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J Nanopart Res (2013) 15:1537

DOI 10.1007/s11051-013-1537-1

REVIEW

Advances of Ag, Cu, and Ag–Cu alloy nanoparticles


synthesized via chemical reduction route
Kim Seah Tan • Kuan Yew Cheong

Received: 27 December 2012 / Accepted: 23 February 2013 / Published online: 10 March 2013
Ó Springer Science+Business Media Dordrecht 2013

Abstract Silver (Ag) and copper (Cu) nanoparticles influencing the quality of those nanoparticles have also
have shown great potential in variety applications due to been reviewed thoroughly.
their excellent electrical and thermal properties resulting
high demand in the market. Decreasing in size to Keywords Metal  Alloy  Reducing agent 
nanometer scale has shown distinct improvement in Stabilizer  pH  Temperature
these inherent properties due to larger surface-to-volume
ratio. Ag and Cu nanoparticles are also shown higher
surface reactivity, and therefore being used to improve Introduction
interfacial and catalytic process. Their melting points
have also dramatically decreased compared with bulk and Metal nanoparticles have been attracted great attention
thus can be processed at relatively low temperature. in recent years, mainly due to their properties and
Besides, regularly alloying Ag into Cu to create Ag–Cu applications in diverse areas such as optics, catalysis,
alloy nanoparticles could be used to improve fast electronic, cosmetic, and biotechnology (Poole and
oxidizing property of Cu nanoparticles. There are Owens 2003; Lines 2008). These applications are
varieties methods have been reported on the synthesis strongly dependent on the size and shape of the
of Ag, Cu, and Ag–Cu alloy nanoparticles. This review nanoparticles. Consequently, controlled synthesis of
aims to cover chemical reduction means for synthesis of metal nanoparticles in different sizes and shapes
those nanoparticles. Advances of this technique utilizing become remarkable important in current nanotechnol-
different reagents namely metal salt precursors, reducing ogy development. Among the metal nanoparticles,
agents, and stabilizers, as well as their effects on controlled syntheses of gold (Au) and silver (Ag)
respective nanoparticles have been systematically nanoparticles are particularly attracted much research-
reviewed. Other parameters such as pH and temperature ers concern than others. Au and Ag are both noble
that have been considered as an important factor metals that possess excellent optical and electrical
properties. Also, they display good corrosion resistant
characteristic, this resulting synthesis of their nano-
particles can be easily achieved compare to other
K. S. Tan  K. Y. Cheong (&) metals that tend to oxidize during synthesis. Copper
Electronic Materials Research Group, School of Materials (Cu) is another metal that has comparable optical,
and Mineral Resources Engineering, Universiti Sains
thermal, and electrical properties with Au and Ag. The
Malaysia, Engineering Campus, 14300 Nibong Tebal,
Penang, Malaysia only drawback is that Cu suffers for oxidation during
e-mail: cheong@eng.usm.my nanoparticles synthesis process, and this becomes the

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major challenge. However, Au is expensive than Ag are most favored in review. Moreover, the trend also
and Cu; therefore, the synthesis of the latter nanopar- shows more concerned on Ag nanoparticles synthesis
ticles become more favorable on current research. techniques instead of Cu and Ag–Cu alloy. The lack of
In general, controlled synthesis of Ag and Cu review papers that discuss about Cu and Ag–Cu alloy
nanoparticles can be categorized into top-down and nanoparticles synthesis techniques have motivated us
bottom-up approaches. These two approaches can be to review on this topic.
subcategorized into variety synthesis techniques and The main aim of this review is on synthesis of Ag,
this article is no intention to cover in detail of all Cu, and Ag–Cu alloy nanoparticles via chemical
techniques as several articles have been widely reduction route. The context first reviews on chemical
covered (Biswas et al. 2012; Parak et al. 2010). In reduction mechanism in metal nanoparticles synthesis.
brief, top-down approach refers to use bulk Ag or Cu Next, the metal salt precursors, reducing agents, and
mechanically reduces its size into nanoscale (Gates stabilizers that used for respective nanoparticles
et al. 2005; Niemeyer 2001). Conversely, bottom-up synthesis will be summarized and evaluated. The
approach refers to build up of Ag or Cu nanoparticles other parameters that affect nanoparticles formation
by self assembly of atoms or molecules (Zhang 2003; also will be covered, such as pH and temperature.
Liz-Marzán and Kamat 2003). It is well known Finally, challenges face during synthesis and future
synthesis nanoparticles with bottom-up approach are scope in nanoparticles synthesis will also be presented.
better than top-down approach because more homo-
geneous chemical composition and lesser defects
nanoparticles can be obtained (Biswas et al. 2012). Metal nanoparticles formation mechanism
Moreover, bottom-up approach also eases in control- by chemical reduction route
ling the synthesis nanoparticles with narrow distribu-
tion of size and shape (Cao and Wang 2010). These The chemical reduction is one of the simplest methods
advantages consequently have attracted researchers’ uses to synthesis metal nanoparticles in various size
interest to synthesis Ag and Cu nanoparticles via and shape. This synthesis method is not a time
bottom-up approach. consuming process and has an immense potential to
There are twenty-five published review articles scale up when required to meet mass production needs.
about synthesis of Ag, Cu, and Ag–Cu alloy nanopar- However, a good understanding in mechanism is
ticles. By analyzing these review articles, the bottom- important to control the growth of metal nanoparticles
up approach is predominantly used in synthesizing of to the desired size and shape. Therefore, this section
Ag, Cu, and Ag–Cu alloy nanoparticles relatively to aims to provide an overview of the growth mechanism.
top-down approach (Only three articles). Further In general, metal nanoparticle formation in chem-
analysis: three papers reviewed solely about micro- ical reduction method consists of two stages, which are
emulsion synthesis (Capek 2004; Zhang et al. 2007; nucleation and successive growth. During nucleation,
Solanki and Murthy 2011), one paper reviewed solely cations contain within the metal salt solution are
about chemical reduction synthesis (Manikam et al. reduced to form metal atoms. These metal atoms are
2011), four papers about biological green synthesis randomly moved within the solution and collision
(Sharma et al. 2009; Thakkar et al. 2010; Kaler et al. between cations and atoms has resulted formation of
2010; Narayanan and Sakthivel 2011), and seventeen clusters. The nucleus is next to form through contin-
papers reviewed about variety synthesis techniques in uous collision of cations, atoms, and clusters. The
brief (Liz-Marzán 2005; Kuchibhatla et al. 2007; nucleus is subsequently growth to a critical size and
Rozenberg and Tenne 2008; Castonguay and Kakkar finally formation of nanoparticle is done. However,
2010; El-Nour et al. 2010; Meng et al. 2010; Sau and this mechanism is not sufficient to understand forma-
Rogach 2010; Tolaymat et al. 2010; Cortie and tion theory of metal nanoparticle, and thus other
McDonagh 2011; Martı́nez et al. 2011; Moon et al. perspectives must be sought. In essence, thermody-
2011; Muñoz-Flores et al. 2011; Rycenga et al. 2011; namics and kinetic rate are two theories best to cover
Tran and Nguyen 2011; Wang and Li 2011; Lu et al. the weaknesses of aforementioned mechanism. Ther-
2012; Rao et al. 2012). Among these seventeen papers, modynamics view free energy barrier need to be
seed mediate and template growths of nanoparticles surmounted during nucleation before the growth can

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be spontaneous continue (Fig. 1) (Zhang et al. 2011b). to growth (Burda et al. 2005; Tanaka et al. 2012). The
The overall free energy change (DG) is the sum of free high nucleation rate increases the number of nuclei
energy due to new volume formation and free energy being formed and these nuclei will grow indepen-
due to new surface created. Equation (1) is the dently to yield many small nanoparticles. The high
thermodynamics equation used to calculate the overall nucleation rate also produces nanoparticles with better
free energy change during spherical particles forma- uniformity of size distribution (Burda et al. 2005;
tion (Burda et al. 2005). Tanaka et al. 2012). In addition, secondary growth is
4 growing nanoparticles by collision and aggregation
DG ¼  pr 3 DGv þ 4pr 2 c ð1Þ between particles (Burda et al. 2005). The relative rate
3
of particles growth by aggregation is much higher than
where DGv is the free energy of new volume formed, r that of molecular addition, and thus larger nanoparti-
is the radius of the nuclei, and c is the surface free cles could be formed. However, after the nanoparticles
energy per unit surface area. Refer to Fig. 1, the are grown to a stable size, they will grow by consume
overall free energy has a positive maximum value at a smaller unstable nuclei instead of collision with other
critical size (r*), which is known as maximum free stable particles (Burda et al. 2005; Tanaka et al. 2012;
energy (DG*). This maximum free energy is the Cushing et al. 2004). This process is known as Ostwald
activation energy for nucleation and thus must be ripening phenomenon, where the large particles con-
surmounted during nucleation process. Nuclei larger tinue to grow larger, and small particles get smaller
than critical size will further decrease their free energy and finally dissolved (Burda et al. 2005; Cushing et al.
for subsequent growth into nanoparticles. Lower the 2004).
free energy indicates the nanoparticles growth process In summary, nucleation and growth of metal
have became spontaneous process. Besides, the crit- nanoparticles can be easily understood with prescribe
ical nuclei size r* can be obtained by setting dDG/ mechanism and theories. The relative rate of nucle-
Ddr = 0 and Eq. (2) has been derived (Burda et al. ation to growth is critical to control the size of metal
2005). Any nuclei with r [ r* will be grown to nanoparticles. This relative rate can be manipulated
nanoparticles and any r \ r* will be dissolved. using different metal salts, reducing agents, and
2c stabilizers. For example, employed reducing agent
r ¼ ð2Þ with strong reducing power could result high nucle-
DGv
After the nuclei are formed from metal salt solution, ation rate during metal salt reduction process, and
kinetic rate is a good theory to explain the nuclei finally smaller nanoparticles could be yielded. There-
growing and dissolving phenomena. The nuclei can fore, these reagents are reviewed in the following
grow continuously to nanoparticles either via molec- sections as they are directly affecting the product of
ular addition, secondary growth, or Ostwald ripening. metal nanoparticles being formed.
Molecular addition is growing nuclei to nanoparticles
by the addition of metal atoms on the surface of nuclei,
and it is strongly depends on relative rate of nucleation Synthesis of Ag nanoparticles via chemical
reduction

In general, chemical reduction synthesis technique


consists of three elements, which are metal salt
precursor, reducing agent, and stabilizer or surfactant.
Sometimes, solvent may be introduced to solubilize
the metal salt and other chemicals that involved in the
synthesis process. It also acts as an interacting media
for chemical reactions to be occurred. In addition, heat
or catalyst can also be introduced to speed up the
reaction and synthesis process if circumstance is
Fig. 1 Illustration of overall free energy change DG as function needed. Tolaymat et al. (2010) had performed an
of the growth particle size r (Zhang et al. 2011b) analysis on type of Ag salt precursors that had been

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used in synthesis of Ag nanoparticles. They (Tolaymat NaBH4 also started being widely used until today.
et al. 2010) found that silver nitrate (AgNO3) is the Song et al. (2009) has successfully produced Ag
most widely used Ag salt precursor compare to others nanoparticles by slowly dropped AgNO3 into NaBH4
as shown in Fig. 2. AgNO3 is a commonly used in the presence of a stabilizer named sodium dodecyl
precursor due to its low cost and chemical stability sulfate (SDS). This reverse order of reactant addition
(Lee et al. 2007) although silver acetate, silver citrate, to the reducing agent can cause immediate precipita-
silver sulfate, silver perchlorate, and silver 2-ethyl- tion and formation of stable Ag nanoparticles (Eq. 3)
hexonate have also been used (Manikam et al. 2011). (Song et al. 2009). This finding is also agreed by Van
Ag salt precursors are mainly used to produce ionic Hyning and Zukoski (1998) and Liu et al. (2007).
silver, which can be reduced and precipitated to form
Agþ þ BH 0
4 þ 3H2 O ! Ag þ BðOHÞ3 þ3:5H2 ð3Þ
silver atoms, clusters, and nanoparticles later. How-
ever, appropriate reducing agents should be chosen for Li et al. (2003) and Zhao et al. (2006a, b) utilized a
the reduction before precipitation can happen, and thus similar process to synthesis Ag nanoparticles with
it plays a key point in the synthesis of Ag NaBH4 as the reducing agent, but different stabilizers
nanoparticles. have been used. In Li et al. (2003) work, AgNO3 and
mercaptoacetic acid were added into a triply distilled
Reducing agents water with stirring condition. Next, KI was slowly
dripped into the above mixture with vigorous stir and a
According to Tolaymat et al. (2010), reducing agent is light yellow-green AgI colloid was formed. NaBH4
either a chemical agent, plant extract, biological agent, was then added into the AgI colloid, and Ag nanopar-
or irradiation means that is used to reduce Ag ions ticles were finally formed. The above process was also
during production of Ag nanoparticles. Sodium boro- utilized by Zhao et al. (2006a, b) except mercapto-
hydride (NaBH4) was first utilized as reducing agent in sulfonic acid and NaI were used instead of mercap-
1979 by Creighton et al. (1979). They succeed in toacetic acid and KI, respectively. The finding of their
preparing Ag nanoparticles by reduction of AgNO3 works is common, i.e., spherical Ag nanoparticles with
with rapid mixing and vigorous shaking of NaBH4 narrow distribution of sizes and shapes were obtained.
(Creighton et al. 1979). After that, Creighton method NaBH4 is the most widely used reducing agent in
has become a prominent Ag nanoparticles synthesis synthesis of Ag nanoparticles as reported in many
method (Hegde et al. 2006; Lundahl et al. 2008) and other works (Shon and Cutler 2004; Limsavarn et al.
2007; Van Hyning et al. 2001a, b; Doty et al. 2005;
Zou et al. 2006; Medina-Ramirez et al. 2009; Liu et al.
2010, 2012b; Pinto et al. 2010; Vorobyova et al. 1999;
Angelescu et al. 2012; Radziuk et al. 2007; Krutyakov
et al. 2010; Lee and Meisel 1982). This statement is
also agreed by Tolaymat et al. statistics work (Tolay-
mat et al. 2010). However, the amount of NaBH4 being
used is always in excess for the reduction of Ag salts
(Creighton et al. 1979; Radziuk et al. 2007; Angelescu
et al. 2012; Liu et al. 2007; Song et al. 2009). This is
because when a small amount of NaBH4 is used, the
boron hydroxide being produced through hydrolysis of
borohydride (Eq. 3) tends to be adsorbed onto the
surfaces of Ag nanoparticles (Song et al. 2009; Liu
et al. 2007; Davis et al. 1962). This reduces the
electron density of surfaces and causes profound
aggregation of Ag nanoparticles. Excess amount of
Fig. 2 Analysis of Ag salt precursors reported in Ag nanopar- NaBH4 may produce a thick layer of BH4-, which
ticles synthesis (Tolaymat et al. 2010) serves as an electrostatic barrier and prevents the

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formation of boron hydroxide on the surface that utilized AgNO3 and poly(vinylpyrrolidone) (PVP) as
resulting in well dispersion of Ag nanoparticles (Song precursor and stabilizer, respectively. The aqueous
et al. 2009; Liu et al. 2007). In fact, the aggregation AgNO3 solution and PVP were first mixed and stirred;
and dispersion phenomena among Ag nanoparticles the mixture was then heated near to boiling temper-
can be detected with UV–Vis absorption spectra. ature and 1 % sodium citrate was added with vigorous
Figure 3 depicts typical UV–Vis absorption spectra of stirring. The Ag nanoparticles with size between 17
Ag nanoparticles with vary molar ratios of NaBH4/ and 94 nm were obtained, but the product was
AgNO3 (Song et al. 2009). Obviously, a weak plasmon unstable at room temperature (Li et al. 2007). This is
peak centered at 400 nm was observed at low molar a drawback of Turkevich method (Krutyakov et al.
ratio of 0.5. The intensity of the plasmon peak at 2008).
400 nm was later increased with increasing molar Lee and Meisel (1982) had extended the sodium
ratios from 0.5 to 15, which indicates much Ag citrate reduction method to synthesis Ag nanoparti-
nanoparticles were being produced at higher molar cles. In their method (Lee and Meisel 1982), AgNO3
ratio of NaBH4/AgNO3. Moreover, the broad plasmon was dissolved in deionized water and the solution was
peaks obtained at low molar ratios of NaBH4/AgNO3 heated until it was boiling. Then, 1 % sodium citrate
were actually confirming to the aggregation of Ag was added drop by drop into the boiling AgNO3
nanoparticles. Conversely, the narrow plasmon peaks solution, accompanied by a vigorous stirring and
obtained at high molar ratios of NaBH4/AgNO3 were finally Ag nanoparticles were obtained. Lee and
confirming to the well dispersion of Ag nanoparticles. Meisel method has become another prominent method
In conclusion, NaBH4 can serve not only as a reducing in synthesis of Ag nanoparticles and often repeat used
agent but also as a stabilizer, which may protect Ag by many researchers (Tan et al. 2003; Cañamares et al.
nanoparticles from aggregation. 2005; Zhao et al. 2006c; Sileikaite et al. 2006;
Sodium citrate, also known as trisodium citrate Ratyakshi and Chauhan 2009). Of them, Ratyakshi
(Na3C6H5O7), is another widely used reducing agent and Chauhan (2009) have successfully produced Ag
in synthesis of Ag nanoparticles. In 1951, sodium nanoparticles with 10–20-nm size. Overall, the reac-
citrate was first used by Turkevich et al. (1951) in the tion of Ag salts and sodium citrate is shown in Eq. (4)
synthesis of Au nanoparticles. However, their method (Ratyakshi and Chauhan 2009; Sileikaite et al. 2006;
was then adapted and refined to work on synthesis of Mulfinger et al. 2007). Moreover, several other works
Ag nanoparticles as reported by Li et al. (2007) and also did mention about the use of sodium citrate as
Dong et al. (2009). The authors (Li et al. 2007) had reducing agent in Ag nanoparticles synthesis (Wang
et al. 2008; Naik et al. 2010; Medina-Ramirez et al.
2009; Guzmán et al. 2009; Khanna et al. 2007b).
4Agþ þ C6 H5 O7 Na3 þ 2H2 O
! 4Ag0 þ C6 H5 O7 H3 þ 3Naþ þ Hþ þ O2 " ð4Þ
Hydrazine (N2H4) is another interesting reducing
agent being used for the reduction of Ag salts.
However, hydrazine hydrate is more frequently being
in used as reported by Guzmán et al. (2009), Nersisyan
et al. (2003), Szczepanowicz et al. (2010), and Khan
et al. (2009). In their works, AgNO3 and sodium
dodecyl sulfate (SDS) were used as Ag salt and
stabilizer, respectively. They managed to synthesis
spherical Ag nanoparticles, but the size distribution
was wide from 8 to 120 nm (Nersisyan et al. 2003;
Szczepanowicz et al. 2010; Khan et al. 2009; Guzmán
Fig. 3 Typical UV–Vis absorption spectra of the Ag nanopar-
ticles with vary molar ratios of NaBH4/AgNO3 (Song et al. et al. 2009). Furthermore, hydrazine hydrate was also
2009) incorporated as the reducing agent in the works

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reported by Zhang et al. (1996, 2011a), Khanna et al. (2010), Suber et al. (2005) reported the similar use of
(2005), and Patil et al. (2012), but different Ag salts ascorbic acid to reduce AgNO3 solution in the presence
and stabilizers were used by them. Patil et al. (2012) of sodium naphthalene sulfonate-formaldehyde
noted the use of hydrazine hydrate for AgCl reduction copolymer (Daxad 19) as stabilizing agent. These
in the presence of polyvinyl alcohol (PVA) as the authors suggested two common findings. First, ascor-
stabilizer. Ammonia also utilized by them to maintain bic acid is a powerful reducing agent in acidic solutions
the pH of solution between 8 and 9, finally spherical because of its ability to completely convert Ag ions
Ag nanoparticles with size of 10–60 nm was obtained into metallic Ag according to Eq. (6) (Sondi et al. 2003;
and the particles with surface plasmon resonance Suber and Plunkett 2010; Suber et al. 2005). Second,
absorption peak at 410 nm were recorded (Fig. 4) Daxad 19 is effective not only in preventing dissolution
(Patil et al. 2012). of fresh formed Ag nanoparticles, but it is also having
Hydrazine dihydrochloride is another hydrazine excellent ability to prevent aggregation of Ag nano-
that had been used in synthesis of Ag nanoparticles. particles in a highly acidic aqueous solutions (Sondi
Nickel et al. (2000) employed hydrazine dihydrochlo- et al. 2003; Suber and Plunkett 2010; Suber et al. 2005).
ride in weak alkaline solution for AgNO3 reduction
2Agþ þ C6 H8 O6 ! 2Ag0 þ C6 H6 O6 þ 2Hþ ð6Þ
without adding any stabilizer. They (Nickel et al.
2000) managed to produce spherical particles with Besides, Suber et al. (2005) also noted an interesting
size ranging between 40 and 70 nm and stable for finding. By varying addition rate of reducing agent and
many months. Equation (5) shows the overall reaction concentration of Ag salt, different morphologies of Ag
of Ag salts reduction with hydrazine (Nickel et al. particles could be produced. In first condition, 0.5–2.0-
2000). lm spherical Ag particles (Fig. 5a) were obtained by
adding ascorbic acid at flow rate of 1.5 cm3 min-1 into
4Agþ þ N2 H4 ! 4Ag0 þ N2 þ 4Hþ ð5Þ
mixture solution of AgNO3, Daxad 19 and HNO3.
In addition, Zielińska et al. (2009), Maillard et al. Additionally, by using the same condition above but
(2002, 2003), and Seo et al. (2004) have also reported increasing the concentration of AgNO3, size of Ag
the use of hydrazine as reducing agent in their nanoparticles approximately 100 nm was obtained
respective works in Ag nanoparticles synthesis. These (Fig. 5b). Again, the first condition was maintained
authors believed that the size of Ag nanoparticles and then ascorbic acid was added at a flow rate of
synthesis was strongly dependent on the concentration 0.5 cm3 min-1 for first 5 min, following by slow down
of Ag salts and hydrazine being used. They manage to the flow rate to 0.3 cm3 min-1. Hence, the hexagonal
create a wide size range of Ag nanoparticles by Ag nanoparticles (Fig. 5c) were finally formed with
controlling these two parameters. These findings were continuous stirring for another 1 h after completed
also agreed by aforementioned works. addition of ascorbic acid. Furthermore, the use of
Ascorbic acid (C6H8O6) is another choice of ascorbic acid in Ag salts reduction has also reported in
reducing agent. Sondi et al. (2003), Suber and Plunkett other six research works (Yang et al. 2005; Shon and

Fig. 4 a Transmission
electron micrograph of Ag
nanoparticles. b UV–Vis
spectra of Ag nanoparticles
(Patil et al. 2012)

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Fig. 5 Scanning electron micrographs of Ag particles prepared under different conditions (Suber et al. 2005)

Cutler 2004; Al-Thabaiti et al. 2008; Szczepanowicz nanoparticles can be obtained easily in final product
et al. 2010; Qin et al. 2010; Chen et al. 2007). Of these, without any contamination. Khanna and Subbarao
Chen et al. (2007) noted that ascorbic acid is a weak (2003) first reported formaldehyde can be incorporated
reducing agent if compared with sodium borohydride with sodium formaldehydesulfoxylate (SFS) as reduc-
and hydrazine, and therefore much larger size of Ag ing agents for Ag nanoparticles synthesis, but acidic pH
nanoparticles would produce. The explanation could is preferable. The mechanism involves the addition of
be related to the kinetic rate theories that being formaldehyde into AgNO3 solution to produce formate
described in previous section. Weak reducing agent ions and hydride. The formate ions will then combine
is having a low nucleation rate and thus low concen- with the released sodium ions from SFS and sodium
trations of nuclei were generated. Finally, larger Ag formate were formed. The sodium formate will next
nanoparticles were formed. react with Ag ions from AgNO3 and finally metallic Ag
Formaldehyde (HCOH) is another reported reducing was formed. In this method, Ag nanoparticles with
agent and it was studied by Nersisyan et al. (2003), Chou diameter ranging from 100 to 200 nm were yielded and
and Ren (2000), Chou et al. (2005), Yu et al. (2010), Hsu formaldehyde is confirmed to play a role in precipitating
and Wu (2010). These authors found that reducing finer particles (Khanna and Subbarao 2003).
ability of formaldehyde is a function of pH. They Poly(ethylene glycol) (PEG) (Chen and Huang
explained formaldehyde has higher reducing power at 2002; Yan et al. 2006; Lah and Johan 2009; Luo et al.
higher pH and therefore alkaline solutions or basic 2005; Lah and Johan 2011), glycerol (Ullah et al.
catalysts are usually added during the reduction of Ag 2006), and ethanol (Frattini et al. 2005; Kim 2007; Pal
salts. Conversely, if only formaldehyde is used, the et al. 2009; Ayyappan et al. 1997) are reported alcohol
reduction rate of Ag salts would be too slow due to low based reducing agents in the synthesis of Ag nano-
pH. Hsu and Wu (2010) reported that reduction of particles. According to Luo et al. (2005) work, AgNO3
AgNO3 solution with formaldehyde in the presence of a was dissolved in PEG at 80 °C with continuous
stabilizer, either poly(N-vinyl-2-pyrrolidone) (PVP), stirring for 1 h, and next Ag nanoparticles with size of
thiosaliclic acid (TSA), or triethylamine (TEA) was 10 nm were formed. They (Luo et al. 2005) further
used. The triethylamine or pyridine that served as increased the reactant temperature from 80 to 100 °C
organic base catalyst was then added drop wise to the and 120 °C, the average particles size also follow
mixture solution, and the color of the solution turned enlargement from 10 to 20 nm and 80 nm, respec-
from clear to black. As a result, they had prepared stable tively. Moreover, the shapes of Ag nanoparticles also
Ag nanoparticles with average diameter of 15, 7.99, and demonstrated a change from spherical at 80 and
2.74 nm when PVP, TSA, and TEA were used, 100 °C to polygonal at 120 °C (Luo et al. 2005). These
respectively. The authors (Hsu and Wu 2010) also results indicate the reaction temperature plays a key
mentioned that triethylamine or pyridine as organic base role to determine the size and shape of the particles
catalyst are easily washed out after reaction and pure Ag being formed. Lah and Johan (2011) have a common

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finding with Luo et al. (2005). Lah and Johan (2011) Ag salts, reducing agents, stabilizers, and particle sizes
employed a method similar to Luo et al. (2005) except that had been reported in synthesis of Ag nanoparticles
stabilizer Daxad 19 was added. Lah and Johan (2011) via chemical reduction route.
noted the average particle sizes were increased from
4.5 to 7.5 nm and 56 nm, when temperatures were Stabilizers and surfactants
raised from 80 to 100 °C and 120 °C, respectively.
Compare these two works; obviously addition of Stabilizer, also known as capping agent, is a chemical
stabilizer Daxad 19 is very effective to produce agent used in the synthesis process to prevent nano-
smaller size nanoparticles. particles from aggregation and to control the size of
On the other hand, Ayyappan et al. (1997) reported the particles being formed. The aggregation is mainly
the synthesis of Ag nanoparticles using ethanol and caused by high surface energy and thermodynamic
PVP as reducing agent and stabilizer, respectively. instability of the nanoparticle surfaces. Therefore,
They started with AgNO3 in ethanol and employed stabilizer serves as a barrier, is needed to cover the
AgNO3:PVP weight ratios of 1:5 and 1:10. The nanoparticle surfaces and avoid excessive reactions
mixture solution was heated to 87 °C under stirring between nanoparticle surfaces as well as between
for 12 h and finally Ag nanoparticles were obtained. chemicals and nanoparticle surfaces. In addition,
The Ag nanoparticles obtained is having an average surfactant is another chemical agent used to prevent
size of 13 and 5 nm for AgNO3: PVP ratios of 1:5 and aggregation of nanoparticles. It also helps to lower the
1:10, respectively. This result shows that ethanol is surface tension in a suspension and make the particles
also a suitable reagent for Ag salts reduction and by easy to disperse within it. Sometimes, surfactant can
tailoring the PVP amount is having an obvious effect also be considered as stabilizer.
on particle sizes. Steric stabilization is a good mechanism to explain
Other reported reducing agents include amines and the role of stabilizer on nanoparticles in against of
amino acid (Khan et al. 2011; Yang et al. 2011; Rao aggregation (Shi 2002; Dobbie et al. 1973; Pomogailo
and Trivedi 2005, 2006; Zhang et al. 2008; Ma et al. and Kestelman 2005). The steric stabilization is
2005; Selvakannan et al. 2004), tannic acid (Dadosh achieved by attaching macromolecules of stabilizer
2009; Bulut and Özacar 2009), gallic acid (Martinez- to the nanoparticle surface through physical-grafting
Castanon et al. 2008), ammonia (Sun et al. 2003), or chemisorptions (Shi 2002; Dobbie et al. 1973;
dimethyl sulfoxide (Rodrı́guez-Gattorno et al. 2002; Pomogailo and Kestelman 2005). The macromolecule
Patakfalvi et al. 2008), and saccharide (Nersisyan et al. of stabilizer consists of a combination of functional
2003; Janardhanan et al. 2009; Wang et al. 2005; Lu groups and long hydrocarbon chains. Whereby, the
and Chou 2008; Yu 2007; Panáček et al. 2006; Chou functional groups, such as carboxyl, hydroxyl, amine,
et al. 2005; Xia et al. 2011). Saccharide-based and ester, serve to interact with the nanoparticle
reducing agents are environmental friendly substances surface and consequently anchor entire macromole-
and therefore green synthesis term is always used to cule on it (Shi 2002; Dobbie et al. 1973; Pomogailo
relate with it. Among the saccaride-based reducing and Kestelman 2005). Besides, the long hydrocarbon
agents, glucose is more often to be used for Ag chains in the macromolecule could extend from the
nanoparticles synthesis. Nersisyan et al. (2003) and nanoparticle surface into solvent and act as stabilizing
Wang et al. (2005) have reported a similar method to moieties. These stabilizing moieties provide mutually
produce Ag nanoparticles using AgNO3, NaOH, and repulsive between nanoparticles and effectively keep
glucose as precursor, catalyst, and reducing agent, the nanoparticles at a distance from each other, as
respectively. However, two different stabilizers were shown in Fig. 6 (Shi 2002). Usually, long hydrocarbon
utilized by them. Nersisyan et al. (2003) and Wang chains could impart better stabilization effect on
et al. (2005) were, respectively, utilized SDS and PVP nanoparticles in against of aggregation. From preced-
as stabilizer, and both works also successfully pro- ing review, variety stabilizers have reported used in
duced spherical Ag nanoparticles. Nevertheless, Ner- Ag nanoparticle synthesis. However, based on their
sisyan et al. (2003) have obtained smaller size particles characteristics and functional groups, these stabilizers
(10–50 nm) compared with Wang et al. (2005) can be classified into seven groups, name as polymer,
(20–80 nm). Table 1 summarizes all combination of acid, amine, bromide, ligand, alcohol, and silicate

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Table 1 Summary combination of Ag salts, reducing agents, stabilizers, surfactants, and particle sizes been reported in Ag nano-
particles synthesis via chemical reduction route
Ag salt precursor Reducing agent Stabilizer/surfactant Reported size

Silver nitrate Sodium borohydride – 1–50 nm (Creighton et al. 1979)


20–180 nm (Vorobyova et al. 1999)
SDS 30–40 nm (Song et al. 2009)
Laponite \10 nm (Liu et al. 2007)
Mercaptoacetic acid 17 nm (Li et al. 2003)
Mercaptosulfonic acid 8 nm (Zhao et al. 2006a, b)
Alkanethiolate 2–5 nm (Shon and Cutler 2004)
Poly(styrene sulfonate-co-maleic) – (Limsavarn et al. 2007)
Peptide 5.8–20.8 nm (Doty et al. 2005)
Thioalkylated poly-(ethylene glycol) 4.3–6.3 nm (Doty et al. 2005)
Mercaptoethanesulfonate 3.2–3.8 nm (Zou et al. 2006)
Gum arabic 2.5–4.3 nm (Medina-Ramirez et al.
2009)
Poly(N-isopropylacrylamide) 8–11 nm (Liu et al. 2012b)
Sodium citrate 4.6–5.0 nm (Pinto et al. 2010)
Pluronic F127 8–16 nm (Angelescu et al. 2012)
Sulfonatedpolyaniline 2–4 nm (Krutyakov et al. 2010)
Sodium citrate – 56–71 nm (Dong et al. 2009)
35–100 nm (Tan et al. 2003)
60 nm (Zhao et al. 2006c)
100 nm (Sileikaite et al. 2006)
10–20 nm (Ratyakshi and Chauhan 2009)
PVP 17–94 nm (Li et al. 2007)
Gum arabic 10.0–31.6 nm (Medina-Ramirez
et al. 2009)
SDS ? isopentanol 2–11 nm (Wang et al. 2008)
Hydrazine
(i) Hydrazine hydrate SDS 8–50 nm (Guzmán et al. 2009),
60–120 nm (Nersisyan et al. 2003),
\20 nm (Szczepanowicz et al. 2010)
Cetyltrimethylammonium bromide (CTAB) 15 nm (Khan et al. 2009)
Triton X-100 (Khan et al. 2009) –
Tetra-n-butylammonium 3 nm (Zhang et al. 2011a)
bromide (TBAB) ? 1-dodecanethiol
PVA 20 nm (Khanna et al. 2005)
PVP 50–100 nm (Zhang et al. 1996)
Tween20 50 nm (Seo et al. 2004)
(ii) Hydrazine dihydro-chloride – 40–70 nm (Nickel et al. 2000)
Ascorbic acid Daxad 19 14–42 nm (Sondi et al. 2003),
20–100 nm (Suber et al. 2005)
SDS 10 nm (Al-Thabaiti et al. 2008)
CTAB 50 nm (Al-Thabaiti et al. 2008)
Sodium citrate 31–73 nm (Qin et al. 2010)
Oleylamine 5–21 nm (Chen et al. 2007)

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Table 1 continued
Ag salt precursor Reducing agent Stabilizer/surfactant Reported size

Formaldehyde SDS 10–20 nm (Nersisyan et al. 2003)


PVP 7–20 nm (Chou and Ren 2000),
15 nm (Hsu and Wu 2010)
PVA 7–20 nm (Chou and Ren 2000)
CTAB 30 nm (Yu and Zhang 2010)
TSA 7.99 nm (Hsu and Wu 2010)
TEA 2.74 nm (Hsu and Wu 2010)
Alcohol
(i) PEG – 3.8–9.0 nm (Chen and Huang 2002),
8–10 nm (Yan et al. 2006),
10–80 nm (Luo et al. 2005)
Daxad 19 4.5–56 nm (Lah and Johan 2009;
Lah and Johan 2011)
(ii) Glycerol m-Phenylenediamine (m-PDA) 153 nm (Ullah et al. 2006)
(iii) Ethanol Aminosilane 3–8 nm (Frattini et al. 2005)
PVP 4–9 nm (Kim 2007),
5–15 nm (Pal et al. 2009),
5–13 nm (Ayyappan et al. 1997)
Amine
(i) Aniline CTAB 10–30 nm (Khan et al. 2011)
Dodecylbenzenesulfonic acid 7.8–10.0 nm (Yang et al. 2011)
(DBSA)
(ii) Hydroxy-lamine hydro- Ethylenediaminetetraacetic acid 50–100 nm (Lundahl et al. 2008)
chloride (EDTA)
(iii) Triethanol amine Stearic acid 24 nm (Rao and Trivedi 2005, 2006)
(iv) Hyper-branched poly- – 4.5–14.3 nm (Zhang et al. 2008)
(amidoamine)
(v) Amino dextran – –(Ma et al. 2005)
(vi) Amino acid tyrosine – 1–10 nm (Selvakannan et al. 2004)
Tannic acid – 18–30 nm (Dadosh 2009)
Gallic acid – 7–89 nm (Martinez-Castanon et al. 2008)
Ammonia Pyridinium di-n- 20 nm (Sun et al. 2003)
hexaoctyldithiophosphate
(PyDDP)
N,N0 -dimethyl-formamide b-cyclodextrin 7.2 nm (Patakfalvi et al. 2008)
Cholic acid 3.7 nm (Patakfalvi et al. 2008)
Saccharides
(i) Glucose – 40–80 nm (Janardhanan et al. 2009),
44–53 nm (Panáček et al. 2006)
SDS 10–50 nm (Nersisyan et al. 2003)
PVP 20–80 nm (Wang et al. 2005)
(ii) Dextrose PVP 22 nm (Lu and Chou 2008)
Poly(c-glutamic acid) (PGA) 15–60 nm (Yu 2007)
(iii) Galactose – 50–343 nm (Panáček et al. 2006)
(iv) Maltose – 25–262 nm (Panáček et al. 2006)
(v) Lactose – 35–286 nm (Panáček et al. 2006)
(vi) Hyaluronan – 7–40 nm (Xia et al. 2011)
Silver perchlorate Sodium borohydride – 6–12 nm (Van Hyning and Zukoski 1998; Van
Hyning et al. 2001a),
5–30 nm (Van Hyning et al. 2001b)

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Table 1 continued
Ag salt precursor Reducing agent Stabilizer/surfactant Reported size

Silver chloride Hydrazine PVA 10–60 nm (Patil et al. 2012)


Silver citrate Sodium borohydride – 140 nm (Zielińska et al. 2009)
Hydrazine PVP 67 nm (Zielińska et al. 2009)
PVA 48 nm (Zielińska et al. 2009)
Ascorbic acid PVP 36–82 nm (Zielińska et al. 2009)
PVA 44–45 nm (Zielińska et al. 2009)
Silver di(2-ethylhexyl) Hydrazine Dodecanethiol 30–100 nm (Maillard et al. 2002, 2003)
sulfosucci-nate
Silver 2-ethylhexanoate Dimethyl sulfoxide Sodium citrate 4.4 nm (Rodrı́guez-Gattorno et al. 2002;
Patakfalvi et al. 2008)

(Table 2). Typically, polymer is the most used stabi- the inter-diffusion between nanoparticles, as well as
lizer if compared to others, but this argument is too between nanoparticle and suspension; therefore, it is
general because not all polymeric stabilizers listed in very effective against agglomeration. Kim (2007), Chou
Table 2 are often in used. This section therefore aims and Ren (2000) further commented that increasing the
to specific review on the most frequent used stabilizers PVP concentration tends to produce smaller Ag parti-
in Ag nanoparticles synthesis. cles, but appropriate amount should be added. It is
Based on Table 1, SDS (Song et al. 2009; Szczepa- because too much PVP will slow down the reduction
nowicz et al. 2010; Guzmán et al. 2009; Al-Thabaiti rate of Ag ion into Ag atom, and thus not suitable for
et al. 2008; Nersisyan et al. 2003), PVP (Lu and Chou practical uses (Chou and Ren 2000). In addition, the
2008; Zhang et al. 1996; Kim 2007; Chou and Ren 2000; preceding explanation about protective barrier also
Pal et al. 2009; Wang et al. 2005), and PVA (Chou and applicable for PVA case (Patil et al. 2012; Zielińska
Ren 2000; Patil et al. 2012; Zielińska et al. 2009; et al. 2009; Khanna et al. 2005; Chou and Ren 2000),
Khanna et al. 2005) are the most used stabilizers and but increasing the concentration of PVA does not lead to
surfactants in synthesis of Ag nanoparticles. Song et al. the reduction of Ag nanoparticle size (Patil et al. 2012).
(2009), Szczepanowicz et al. (2010), and Al-Thabaiti Therefore, PVA only serves for preventing Ag nano-
et al. (2008) used SDS as stabilizer. They found the size particles from agglomerate. Furthermore, Chou and Ren
and stability of the particles can be controlled by varying (2000) did a comparison between PVP and PVA; they
the concentration of SDS being added during the found PVP is somewhat better than PVA for protecting
synthesis process. Song et al. (2009) reported that as Ag particles from agglomeration.
the SDS concentration increased relative to AgNO3, a In addition, cetyltrimethylammonium bromide
narrow surface plasmon absorption peaks at 400 nm (CTAB) (Khan et al. 2009; Al-Thabaiti et al. 2008;
was observed, confirming the formation of Ag nano- Yu and Zhang 2010; Ghosh and Kolay 2008), tetra-n-
particles were in a well disperse state. Conversely, when butylammonium bromide (TBAB) (Zhang et al.
low concentration of SDS was used, the absorption
peaks became broad, indicating that Ag nanoparticles
were aggregated (Song et al. 2009).
Zhang et al. (1996), Lu and Chou (2008), and Kim
(2007) on the other hand reported the use of PVP as
stabilizer in their synthesis works. They found that PVP
not only uses for stabilizing Ag nanoparticles but also
plays an important role in controlling the size and shape
of Ag nanoparticles. Zhang et al. (1996), Lu and Chou
(2008) pointed out that PVP will be absorbed onto Ag
Fig. 6 The schematic of steric stabilization (enlarge is illus-
surface during synthesis and then provides a protective
tration small portion of stabilizer macromolecule anchor to the
barrier for the particle. This protection barrier can inhibit nanoparticle surface) (Shi 2002)

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Table 2 Classification of stabilizers


Group Stabilizer/surfactant

Polymer SDS, PVP, PVA, Daxad 19, poly(styrene sulfonate-co-maleic), peptide, poly(N-isopropylacrylamide), Pluronic F127,
sulfonated polyaniline, Triton X-100, Tween 20, pyridinium di-n-hexaoctyldithiophosphate, b-cyclodextrin
Acid Mercaptoacetic acid, mercaptosulfonic acid, sodium citrate, TSA, TEA, dodecylbenzenesulfonic acid,
ethylenediaminetetraacetic acid, stearic acid, cholic acid, poly(c-glutamic acid)
Amine Oleylamine, m-Phenylenediamine, aminosilane,
Bromide CTAB, DTAB, TTAB, TBAB
Ligand Alkanethiolate, thioalkylated poly-(ethylene glycol), mercaptoethane sulfonate
Alcohol/ Isopentanol, 1-dodecanethiol
thiol
Silicate Laponite

2011a), dodecyltrimethylammonium bromide excellent long-term stabilizer even though it is com-


(DTAB) (Ghosh and Kolay 2008), and tetradecyltri- monly used as reducing agent. The reason is because
methylammonium bromide (TTAB) (Ghosh and Ko- Ag nanoparticles capped with sodium citrate have
lay 2008) were also used as stabilizers and surfactants. demonstrated an outstanding stability, as they can
Among these, CTAB is most favorably used in Ag remain stable more than 6 months (Rodrı́guez-Gat-
nanoparticles synthesis. Yu and Zhang (2010) have torno et al. 2002; Patakfalvi et al. 2008), and ultimately
studied the effect of CTAB amounts on the morphol- stable up to 1 year if Ag nanoparticles were stored in
ogy of Ag nanoparticles. They (Yu and Zhang 2010) dark conditions (Pinto et al. 2010). Nevertheless, in Ag
found that when small quantity of CTAB was added, nanoparticles synthesis, sodium citrate is more favor-
particles with large size, irregular shape, and signif- ably used as both reducing agent and stabilizer instead
icant agglomeration were obtained. Nevertheless, with of stabilizer only. Zhang et al. (2011a) reported use of
increasing the amount of CTAB being added, the 1-dodecanethiol as stabilizer in their synthesis work.
particles showed a reduction in size with better They (Zhang et al. 2011a) had performed EDS
dispersion. They (Yu and Zhang 2010) further pointed quantitative analysis on 1-dodecannethiol capped Ag
out that excessive amount of CTAB could wrap the nanoparticles at different reaction time as shown in
surrounding of particles well and then prevent the Table 3. The sulfur content is gradually increased with
growth; therefore, tiny particles of a few nanometers longer reaction time. The authors (Zhang et al. 2011a)
in size can be yielded. This finding is also agreed by noted that the increment of sulfur content indicates that
Ghosh and Kolay (2008), they viewed CTAB is an Ag nanoparticles were gradually caped by the 1-dode-
excellent stabilizer to cap Ag nanoparticles. canethiol. They also found that nanoparticles have a
Daxad 19 (Sondi et al. 2003; Suber et al. 2005; better arrayed order with more 1-dodecanethiol
Suber and Plunkett 2010; Lah and Johan 2011), capped onto Ag nanoparticle surfaces.
sodium citrate (Rodrı́guez-Gattorno et al. 2002; As shown in Tables 1 and 2, other reported
Patakfalvi et al. 2008; Pinto et al. 2010; Qin et al. stabilizers and surfactants include laponite, mercap-
2010), and thiols (Maillard et al. 2002, 2003; Zhang toacetic acid, peptide, mercaptoethane sulfonate, gum
et al. 2011a) are another reported stabilizers and
surfactants. Daxad 19 is a copolymer display excellent
ability to prevent aggregation of Ag nanoparticles in Table 3 The components of silver and sulfur at different
reaction time (Zhang et al. 2011a)
highly acidic conditions (Sondi et al. 2003; Suber et al.
2005; Suber and Plunkett 2010). In addition, a Reaction time (h) Silver (wt %) Sulfur (wt %)
reduction in particle size can also be observed with 3 91.11 8.89
increasing of Daxad 19 concentration, as slightly blue-
5 86.59 13.41
shift and narrow absorption peaks can be observed in
8 79.27 20.73
surface plasmon resonance (Lah and Johan 2011). On
12 76.56 23.44
the other hand, sodium citrate can be known as an

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arabic, poly(N-isopropylacrylamide), Pluronic F127, reduce AgNO3 and Ag2SO4, respectively. Alkaline
Tween20, and others. But, this literature work shows conditions with pH value from 10.0 to 10.5 were
most of them were only reported once, therefore, utilized and 1–30 nm Ag nanoparticles were success-
further research works should be carry out to prove fully synthesized (Khan et al. 2011). Selvakannan
their effectiveness as stabilizer and surfactant. et al. (2004) further pointed out that reducing ability of
amino acid tyrosine occurred only at alkaline pH.
Effect of pH on Ag nanoparticles synthesis Other works that employed glucose (Wang et al. 2005)
and dextrose (Lu and Chou 2008) as reducing agents
In chemical reduction, the pH of reaction solution also found favored reduction of AgNO3 in alkaline pH
could affect the size and shape of the final Ag conditions. Even though aforementioned works have
nanoparticles being formed. Dong et al. (2009) have shown Ag nanoparticles syntheses are more favored in
performed a study on Ag nanoparticles synthesis by alkaline pH, but it could not apply for all combination
sodium citrate reduction of AgNO3 from pH 5.7 to of reducing agents and Ag salts. This is because when
11.1. They found that under high pH, both spherical NaBH4, hydrazine, and ascorbic acid were used as
and rod-like Ag nanoparticles were formed as a result reducing agents, they showed reducing ability were
of fast reduction rate of the precursor. In contrast, independent of pH.
triangle and polygon Ag nanoparticles were domi-
nated under low pH due to a slow reduction rate of the Effect of temperature on Ag nanoparticles
precursor. The average particle size also increased synthesis
from 30 to 96 nm when the pH was decreased from
11.1 to 5.7, consistent with the red-shift of the UV– In Ag nanoparticles synthesis, temperature is playing a
Visible absorption peaks (Fig. 7) (Dong et al. 2009). role to speed up the synthesis process. However, it is
Their finding was also supported by other research difficult to summarize all temperatures employed in
works, where higher pH is more favored for Ag Ag nanoparticles synthesis due to wide range of
nanoparticles synthesis. Chou and Ren (2000) used temperatures being employed in numerous research
formaldehyde to reduce AgNO3 and found the reduction works. Sometimes, repeated heating for two or three
rate would be too slow due to a low pH. Thus, different times during synthesis were employed by researchers
quantities of NaOH and/or Na2CO3 were added to raise and these are the challenging parts to summarize.
the pH of the solution stayed above 7. As a result, Therefore, we decided to explore the effect of
99.7 % of AgNO3 manage to be reduced to Ag atoms temperature on particle size and shape.
and growth into nanoparticles after 60 min of reaction Yu and Zhang (2010) did a study on effect of
(Chou and Ren 2000). Khanna and Subbarao (2003) also temperature on morphologies of Ag nanoparticles.
noted a similar finding in their work, but they only Three reaction temperatures were utilized in their
success to reduce 95 % of AgNO3 to Ag nanoparticles. work, which were 20, 40, and 60 °C. They (Yu and
In addition, Khan et al. (2011) and Selvakannan Zhang 2010) found that when the reaction temperature
et al. (2004) used of aniline and amino acid tyrosine to was increased, the particles became smaller in size and

Fig. 7 a Transmission
electron micrographs for the
Ag nanoparticles synthesis
at different pH conditions.
b UV–Visible spectra for Ag
nanoparticles synthesis at
different pH conditions
(Dong et al. 2009)

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more uniform in shape. As shown in Fig. 8, large and CuO rather than metal Cu. Hence, literature works on
non-uniform nanoparticles were formed at 20 °C. the synthesis of Cu nanoparticles via chemical reduc-
Next, when the temperatures were increased to 40 and tion route are lesser if compared with Ag nanoparti-
60 °C, the particles formed were in flaky and spherical cles. Similar to previous Ag nanoparticles synthesis,
shapes, respectively. Also, Fig. 8 shows obvious reducing agents and stabilizers employed in Cu
decrease in particles size with increasing in the nanoparticles synthesis via chemical reduction route
reaction temperatures. The authors (Yu and Zhang will be systematically review and summarize.
2010) also pointed out the reducing ability of form- Sodium borohydride (NaBH4) again is the most
aldehyde and capabilities of CTAB to impede the frequent used reducing agent in Cu salts reduction.
growth of particles were very weak at low temperature Zhang et al. (2009) and Hashemipour et al. (2011)
and thus lead to the formation of larger size particles. reported the similar use of NaBH4 to reduce copper
Nevertheless, Luo et al. (2005), Lah and Johan sulfate (CuSO4) solution in the presence of PVP and
(2011) have opposite finding compare to Yu and purge of nitrogen. The major different between their
Zhang (2010). They utilized PEG as reducing agent for works was the solvent being employed during synthe-
AgNO3 reduction. The results (Luo et al. 2005; Lah sis, where ethylene glycol and distilled water were,
and Johan 2011) showed that Ag nanoparticle sizes respectively, used by Zhang et al. (2009) and
were increased, when temperatures were raised from Hashemipour et al. (2011). At the end, finer Cu
80 to 120 °C. With the same increment in temperature, nanoparticles were produced with ethylene glycol
the nanoparticle shapes also growth from spherical to solvent if compared with distilled water solvent
polygonal. From the preceding literature works, we because ethylene glycol has a better ability to prevent
could conclude that temperature effect is depending on the oxidation and aggregation of the nanoparticles
reducing agents. No one temperature could apply for (Hashemipour et al. 2011; Zhang et al. 2009).
all Ag nanoparticles synthesis process, because dif- Liu et al. (2012a) has performed a study on the effect
ferent combination of reducing agents and Ag salts of NaBH4 concentration on the formation of Cu
will show different reducing ability with temperature nanoparticles. In the work, CuSO4 and gelatin were
and finally yielding different size and shape of Ag used as Cu salt precursor and dispersant, respectively.
nanoparticles. The average size of Cu nanoparticles was decreases
with the increase of NaBH4 concentration, but stoichi-
ometric ratio of Cu2? ions to NaBH4 must maintained
Synthesis of Cu nanoparticles via chemical at least 4:1 according to Eq. (7) (Liu et al. 2012a).
reduction 
4Cu2þ þBH 
4 þ8OH !4CuþBðOHÞ4 þ4H2 O ð7Þ
In contrast to preceding Ag nanoparticles synthesis, The authors (Liu et al. 2012a) noted at low concen-
synthesis of Cu nanoparticles is much challenging tration of NaBH4, the final product contains Cu2O,
because of its fast oxidizing property during synthesis Cu(OH)2 and Cu nanoparticles. If compared to a
process and lead to formation of Cu2O, Cu(OH)2 and higher NaBH4 concentration, Cu(OH)2 contaminant

Fig. 8 TEM images of Ag nanoparticles formed at different temperatures: a 20 °C, b 40 °C, and c 60 °C (Yu and Zhang 2010)

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J Nanopart Res (2013) 15:1537 Page 15 of 29

disappears, but Cu2O contaminant disappears only as Cu salts to form Cu particles with size of 80–130 nm
when the NaBH4 concentration reaches 8 times of the and 23–30 nm. There are also other works using
stoichiometric value. Since NaBH4 is the most used hydrazine to produce Cu nanoparticles (Liu et al. 2006;
reducing agent, there are plenty of other works have Ren et al. 2005; Khanna et al. 2007a). But so far,
also been reported (Song et al. 2004; Chang et al. hydrazine is likely used to reduce CuCl2, even though it
2011; Dadgostar et al. 2010; Jin et al. 2008; Abdulla- is also used to reduce Cu(CH3COO)2 and Cu(NO3)2.
Al-Mamun et al. 2009; Solanki et al. 2010; Chen et al. Sodium hypophosphite (NaH2PO2), although is not
2006). In addition to sodium borohydride, potassium a favorite reducing agent used in Ag salts reduction, is
borohydride and sodium cyanoborohydride are widely used in Cu salts reduction. This reducing agent
another two borohydride based reducing agents. But, is favor used to reduce CuSO4 solution as being
these two reducing agents are seldom in used, as only reported in six research works (Yu et al. 2010; Zhu
few articles have reported the used (Cheng et al. 2011; et al. 2004a, b; Park et al. 2007; Tang et al. 2010). Of
Zhang et al. 2010; Ohde et al. 2001). these, ethylene glycol and diethylene glycol were the
Hydrazine (N2H4) is another excellent reducing most used solvents, in which it is often termed as
agent that widely used in Cu nanoparticles synthesis. modified polyol process. For the case of ethylene
It is usually used to reduce CuCl2 solution incorporated glycol as the solvent, Yu et al. (2010), Zhu et al.
with stabilizer CTAB as reported in Pham et al. (2011), (2004a), and Zhu et al. (2004b) have successful
Wu and Chen (2004), and Kobayashi et al. (2011, 2012) synthesized Cu nanoparticles with size of 5–10 nm,
works. According to Kobayashi et al. (2011), hydrazine 30–80 nm, and 30–70 nm, respectively. Next for the
solution was added to CuCl2 solution that containing case of diethylene glycol as the solvent, Park et al.
citric acid and CTAB under vigorous stirring condition (2007) and Tang et al. (2010), respectively, obtained
at room temperature in air. Next, the effect of citric acid Cu nanoparticles in the sizes 37–88 nm and 10–
and hydrazine concentration were studied. They (Ko- 60 nm. There are two similarities also found in their
bayashi et al. 2011) found that by increasing the works: first, the mixture of Cu salt, solvent, and
concentration of citric acid or hydrazine, the Cu stabilizer is required to heat until pre-determined
nanoparticles could yield much smaller in size and less temperatures for reaction to occur. Second, PVP was
Cu2O byproduct. It is because citrate ions can be the common stabilizer being employed. Overall, the
absorbed on the surface of metallic Cu particle, reaction of Cu salts reduction with sodium hypo-
consequently protecting the Cu particle against oxida- phosphite is shown in Eq. (8) (Tang et al. 2010).
tion (Kobayashi et al. 2011). Also, the higher concen-
tration of hydrazine will induced faster reduction rate Cu2þ þ 2H2 PO 
2 þ 2H2 O ! Cu þ 2H2 PO3 þ 2H
þ

and thus finer Cu particle could be formed (Kobayashi þ H2 ð8Þ


et al. 2011, 2012). On the other hand, Kobayashi et al.
(2012) has also employed different Cu salts in the Tang et al. (2010) also noted that the higher the
synthesis of Cu nanoparticles. As a result, Cu nanopar- concentration of reducing agent being added, the more
ticles with quasi-angular shape, but different sizes were the Cu nanoparticles formed, the smaller the particles
formed. The sizes of the particles were 64 ± 16 nm for are. But, this finding is limited up to 3:1 for molar ratio
CuCl2, 55 ± 15 nm for Cu(NO3)2, and 54 ± 15 nm for of reducing agent and Cu salt. Excessive amount of
Cu(CH3COO)2 (Kobayashi et al. 2012). reducing agent being added could result in a very fast
In addition, hydrazine is always used together with the reaction leading to a poor size distribution and
presence of PVP stabilizer, mainly due to PVP has shown agglomeration of Cu nanoparticles.
great ability to stabilize Cu nanoparticles. Particularly Wen et al. (2011) had invented a novel method,
highlighting Pham et al. (2011), Raut et al. (2009), and named as two-step reduction process, to synthesize
Singh et al. (2010) synthesis works, they had utilized spherical Cu nanoparticles. In their method, CuSO4
hydrazine and PVP together with different Cu salts. was first mixed with an appropriate amount of
Pham et al. (2011) have utilized CuCl2 as Cu salt and ethylendiaminetetraacetate (EDTA) in an aqueous
average size of Cu particles being produced was 100 nm. solution. Second, Cu2? ions in the aqueous solution
Raut et al. (2009) and Singh et al. (2010) were, were extracted into oleic acid and the consequent
respectively, employed Cu(CH3COO)2 and Cu(NO3)2 synthesis process was carried out in this organic phase.

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Page 16 of 29 J Nanopart Res (2013) 15:1537

Next, the two-step reduction process can be demon- nanoparticles, except that SDS and PEG-6000 mixture
strated as follows: (1) Cu2? ions were first reduced to has yielded smaller size and narrower size distribution
Cu2O by glucose at 60 °C. (2) An appropriate amount of Cu nanoparticles. On the other hand, Biçer and
of sodium hypophosphite was added to the solution to Şişman (2010) also utilized ascorbic acid to reduce
completely reduce Cu2O to Cu nanoparticles. At the CuSO4, but stabilizer has been change to CTAB and
end, well-dispersed spherical Cu nanoparticles with NaOH was added to control the mixture pH. The
the size ranging between 20 and 40 nm had been authors (Biçer and Şişman 2010) further noted that the
produced (Wen et al. 2011). No stabilizer is needed in reactions which occured were pH dependent as
this method because oleic acid can serve as both expressed in Eqs. (9) to (11).
extractant and surfactant to prevent the Cu nanopar-
AtpH3:0: Cu2þ þC6 H8 O6 !CuþC6 H6 O6 þ2Hþ ð9Þ
ticles from oxidizing and agglomerating. From the
preceding review, we found that all synthesis works 2þ 
At pH 6:5 : Cu þ 2OH ! CuðOHÞ2 ð10Þ
which employed sodium hypophosphite as the reduc-
CuðOHÞ2 þC6 H8 O6 ! Cu þ C6 H6 O6 þ 2H2 O ð11Þ
ing agent can produce Cu nanoparticles at atmosphere
condition. This is an interesting finding as no inert Various nano- to microstructures were obtained in
environment is needed during the synthesis process. their work, including polyhedrons, rods, particles, and
Ascorbic acid (Cheng et al. 2006; Biçer and Şişman wires by adjusting the reaction parameters such as
2010; Yang et al. 2006; Blosi et al. 2011) and sodium reactants concentration, pH, temperature, etc.
formaldehyde sulfoxylate (SFS) (Khanna et al. 2007a, Synthesis of oleic acid capped Cu nanoparticles has
2008) are other reported reducing agents being used in been carried out by Khanna et al. (2008), in which SFS
Cu nanoparticles synthesis. Cheng et al. (2006) has was used to reduce CuCl2 solution. Two different
reported size-controlled synthesis of Cu nanoparticles solvents, either acetone or ethylene glycol, were used
from CuSO4 using sodium dodecyl benzene sulfonate throughout the synthesis process. The result showed
(SDBS), sodium dodecyl sulfate (SDS), Polyethylene that the synthesis in acetone has yielded phase pure Cu
glycols (PEGs), or the mixture of them as surfactants nanoparticles alongside with minor Cu2O impurity.
and ascorbic acid as reducing agent. They found that Even though synthesis in ethylene glycol has yielded a
average particle size and size distribution of the Cu product similar to acetone, large amount of Cu2O
nanoparticles are depending upon the type of surfac- impurity was obtained too. From that, the authors
tants, as presented in Table 4 (Cheng et al. 2006). The believe that oleic acid does not offer effective surface
result also shows that the use of mixed surfactants is capping in ethylene glycol solvent (Khanna et al.
beneficial to produce larger size and broader size 2008). Next, PVA was added to improve the first
distribution of spherical and sphere-like Cu reduction of CuCl2 with SFS in oleic acid and acetone

Table 4 The particle size and size distribution of Cu nanoparticles with different surfactants (Precursor: 0.25 M CuSO4; reducing
agent: 6 g ascorbic acid) (Cheng et al. 2006)
Surfactant Particle size (nm) Particle size distribution (nm) Particle shape

SDBS (6 g) 3.8 2–6 Spherical


SDS (6 g) 4.8 2–9 Spherical
PEG-600 (6 ml) 4.6 2–9 Spherical
PEG-2000 (6 ml) 2.5 0.5–6 Spherical
PEG-6000 (6 ml) 17.0 5–25 Spherical
SDBS (4 g) ? PEG-600 (2 ml) 14.0 2–20 Spherical
SDS (4 g) ? PEG-600 (2 ml) 6.4 3–10 Spherical
SDBS (4 g) ? PEG-2000 (2 ml) – – Strip
SDS (4 g) ? PEG-2000 (2 ml) 9.5 3–18 Spherical ? elliptical
SDBS (4 g) ? PEG-6000 (2 ml) 21.8 2–38 Spherical ? elliptical
SDS (4 g) ? PEG-6000 (2 ml) 4.1 0.5–9 Spherical

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mixture. Almost phase pure Cu and better dispersion Effect of pH on Cu nanoparticles synthesis
nanoparticles were obtained at the end, which the
authors concluded that the Cu nanoparticles could For Cu-nanoparticles synthesis, the reducing ability of
effectively first capped by oleic acid followed by PVA four reducing agents is depending on the pH of the
to avoid agglomeration (Khanna et al. 2008). Indeed, solution. They are sodium borohydride, hydrazine,
20-nm size of Cu particle could be prepared by those sodium hypophosphite, and ascorbic acid. Zhang et al.
three methods mentioned above. (2009) have performed a study to relate the pH effect on
Other reported reducing agents include ethanol the final Cu product when sodium borohydride was used
(Das et al. 2011; Chandra et al. 2011), ethylene glycol to reduce CuSO4. They (Zhang et al. 2009) found that at
(Ramyadevi et al. 2012), isopropanol (Athawale et al. too low pH, rapid release of strong hydrogen bubbles
2005), and diethanolamine (Wen et al. 2012). Of these, could produce large amount of Cu nuclei, which tend to
ethanol, ethylene glycol, and isopropanol are used as aggregate into large agglomerates, while at very high
reducing agents cum solvents, and therefore polyol pH, newly produced Cu atoms like to deposit onto the
process is the specific term for this method. Ramya- pre-formed Cu nuclei and eventually growth to a larger
devi et al. (2012) had synthesized Cu nanoparticles by Cu nanoparticle. Finally, they concluded that pH 11 was
polyol method, whereby ethylene glycol was used to the optimized pH for the production of ultrafine Cu
reduce copper acetate. Tween 80 and ethylene glycol nanoparticles. Besides, Pham et al. (2011), Wu and
were chosen as stabilizer and solvent, respectively. Chen (2004) reported the similar reduction of CuCl2
The authors (Ramyadevi et al. 2012) were able to with hydrazine in aqueous CTAB solution. Ammonia
synthesize phase pure Cu nanoparticles with the was added to the mixture solution for pH adjustment
support of XRD analysis (Fig. 9a). The UV–Vis purpose, and they confirmed pH 10 was critical to
spectrum recorded at 580nm absorption peak has produce a finer phase pure Cu nanoparticles (Wu and
again attributed to the existence of Cu nanoparticles Chen 2004; Pham et al. 2011). Ammonia was used to
(Fig. 9b). This work proved that ethylene glycol has adjust solution pH up to 10 instead of NaOH, because
great ability to prevent nanoparticles from oxidation ammonia ions were not only can adjust the solution pH
and aggregation. Athawale et al. (2005) also synthe- but also acted as complex agent to prevent formation of
sized Cu nanoparticles by polyol method, where Cu2O. However, when solution pH \ 10, a low ammo-
isopropanol functions as solvent and reducing agent nia ions concentration was insufficient for the complex-
that reduces Cu(NO3)2 to Cu nanoparticles in the ation of Cu ions and thus Cu2O could be formed (Wu and
presence of CTAB stabilizer. The spherical Cu Chen 2004).
nanoparticles with particle size of 2–20 nm were In addition, Wen et al. (2011) had performed the
obtained in their final product. An overview of Cu reduction of CuSO4 with sodium hypophosphite
salts, reducing agents, and stabilizers being used to under different pH in order to reveal its optimum pH
produce respective particle sizes has been summarized condition. In their work, very small spherical
in Table 5. products were produced at pH values of 2 and 3,

Fig. 9 XRD diffractogram (a) and UV–Vis spectrum (b) of Cu nanoparticles (Ramyadevi et al. 2012)

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Table 5 Summary combination of Cu salts, reducing agents, stabilizers, surfactants, and particle sizes has been reported in Cu
nanoparticles synthesis via chemical reduction route
Cu salt precursor Reducing agent Stabilizer/surfactant Reported size

Copper sulfate Sodium borohydride PVP 0.8–3.6 nm (Zhang et al. 2009)


25–70 nm (Hashemipour et al. 2011)
Gelatin 37 nm (Liu et al. 2012a)
Dendrimers with a trimesyl core 2.6–6.9 nm (Jin et al. 2008)
CTAB ? decanethiol 1–40 nm (Chen et al. 2006)
Sodium hypophosphite PVP 5–10 nm (Yu et al. 2010),
30–80 nm (Zhu et al. 2004a),
30–70 nm (Zhu et al. 2004b),
37–88 nm (Park et al. 2007),
10–60 nm (Tang et al. 2010)
CTAB 15–100 nm (Tang et al. 2010)
Oleic acid 20–40 nm (Wen et al. 2011)
Ascorbic acid SDBS 2–6 nm (Cheng et al. 2006)
SDS 2–9 nm (Cheng et al. 2006)
PEGs 0.5–25 nm (Cheng et al. 2006)
SDBS ? PEGs 2–38 nm (Cheng et al. 2006)
SDS ? PEGs 0.5–18 nm (Cheng et al. 2006)
CTAB 90–250 nm (Biçer and Şişman 2010)
Oleic acid 30–40 nm (Yang et al. 2006)
Potassium borohydride PVP 5–50 nm (Cheng et al. 2011)
Copper chloride Sodium borohydride Bis(ethylhexyl)hydrogen phosphate 50–60 nm (Song et al. 2004)
2-propanol 50 nm (Chang et al. 2011)
Polyoxyethyleneoctyl phenyl ether ? 10–69.2 nm (Solanki et al. 2010)
di-octyl sodium sulphosuccinate
Hydrazine – 155–178 nm (Ren et al. 2005)
PVP ? CTAB \100 nm (Pham et al. 2011)
CTAB 5–15 nm (Wu and Chen 2004)
CTAB ? citric acid 57–85 nm (Kobayashi et al. 2011)
48–80 nm (Kobayashi et al. 2012)
SFS Oleic acid 20 nm (Khanna et al. 2008)
Oleic acid ? PVA 20 nm (Khanna et al. 2008)
Ethanol – 11–12 nm (Das et al. 2011)
Copper nitrate Sodium borohydride Acetonitrile \100 nm (Abdulla-Al-Mamun et al. 2009)
Hydrazine CTAB ? citric acid 40–70 nm (Kobayashi et al. 2012)
PVP 23–30 nm (Singh et al. 2010)
PVA 14–34 nm (Singh et al. 2010)
Starch 21–22 nm (Singh et al. 2010)
Ethanol Ligand benzyl diethylene-triamine 15–20 nm (Chandra et al. 2011)
Isopropanol CTAB 2–20 nm (Athawale et al. 2005)
Diethanolamine – 10–20 nm (Wen et al. 2012)
Copper acetate Hydrazine – 50–100 nm (Liu et al. 2006)
CTAB ? citric acid 39–69 nm (Kobayashi et al. 2012)
PVP 80–130 nm (Raut et al. 2009)

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but the particles at pH 3 showed better dispersion. et al. 2011), have shown obvious effect against
When pH [ 3, the product became non-uniform in temperature. First, the Cu nanoparticle does not form
size and showed partly agglomeration to yield bulk at temperature 50 °C, and it is only begin to form at
product. When pH = 6, only bulk product was temperature 60 °C with average size of 30 nm. Next,
formed. Thus, they noted that pH 3 was the most further increases the temperature to 70 °C has lead to
efficient pH to produce spherical Cu nanoparticles the formation of nanoparticles with average size of
with smaller size and good dispersion (Wen et al. 70 nm. The result showed that Cu nanoparticles
2011). formed at a higher temperature not only larger in size,
On the other hand, the pH values also play a crucial but also poor in dispersion (Hashemipour et al. 2011).
role in the reduction of Cu ions by using ascorbic acid. Besides, when CuSO4 remain same, ascorbic acid and
In previous section, we have cited Biçer and Şişman’s CTAB were respectively used as reducing agent and
work (Biçer and Şişman 2010) that the reduction stabilizer (Biçer and Şişman 2010). Decreasing in
reactions were pH dependent (Eqs. 9–11) and NaOH reaction temperature from 85 to 60 °C has no signif-
was added to control the pH. They found that the size icant effect on the size of nanoparticles, but Cu2O
of Cu particles produced was decreased dramatically along with Cu nanoparticles were obtained at 60 °C in
with increasing of pH from 3.0 to 6.5 (Fig. 10) (Biçer contrast to 85 °C that only pure Cu nanoparticles was
and Şişman 2010). This trend is due to the increase in obtained. Nevertheless, when reaction temperature
reduction power of ascorbic acid at a higher pH value maintains at 60 °C for 2.5 h, submicron wires with
(Biçer and Şişman 2010); this finding was also diameters in the range of 300–400 nm and lengths up
supported by Wu (2007). From this review, we can to 10 lm were obtained (Biçer and Şişman 2010).
conclude that the pH value has significant effect on the Again, CuSO4 remains the same, sodium hypo-
synthesis of Cu nanoparticles. phosphate and PVP were used as reducing agent and
stabilizer, respectively (Tang et al. 2010; Park et al.
Effect of temperature on Cu nanoparticles 2007). No immediate reduction upon addition of
synthesis sodium hypophosphate into the CuSO4 solution at
70 °C. However, when this reaction temperature
Temperature is another important factor that has great persists for 1 h, about 15-nm size of Cu nanoparticles
influence on the formation of Cu nanoparticles. This was obtained. On further increment in temperature to
section will review the effect of temperature on the 80 °C, the reaction completed in 20 min and the
morphology of Cu nanoparticles. particle size was similar as 70 °C. Moreover, the
In chemical reduction synthesis, Cu nanoparticles reaction completion times were shortened to 5 min
that prepared in a CuSO4 solution using NaBH4 as and less than 1 min along with the increment in
reducing agent and PVP as stabilizer (Hashemipour temperature to 90 and 100 °C, respectively. These

Fig. 10 SEM images of Cu nanoparticles formed at different pH: a pH 3, b pH 6.5 (Biçer and Şişman 2010)

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increments of temperatures to 90 and 100 °C also solution, leading to a uniform nucleation of small Cu
accompanied by the reduction of particles size to 20 nanoparticles (Zhu et al. 2004b).
and 25 nm, respectively (Tang et al. 2010). Next, with
further increment of reaction temperature, the
obtained particle sizes became 45 nm at 140 °C and Synthesis of Ag–Cu alloy nanoparticles
53 nm at 200 °C (Park et al. 2007). via chemical reduction
From the preceding review, a common conclusion
is made. At a relatively low temperature, the particles Ag–Cu alloy nanoparticles are emerging as another
size of Cu nanoparticles is relatively small, uniform, important material in this new era due to its great
and good in dispersion. Nucleation is the dominant variety applications in electronic devices, dental, and
process and primary influencing factor on particle size. biological (Johnston 2002). We intend to highlight that
While at a high temperature, the particle size becomes the previous section has mentioned that Cu nanopar-
larger, non-uniform, and poor in dispersion. This ticles are often easily get oxidize and unstable in
phenomenon can be explained by that reduction rate of atmosphere. Formation of Ag–Cu alloy nanoparticles
Cu2? ions increases with an increasing of the reaction with Ag addition could effectively prevent Cu nano-
temperature. Both nucleation and particle growth particles from oxidation and thus increase its stability
process are comparable important in determining the in atmosphere. This could be one of the advantages
particle size. Also, the rate of nucleation and particle demonstrated by Ag–Cu alloy nanoparticles. Ag–Cu
growth are coincidently accelerated with the rise of alloy nanoparticles have been synthesized via various
temperature to a high temperature. Finally, at an methods to fit its application. Typically, chemical
excessive high temperature, the particle size again reduction is a good method to yield large amount of
becomes larger, broad size distribution, and severe high purity, uniform shape, and small size of Ag–Cu
agglomeration. This is due to too intense reduction alloy nanoparticles to fit industry needs.
reaction at this temperature and entire reaction would For Ag–Cu alloy nanoparticles synthesis, hydrazine
be strongly disturbed. Particle growth becomes crucial (Singh et al. 2009, 2011; Taner et al. 2011) and NaBH4
in the process because surfactant cannot cover the (Wang et al. 2010; Ang and Chin 2005) are the two
surface of Cu nanoparticle quickly. Therefore, a commonly used reducing agents. Singh et al. (2009,
smaller particle that without surface protection can 2011) reported the co-reduction of AgNO3 and
be easily absorbed and growth onto the large particle Cu(NO3)2 with hydrazine in the presence of starch or
surface and lead to severe agglomeration; sometimes, PVP. When low concentration of Cu(NO3)2 was used,
flaky and bulky products also could be formed. Ag–Cu alloy nanoparticles with size of 11–13 nm
In addition, Zhu et al. (2004a, b) had utilized two were formed and proved to have less than 4 at.% of Cu
heating methods, which are microwave irradiation and content in the Ag–Cu alloy nanoparticles. However,
conventional heating, to reveal their effect on the with increasing concentration of Cu(NO3)2, the Cu
particle size. In their work, sodium hypophosphate content also increased in the Ag–Cu alloy accompa-
was used to reduce CuSO4 solution in the presence of nied by larger in nanoparticles size. The maximum
PVP. They found (Zhu et al. 2004a) that, with 5 min of content of Cu that detected in Ag–Cu alloy nanopar-
medium power microwave irradiation, particle sizes ticle was only up to 10 at.% at 1:5 for molar ratio of
less than 20 nm were formed. If compared to conven- AgNO3:Cu(NO3)2.
tion heating at 120 °C for 1 h, particle sizes ranging Wang et al. (2010) demonstrated a chemical
30–80 nm were formed. This indicates microwave reduction synthetic route to obtain Ag50–Cu50 alloy
irradiation can produce a narrower particle distribu- nanoparticles, size ranging from 60 to 130 nm.
tion and smaller particle size than conventional Typically, AgNO3, Cu(C2H3O2)2, and PVP were
heating. The microwave irradiation creates intense dissolved in tetraethylene glycol under sonication
friction and collision among molecules, thus greatly stirring. After stirring about 30 min, NaBH4 was
accelerates the nucleation of Cu and depresses the added, and the mixture solution was heated to 270 °C
straightforward growth of newly born Cu (Zhu et al. for 2 h. Figure 11 depicts the TEM image and
2004a, b). The microwave irradiation also can avoid corresponding SAED pattern of the Ag–Cu alloy
temperature and concentration gradient in reactant particles prepared by the above conditions (Wang

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J Nanopart Res (2013) 15:1537 Page 21 of 29

et al. 2010). The TEM image reveals black and white [Ag(NH3)2]? colloids were dropped into the mixture
contrasts inside the particles, which indicate the solution to yield the final product—130 to 150 nm of
particles were composed of Ag and Cu. These particles Ag-coated Cu particles. They commented that b-
were further confirmed as Ag–Cu alloy by SAED cyclodextrins played an important role in preventing
based on their ordered atomic structure and compo- aggregation of Ag–Cu alloy particles through –OH
sition 48.5:51.1 (Ag:Cu ratio) (Wang et al. 2010). bonding with Cu particles (Zhao et al. 2011). Valodkar
Li and Luo (2007) had studied the effect of different et al. (2011) have improved the ascorbic acid reduc-
reducing agents on the particle shapes of Ag–Cu alloy. tion with aid of full power microwave irradiation for
They found that small and evenly sized spherical Ag– 90 s. Ag–Cu alloy particles in the range of 20 ± 5-nm
Cu alloy nanoparticles were obtained with hydrazine, size were obtained and been used in antibacterial
and the long rod-shaped Ag–Cu alloy nanostructures activity testing in their consequence studies (Valodkar
were obtained with NaBH4 (Fig. 12). PAMAM den- et al. 2011). UV–Vis spectroscopy was used to confirm
drimers that acted as an outer template and dispersant the formation of Ag, Cu, and Ag–Cu alloy nanopar-
were used for both conditions. From EDS analysis, it ticles with vary mole ratio of Ag/Cu (Fig. 14). The
was confirmed that the spherical-shaped nanoparticle surface plasmon adsorption peaks appeared at 416 and
was made up of 21 at.% Ag and 79 at.% Cu and the 584 nm were attributed to Ag and Cu nanoparticles,
rod-shaped nanostructure was made up of 63 at.% Ag respectively. The red shift of surface plasmon adsorp-
and 37 at.% Cu, in agreement with these two tion peaks from 416 to 584 nm was attributed to
nanostructures were Ag–Cu alloy (Li and Luo 2007). increase of Cu content in Ag–Cu alloy nanoparticles
Ascorbic acid (Zhao et al. 2011; Valodkar et al. (Valodkar et al. 2011). On the other hand, Li et al.
2011) and dextrose (Li et al. 2010) are another two (2010) developed a 2-step synthesis process with
eco-friendly reducing agents used in the synthesis of dextrose reduction and with PVP stabilization.
Ag–Cu alloy nanoparticles. Zhao et al. (2011) pre- Wherein, Ag nanoparticles were prepared at first
sented a 3-step synthesis process with ascorbic acid using dextrose to reduce Ag(NO)3. These Ag nano-
reduction as illustrate in Fig. 13. First, CuSO4 and particles were served as seeds for the following
AgNO3 were reacted to form [Cu(NH3)4]2? and reduction of Cu(NO)3 at 85 °C. The authors noted
[Ag(NH3)2]? colloids by adding excess of aqueous that Ag core and Ag–Cu shell were the final structure
ammonia. [Cu(NH3)4]2? colloids were next dropped of nanoparticles (Li et al. 2010).
into the 70 °C reducing solution which consisted of Jiang et al. (2005) used polyol process to synthesis
ascorbic acid and b-cyclodextrins. After 20 min, Ag–Cu alloy nanoparticles for lead-free interconnect

Fig. 11 TEM image (a) and SAED pattern (b) of Ag–Cu alloy nanoparticles synthesis in tetraethylene glycol at 270 °C for 2 h (Wang
et al. 2010)

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Fig. 12 TEM images of Ag–Cu alloy nanostructures formed with different reducing agents: a hydrazine, b NaBH4 (Li and Luo 2007)

Fig. 13 Structures of b-
cyclodextrins and Ag–Cu
alloy formation sequence
(Zhao et al. 2011)

-cyclodextrins
-cyclodextrins
+ [Ag(NH3)2]+
2+
[Cu(NH3)4] + -cyclodextrins + C6H8O6

absorption spectra, which indicates the formation of


Ag–Cu alloy nanoparticles. The authors (Jiang et al.
2005) further noted two individual peaks at 407 and
585 nm should be detected if these nanoparticles are
pure Ag and Cu, respectively. Therefore, the single
peak showed up between these two peaks could be
interpreted as Ag–Cu alloy nanoparticles, rather than a
mixture of Ag nanoparticles and Cu nanoparticles.
Agrawal et al. (2005) demonstrated a preparation
method of Au–Ag–Cu alloy nanofilm at the toluene-
water interface. Au-(PPh3)Cl, Ag(PPh3)4NO3, and Cu-
Cupferron were used as organometallic precursor,
which later reduced by tetrakishydroxymethyl phos-
phonium chloride, to form the nanofilm at the
interface. The nanofilm can be disintegrated into
Fig. 14 UV–Vis absorption spectra of Ag, Cu and Ag–Cu alloy organosol that contains Au–Ag–Cu nanoparticles by
nanoparticles with vary mole ratios of Ag/Cu: a 1:0; b 0.75:0.25; dipping nanofilm in octadecanethiol solution for 48 h.
c 0.5:0.5; d 0.25:0.75; e 0:1 (Valodkar et al. 2011)
EDAX analysis confirmed the Au–Ag–Cu alloy
materials use. In this work, ethylene glycol was used formed has composition of 37:28:35 (Au:Ag:Cu).
as reducing agent cum solvent and PVP was used as Moreover, the absorption peak at 550 nm detected in
surfactant. The authors (Jiang et al. 2005) noted that a UV–Vis spectrum also corresponds to the formation of
single peak at 534 nm was obtained in UV–Vis Au–Ag–Cu alloy nanoparticles.

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J Nanopart Res (2013) 15:1537 Page 23 of 29

Summary and future works application needs; these are other selling points.
Ultimately, chemical reduction method has immersed
In summary, chemical reduction method has shown a potential to scaleup for mass production, this could
great ability to synthesis Ag, Cu, and Ag–Cu alloy result more nanoparticles being produced to the
nanoparticles with wide range of size and various market, and finally the market price of nanoparticles
shapes. Statistically, sodium borohydride and hydra- could be lowered and stabilized. In conclusion,
zine are the most used reducing agents; SDS and PVP chemical reduction method has a bright future in
are the most used stabilizers, in this chemical reduc- nanoparticles synthesis, not only for Ag, Cu, and Ag–
tion means for Ag, Cu, and Ag–Cu alloy nanoparti- Cu alloys, which have been mentioned in this review,
cles’ synthesis. The review shows that small but also applicable for other metals and alloys.
nanoparticles can be easily produced with these
reducing agents, and well-dispersed nanoparticles Acknowledgments This work was supported by Universiti
Sains Malaysia RU-PRGS grant no 8045012. One of the authors
can be produced with capped of these stabilizers.
(K.S.T.) would like to acknowledge MyPhD scholarship support
Besides, Cu nanoparticles are less widely studied if given by Ministry of Higher Education Malaysia.
compared to Ag nanoparticles because of fast oxidiz-
ing property of Cu in atmosphere. Synthesis of Ag–Cu
alloy nanoparticles is much complicated and least
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