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Synthesis of powdered silver nanoparticles using hydrogen in aqueous

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Article  in  Particuology · February 2012

DOI: 10.1016/j.partic.2011.05.005

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 Particuology 10 (2012) 140–143

Contents lists available at SciVerse ScienceDirect

Particuology
journal homepage: www.elsevier.com/locate/partic

Synthesis of powdered silver nanoparticles using hydrogen in aqueous medium

Kushal D. Bhatte a , Krishna M. Deshmukh a , Yogesh P. Patil a , Dinesh N. Sawant a , Shin-Ichiro Fujita b ,
Masahiko Arai b , Bhalchandra M. Bhanage a,∗
a
Department of Chemistry, Institute of Chemical Technology, Matunga, Mumbai 400019, India
b
Chemical Process Engineering Divison, Graduate School of Engineering, Hokkaido University, Sapporo, Japan

a r t i c l e i n f o a b s t r a c t

Article history: Environmentally benign one-pot protocol is used in the synthesis of silver nanoparticles (AgNPs) in pow-
Received 25 February 2011 der form, involving the reduction of silver nitrate in the presence of fully hydrolyzed polyvinyl alcohol
Received in revised form 4 May 2011 (PVA) as stabilizer by hydrogen (H2 ) as reducing agent in aqueous medium. Fully hydrolyzed biodegrad-
Accepted 13 May 2011
able PVA has extremely low cytotoxicity, making it a favorable stabilizer from green perspective. In the
present methodology, essentially naked silver nanoparticles are obtained in good yield. The prepared sil-
Keywords:
ver nanoparticles were characterized by TEM, XRD, EDAX, UV–Vis spectroscopy and DLS histogram, and
Silver nanoparticles
studied for its activity as a recyclable catalyst for synthesis of different enaminones.
Aqueous media
Hydrogen © 2011 Chinese Society of Particuology and Institute of Process Engineering, Chinese Academy of
Catalysis Sciences. Published by Elsevier B.V. All rights reserved.
Enaminones synthesis

1. Introduction
Increased interest in small clusters of metal nanoparticles
results from their exceptional properties due to their high ratio
of surface area to size and unresidual surface energies, hence
potentially applicable in different areas (Hutchison, 2008; Volokitin
et al., 1996). Silver nanoparticles (AgNPs), for instance, have found
applications in catalysis, biosensing, antibacterial activity, surface
enhanced Raman spectroscopy, optoelctronics and textile fabrics
(Abou El-Nour, Eftaiha, Al-Warthan, & Ammar, 2010; Sharma,
Yngard, & Lin, 2009). Synthesis of AgNPs via easy, reliable and scal-
able method which can provide essentially naked nanoparticles
is a challenging task which must satisfy green synthesis with proper
selection of green solvent, benign reducing agent and nontoxic
stabilizers (Anastas & Warner, 1998). Various existing chemical
reductions for AgNPs have limited application due to the use
of toxic reducing agents like sodium borohydride or formalde-
hyde along with stabilizers in harmful organic solvents (Cason,
Khambaswadkar, & Roberts, 2000; Chen & Chen, 2002; Singh &
Khanna, 2007). Some methodologies replace these toxic reducing
agents by using l-arginine, green tea, etc. as reducing agent and
non-conventional heating techniques like microwaves (Moulton
et al., 2010; Nadagouda & Varma, 2008; Pal, Shah, & Devi, 2009).
However scalability of process and yield of naked nanoparticles
still remain major concerns. Water, which on oxidation gives pro-
ton, could be used in the synthesis of naked AgNPs. A few methods
are reported on the synthesis of AgNP’s using hydrogen though
they suffer from several drawbacks such as use of expensive, non
green phosphonated calixarene as a stabilizer (Hartlieb, Saunders,
& Raston, 2009) and suppression of AgNP’s due surface coat-
ing of fluorinated silane (Evanoff & Chumanov, 2004). We have
developed a protocol for making naked AgNPs using hydrogen in
water with fully hydrolyzed PVA as stabilizer, which is a water
soluble, biodegradable polymer having low cytotoxicity (Razzak,
Zainuddin, Dewi, Lely, & Taty, 1999), that is, Ag–PVA composites
are used in textiles for antimicrobial purposes, and in medici-
nal and household applications (Hong, Park, Sul, Youk, & Kang,
2006). In this study, the synthesized AgNPs were then studied
for its catalytic activity for enaminone synthesis. Enaminones are
important structural motifs in organic synthesis widely used as
versatile building blocks for synthesis of important heterocyclic
compounds, nitrogen-containing compounds, naturally occurring
alkaloids, pharmaceuticals with antiepileptic, anticonvulsant and
antitumor properties (Abass & Mostafa, 2005; Li, Watson, Buckheit,
& Zhang, 2007).
2. Experimental
2.1. Chemicals and instruments

∗ Corresponding author. Tel.: +91 22 24145616; fax: +91 22 24145614. All chemicals like AgNO3 (A.R. grade) and PVA (avg. mol. wt.
E-mail addresses: bhalchandra bhanage@yahoo.com, 14,000), amines and carbonyl compounds were purchased from
bm.bhanage@ictmumbai.edu.in (B.M. Bhanage). firms of repute with their highest purity available and used without

1674-2001/$ – see front matter © 2011 Chinese Society of Particuology and Institute of Process Engineering, Chinese Academy of Sciences. Published by Elsevier B.V. All rights reserved.
doi:10.1016/j.partic.2011.05.005
 K.D. Bhatte et al. / Particuology 10 (2012) 140–143 141

further purification. Ultrapure hydrogen was purchased from M/s

Rakhangi Gas Services Pvt. Ltd., India.
The synthesis of nanoparticles was carried out in a 400 mL stain-
less steel autoclave (SS-316, M/s Amar Equipment, Ltd., India). TEM
images were recorded on Philips CM 200 operating at 120 kV. Par-
ticle size histogram was recorded on DLS Beckman Coulter Delsa
Nano C. EDAX analysis was carried out using JEOL – JFC 1600 with
platinum coating. X-ray diffraction measurement was obtained
with XRD Mini Flex Rigaku model using Cu K␣ with a scanning
rate of 2◦ per minute. UV–Vis spectroscopy was carried out using
Shimadzu–1650 UV. TGA analysis was carried out using a Water
India Pvt. Ltd. apparatus under nitrogen atmosphere with tem-
perature rise of 10 ◦ C/min. Characterization of enaminones was
determined by GC analysis (Chemito 1000) and GC-MS analysis
(Shimadzu QP 2010).

2.2. Synthesis of silver nanoparticles

Synthesis of nanoparticles was carried out in a 400 mL stain-

less steel autoclave (SS-316, M/s Amar Equipment, Ltd., India) with
8 cm inner diameter, 11 cm height and 2 cm propeller length. In a
typical experiment, 1.5 g of PVA and 1 g of AgNO3 were dissolved Fig. 1. TEM image of silver nanoparticles with SAED pattern inside.
in 100 mL distilled water and then charged to the autoclave. The
reactor was flushed with hydrogen and pressurized to 2 MPa and
heated to 150 ◦ C. The solution was stirred at 500 rpm for 2 h and
then cooled to room temperature. Upon opening the reactor, AgNPs
were found along the inner autoclave wall in copious amount. The
AgNPs were scraped off and subjected to different characteriza-
tions. In order to study the pathway of AgNPs formation a parallel
run was carried out in absence of hydrogen, and the intermediate
(Ag–PVA) was isolated and subjected to TGA analysis.

2.3. Experimental procedure for enaminones synthesis

In a 25 mL round bottom flask, dicarbonyl compound (1 mmol), Fig. 2. Histogram of silver nanoparticles.

amine (1 mmol) and silver nanoparticles (0.2 mmol) were added

into 5 mL of ethanol and stirred at 60 ◦ C for desired time. Progress
of reaction was monitored by gas chromatography (Chemito 1000).
On completion of reaction, 5 mL of water was added to the reac-
tion mixture and centrifuged at 5000 rpm for 20 min to separate
the AgNPs. The reaction mixture was slowly decanted and the set-
tled AgNPs were then collected and dried. The crude product was
extracted from mixture using ethyl acetate (5 mL × 3) and dried
using Na2 SO4 . All the products were compared with authentic sam-
ples and characterized by GC–MS analysis.
Debey–Scherrar equation is 35 nm and is well in agreement with
DLS measurement. EDAX analysis shows energy peaks correspond-
ing to silver metal (Fig. 5) which proves that the prepared silver
nanoparticles are free from other impurities.
PVA being a water soluble, biodegradable polymer bearing
hydrophilic hydroxyl groups, served well as a stabilizer in the

3. Results and discussion

3.1. Synthesis of AgNPs

The silver nanoparticles prepared were characterized by various

techniques as mentioned in Section 2. The TEM image of prepared
silver nanoparticles confirms that the synthesized nanoparticles
were in the nano size range with uniform morphology (Fig. 1). The
SAED pattern inside the TEM image indicated the well crystalline
nature of silver nanoparticles. The histogram obtained by dynamic
light scattering (DLS) technique shows the particle size distribu-
tion with an average particle diameter of 40 nm ± 10 nm (Fig. 2).
The UV–Vis spectrum of the silver nanoparticles exhibits the sur-
face plasmon band around 400 nm (Fig. 3). The X-ray diffraction
pattern confirms the formation of only silver nanoparticles with
a face centered cubic silver crystal structure (Fig. 4). The promi-
nent peaks at 2 values about 38◦ , 44.2◦ , 64.4◦ and 77◦ represent
the (1 1 1), (2 0 0), (2 2 0), (3 1 1) planes of cubic FCC structure of sil-
ver. The average crystallite size of silver nanoparticles obtained by Fig. 3. UV–Vis spectrum of silver nanoparticles.
142 K.D. Bhatte et al. / Particuology 10 (2012) 140–143

Table 1
Substrate study for enaminones.

Entry Dicarbonyl compound Amine Enaminone Time (h) Yield (%)

NH2 H
O O N

1 24 n.r

NH2 H
O O N

2 7 90

O
O O
N
3 3 85
O O
N
H

H
NH2
O O N

4 3 80

NH2 H
O O N O

5 5 70

O O

O
O O O
N
6 3 78

O O O
N
H

Reaction conditions: dicarbonyl compounds (1 mmol), amines (1 mmol), methanol = 5 mL, AgNPs = 0.2 mmol (except for Entry 1). All products are well known and yield is
based on GC and GC–MS analysis. ‘n.r’ represents no reaction.

present protocol in preventing agglomeration of the nanoparticles.
In the present investigation, silver nanoparticles were not obtained
without the presence of PVA. The proposed mechanism for silver
nanoparticles formation is shown in Fig. 6, to take place in two
steps. First, Ag–PVA complex is formed by co-ordination between
Ag(I) and PVA in refluxing aqueous solution; while in the second
step silver nanoparticles were formed by reduction of the Ag–PVA
complex with hydrogen. This mechanism was further supported by
TGA analyses of PVA alone and of Ag–PVA (Fig. 7). The latter shows

Fig. 4. XRD pattern of silver nanoparticles. Fig. 5. EDAX spectrum of silver nanoparticles.
 K.D. Bhatte et al. / Particuology 10 (2012) 140–143
Fig. 6. Proposed mechanism for the formation of silver nanoparticles.
Fig. 7. TGA analyses of PVA alone and of Ag–PVA.
Fig. 8. Schematic representation of enaminones synthesis.
decomposition profile at higher temperature than PVA alone, indi-
cating improved thermal stability of PVA due to presence of silver.
3.2. Application of AgNPs for enaminones synthesis
Furthermore, we investigated the catalytic activity of nanocrys-
talline AgNPs, for the synthesis of enaminones using aniline and
acetyl acetone as a model reaction (Fig. 8). Initially, the reaction
in the absence of AgNPs catalyst was studied and no product for-
mation was observed even on prolonging reaction time to 24 h
(Table 1, Entry 1). Then, the catalytic activity of AgNPs was exam-
ined for enaminone synthesis using different amines and carbonyl
compounds, resulting in good to excellent yields of the desired
products (Table 1, Entries 2–6). The nanocrystalline AgNPs have
high surface area and hence a larger amount of active sites, thus
ultimately resulting in high yields.
View publication stats
143
4. Conclusions
We developed a novel green synthesis protocol of preparing sil-
ver nanoparticles AgNPs involving the reduction of silver nitrate
in the presence of fully hydrolyzed polyvinyl alcohol (PVA) as sta-
bilizer and hydrogen (H2 ) as reducing agent in aqueous medium.
The prepared silver nanoparticles were characterized by TEM, XRD,
EDAX, UV–Vis spectroscopy and DLS histogram, and studied for
their activity as a recyclable catalyst for the synthesis of different
enaminones.
Acknowledgements
The financial support from UGC-Green Technology Center,
University of Mumbai, India and collaborative support from DST-
JSPS for Indo-Japan project no. DST/INT/JAP/P-67/08 are gratefully
acknowledged.
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