd NPs
R
A new and effective reusable Pd catalyst supported on Artemisia abrotanum extract-modified
GO was suggested for the Suzuki coupling reactions.
15