International Journal of Nanoscience

Vol. 13, No. 2 (2014) 1430001 (22 pages)

#.c World Scienti¯c Publishing Company
DOI: 10.1142/S0219581X14300016

Copper Nanoparticles: Synthetic Strategies, Properties

and Multifunctional Application

A. Tamilvanan*,‡, K. Balamurugan†,§, K. Ponappa*,¶

and B. Madhan Kumar*,||
*Department of Mechanical Engineering
Kongu Engineering College, Erode-638052, Tamil Nadu, India
†Department of Mechanical Engineering

Institute of Road and Transport Technology, Erode-638316

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Tamil Nadu, India

‡
tamilvanan.aj@gmail.com
§
drkbalamurugan@gmail.com
¶kponappa@gmail.com
||kumarbmadhan@gmail.com

Received 7 January 2014

Accepted 26 March 2014
Published 20 May 2014

Copper nanoparticles received much attention due to its high electrical conductivity, high
melting point, low electrochemical migration behavior and low cost. Top down (physical
methods) and bottom up (chemical and biological) approaches adopted for the synthesis
of copper nanoparticles are reported. The property of copper nanoparticles mainly depends
on the synthesis route and their process parameters. The in°uence of process parameters
on the morphology, growth and yield of the nanoparticles by adopting various synthesis
methods are discussed in detail. From the earlier reports, it is proved that electrochemical and
chemical reduction method have received much higher attention due to their simple operation,
low cost, faster reaction rate, high yield, environment friendly and low energy consumption.
The characterization techniques, advantages and limitations of each synthesis methods are also
discussed. The extensive applications of copper nanoparticles in various ¯elds are also
highlighted.

Keywords: Copper nanoparticles; synthesis; top-down; bottom-up; electrochemical and chemi-

cal reduction.

1. Introduction at the nanoscale and at dimensions between ap-

Nanotechnology is the most promising technology proximately 1 nm and 100 nm and quantum e®ects
that deals with understanding and control of matter rule the behavior and properties of particles at

‡ Corresponding author.

1430001-1
 A. Tamilvanan et al.
nanoscale range. When a bulk material is divided
into small size particles with one or more dimen-
sions (length, thickness or width) in nanometer
range, the individual particles exhibit unexpected
properties which are di®erent from those of the bulk
material. It is known that the atoms and molecules
present in the small size particles exhibits totally
di®erent behavior than those of bulk materials.
Metallic nanoparticles ¯nd applications in optical,
thermal, magnetic, sensoric devices and catalysis
due to their small dimensions and special properties
such as high surface area to volume ratio and high
heat transfer.1,2 Copper nanoparticles received
much attention due to its high electrical conduc-
tivity, high melting point, low electrochemical mi-
gration behavior, excellent solderability and low
material cost.3
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The synthesis of nanoparticles has received con-
siderable attention because of their unique physical
and chemical properties that are distinct from the
bulk materials. Several methods have been proposed
for synthesis of copper nanoparticles by considering
bottom-up and top-down methods. The major
techniques for preparing copper nanoparticles by
chemical methods are Chemical reduction, sono-
chemical reduction, micro emulsion techniques,
electrochemical, hydrothermal, sol gel synthesis,
polyol process, biological synthesis and microwave
assisted techniques. Physical methods for the syn-
thesis of copper nanoparticles are laser ablation,
vapor phase synthesis, mechanical milling and
pulsed wire discharge. Chemical methods of pre-
paring copper nanoparticles are simple in operation,
high °exible and environment friendly. In electro-
chemical method the copper nanoparticles can be
produced at room temperature without using any
additives. The main advantages of powder produc-
tion by electrolysis are high purity and there is no
need to use high pressure, toxic chemicals and
vacuum systems to produce the product.
Richard Feynman (1959) described molecular
machines with atomic precision from his famous
lecture There's Plenty of Room at the Bottom and
originated the idea of nanotechnology.4
The journey of nanotechnology was started at 1974
when Tanigushi used the term \nanotechnology"
in his paper onion-sputter machining. Drexler origi-
nates the concept of molecular technology at MIT in
1979. The ¯rst technical paper on molecular engi-
neering to build with atomic precision was published
in 1981. The scanning tunneling microscope was
invented in 1981 by Gerd Binnig and Heinrich Rohrer
1430001-2
of IBM's Zurich Lab in Zurich, Switzerland mean-
while Bucky-ball was discovered in 1985. The ¯rst
book on nanotechnology in the name of \Engines of
Creation: The Coming Era of Nanotechnology" was
published in 1986.
The Fullerene is any molecule made up of carbon,
in the form of a hollow sphere, ellipsoid or tube
which was discovered in 1985 by Harry Kroto,
Richard Smalley and Robert Curl. IBM scientists
invented how to move and position individual
atoms on a metal surface using a scanning tunneling
microscope and this technique was exposed in April
1990 at IBM research center, San Jose, California
and they spelled out the company logo in atoms
using 35 xenon atoms on a background of copper
atoms to spell in 1989. The term nano°uid was ¯rst
used by choi in 1995.5 Commercial applications of
nanotechnology, such as the Silver Nanoplatform
for using silver nanoparticles as an antibacterial
agent, carbon nanotubes for stain-resistant textiles
and nanoparticle-based transparent sunscreens
were began in 2000. In 2011, ¯rst programmable
nanowire circuits for nanoprocessors was developed.
Copper (Cu) nanoparticles were used as alter-
natives for other noble metals in many applications
such as heat transfer and inkjet printing.6 Inkjet
printing is the most promising technology that uses
noble metals such as gold and silver for printing
highly conductive elements. The costs of noble
metals are very high when compared with copper.
Therefore, copper is mostly preferred for fabricating
highly conductive Cu patterns on a plastic substrate
by inkjet printing because of its low cost and high
conductivity.7
2. Synthesis of Copper Nanoparticles
The preparation of copper nanoparticles is much
more di±cult in comparison with noble metals due
to the possibility of oxidation of copper with air.
Metallic copper nanoparticles have received much
attention when compared to all other noble metals
such as Ag, Au and Pt because of their small size,
high surface/volume ratio, improvement of size,
shape and oxidation resistance, etc.
Copper particles have the tendency to get oxi-
dized when they are exposed to air and agglomer-
ation of particles take place because of surface
oxidation. To avoid this problem nano copper par-
ticles are produced in an inert gas atmosphere.8
In some cases, protective polymers.9,10 or surfac-
tants11 are utilized to inhibit oxidation.
 Copper Nanoparticles: Synthetic Strategies, Properties and Multifunctional Application

Synthesis

Bottom-Up Top-Down

Electrochemical Biological synthesis

Pulsed wire discharge

Chemical reduction Pulse laser

ablation/deposition method

Sonochemical method
Mechanical/ball milling

Microemulsion
Mechanochemical synthesis
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Sol-gel process
Solvothermal decomposition
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Fig. 1. Classi¯cation of synthesis techniques.

Copper nanoparticles can be produced by using conditions it is very easy to obtain narrow particle size
various techniques typically classi¯ed as bottom-up distribution in chemical methods. Large-scale syn-
or chemical methods and top-down or physical theses are not possible by using chemical methods.26
methods12 which is shown in Fig. 1. The structure of Various methods are available for synthesis of
copper nanoparticles are composed of atoms and copper nanoparticles. Copper nanoparticles re-
clusters or molecules in bottom-up approach where ceived much attention because of large volume of
as in the case of top-down approach a bulk piece of literatures concerning the production and charac-
required material diminished to nanoscale dimen- terization of copper nanoparticles. The statistics of
sions using mechanical milling, cutting, etching and synthesis of nanoparticles is given in Table 1. Based
grinding techniques. Some of the methods like on the collection of literatures a pie chart was
chemical reduction,13 sonochemical reduction,14 drawn. The pie chart is shown in Fig. 2. The total
microemulsion techniques,15 electrochemical,16 hy- number of papers considered for this research is 130.
drothermal,17 sol–gel synthesis,18 polyol process19 Among that electrochemical method concerns large
and microwave-assisted methods20 are the major
techniques for preparing copper nanoparticles from Table 1. The statistics of synthesis of copper nanoparticles.
bottom-up approach. Biological syntheses are also
treated as bottom-up approach.21 Top down No. of
methods for synthesis of copper nanoparticles are S. No. Method of synthesis references %
laser ablation,22 vapor phase synthesis,23 mechani- 1. Electrochemical method 25 19.23
cal milling24 and pulsed wire discharge (PWD).25 2. Chemical reduction method 15 11.54
A wide range of nanoparticles can be produced 3. Sonochemical method 6 4.6
using top-down or physical method with little 4. Microwave method 6 4.6
alterations but the quality of product is not good 5. Microemulsion technique 8 6.15
6. Sol–gel process 3 2.3
when compared to chemical methods and it requires
7. Pulsed wire discharge 11 8.46
special equipments and vacuum systems to produce 8. Solvothermal decomposition 7 5.38
nanoparticles. But in the case of chemical methods 9. Pulse laser ablation/deposition 8 6.15
the size, growth, morphology and distribution of 10. Mechanical/ball milling method 6 4.62
particles can be controlled by optimizing reaction 11. Mechanochemical synthesis 7 5.38
conditions such as reaction time, pH and ratio of 12. Biological synthesis 5 3.85
13. Applications 10 7.69
electrolyte to the surfactant, protective agent, type of 14. Others 13 10
solvent and capping agent. Using these optimum
1430001-3
 A. Tamilvanan et al.
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Fig. 2. Pie chart for synthesis of copper nanoparticles.
volume of literatures (19.23%) which is higher when
compared to all other methods.
3. Electrochemical Method
In electrochemical synthesis method, the copper
nanoparticles are prepared using electricity as a
driving force. It passes and conducts electric current
through an electrolytic solution and results in
chemical changes. The process takes place at elec-
trode–electrolyte interface. Electrolytic synthesis of
copper salt or sulfuric acid is most commonly used
synthesis method for producing copper nano-
particles. The electrochemical process is shown in
Fig. 3. Electrochemical method received consider-
able attention because of its low cost preparation of
nanoparticles, simple operation, high °exibility,
easy availability of equipments and no need of
vacuum systems to produce pure product.27
Fig. 3. Electrochemical synthesis of copper nanoparticles.27
1430001-4
Synthesis of copper nanoparticles were achieved
by passing 4 V, 5 A current into the electrolytic so-
lution of Copper sulfate (CuSO4
5H2O) and sulfuric
acid (H2SO4) for a period of 30 min. The produced
copper nanoparticles were 40–60 nm in size.16
A simple, novel, cost-e®ective and eco-friendly
electrolytic method is proposed to synthesize copper
nanoparticles at a power supply of 15 V and 6 A
under room temperature using copper sulfate as
metal precursor. The synthesized copper nano-
particles were spherical in shape with a particle size
of 24 nm and speci¯c surface area of 28 m2/g. Cop-
per nanoparticles were synthesized without using
any additives and there is no need of pressure, toxic
chemicals and vacuum system.27
Di®erent methods for the synthesis of copper
nanoparticles by applying chemical, physical and
biological techniques considering top-down and
bottom-up methods were reported. The advantages,
applications, characterization techniques and dis-
advantages of each synthesis method were explained.
Chemical methods are simple in operation, possess
high °exibility, less contamination, easy availability
of equipments and no need of vacuum systems to
produce pure product. The size, growth and mor-
phology of copper particles which is produced from
chemical method can be controlled by optimizing
the reaction conditions. The use of toxic chemicals,
reducing agent and stabilizer and capping agent
makes the production costly and hazardous to the
environment.28
 Copper Nanoparticles: Synthetic Strategies, Properties and Multifunctional Application
3.1. E®ect of parameters on electrolysis
Copper deposits on the cathode in electrolytic cell
depend on current density, concentration of elec-
trolytic solution, concentration of metal ions,
temperature, circulation rate, electrode spacing,
removal time of powders from electrolyte, etc. The
e®ects of these parameters on electrodeposition are
discussed.
Technical properties of powders depend on their
particles morphology and granulometry. Changes of
e®ective parameters of the process and morphology
of copper particle deposited galvanostatically cor-
responding to the current density were analyzed. To
prevent oxidation, the produced copper powders
were washed with a solution of distilled water and
0.1% of benzoic acid used as the stabilizer. The
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apparent density shows linear decreasing depen-
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dence on current density, while the apparent den-
sity increases with increase of shape factor. From
the results it was clear that the morphology of
copper nanoparticles was changed from compact
and massive dendrites to disperse dendrites with
corn-like and fern-like surface ending. The increase
in current density results in decrease of mean par-
ticle size, apparent density and enhancement of
speci¯c surface area. The selected process para-
meters of electrolysis such as area, shape factor and
perimeter decreases linearly with current density.29
Pulsing electrolysis method is proposed to pro-
duce copper nanopowders from acidic sulfate solu-
tions in the presence of di®erent organic additives.
The e®ects of polyvinylpyrrlidone (PVP), polyeth-
ylene glycol (PEG), cellulose, thiourea and sodium
dodecyl sulfate (SDS) and their concentrations on
purity, morphology and average particle size were
reported. The presence of additives increases the
nucleation rate and decreases the growth rate.
The best result attained for the concentration of
2 g/L of PVP and the average particle size was
110  10 nm.30
Design of experiments (DOE) was applied to
produce ultra-¯ne copper powders by means of
electrolysis. In this method, the e®ects of current
density, sulfuric acid concentration, copper ion
concentration and chloride ion concentration on
electrolytic process were studied. The considered
parameters were varied as: current density, 0.25–
0.35 A/cm2; [H2SO4], 140–180 g/L; [Cu 2þ ], 2–8 g/L;
[Cl  ], 0–60 ppm. DOE was used to optimize the
parameters. The particle size produced under opti-
mum condition was 0.71
m which was close to the
1430001-5
experimental value of 0.68
m. E®ects of para-
meters were determined using limiting current
density phenomenon. As the overvoltage increased,
the powder became ¯ner. When the overvoltage is
increased, hydrogen evolution took place and the
e±ciency of current became smaller. The increase in
current density increases the number of growth sites
and decreases the grain size of deposit. The increase
of [Cu 2þ ] ion concentration accelerates formation
and growth of copper nuclei. Increase in Cl  ion
concentration does not have a considerable e®ect on
the cathode crystallization of deposits of copper.
When [H2SO4] concentration increased the powder
became coarser.31
The in°uences of cupric ion concentration (5–
35 g/L), temperature (20–60  C), current density
(500–2000 A/m2) and circulation rate of electrolytic
solution (15–120 mL/min) on the physical and
chemical properties of copper powders produced in
electrolysis cells were investigated in this paper.
Full factorial statistical method of DOE was used
for investigating the interaction of main e®ects of
processes. In electro re¯ning, (ER) all experiments
were done in a 2 L glass cell along with two casting
copper plates of (70 mm  100 mm  5 mm) acting
as anode and one pure sheet (50 mm  100 mm
0:05 mm) acting as cathode. Increase in temperature
produces negative impact in terms of industrial usage
but at the same time it reduces the electrical energy
consumption. Increasing the circulation rate increa-
ses the particle size in ER condition but the grain size
decreased in the electro winning (EW) cell.32
The e®ects of parameters such as current
density, electrolyte temperature rotation speed of
cathode and concentration of copper ions on the
morphologies and on the apparent densities of
copper powders were investigated in this paper. The
morphology of copper powders was examined using
the technique of scanning electron microscope
(SEM). Stainless steel cathode and lead anode were
used with the electrolyte volume of 1250 mL. In-
creasing of current density or the electrolyte tem-
perature decreased the size of powder particle by
providing their morphology with dendritic structure
whereas the increase of copper ion concentration or
rotation speed of cathode increases the size of the
particles resulting in cauli°ower-like morphology.
The prepared copper powder was found to be suit-
able for many metallurgical application.33
The e®ect of anode material on the dimensional
characteristics and chemical composition of ultra¯ne
copper powders produced by the electrochemical
 A. Tamilvanan et al.
method from aqueous-organic solutions of copper
sulfate were investigated in this paper. Electro-
chemical production of nanosized copper bearing
powders with the sizes of particles less than 100 nm
illustrates the e±cient use of soluble anode. The
granulometric compositions of powders were no-
ticeably in°uenced by organic solvents. For a cer-
tain concentration of isopropyl alcohol in aqueous
solution of electrolyte a substantial decrease of size
of particles took place. From the peak intensities of
X-ray di®raction (XRD), it was detected that the
powders produced with the use of insolvent anode
contain  90% of copper and  10% Cu2O, and the
powders produced with the help of a copper anode
contain  70% Cu2O and  30% of Cu.34
Copper powders produced from electrolysis using
a conventional electrolysis cell with scraper that
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provides faster ionic movement due to di®usion at
electrode–electrolyte interface. The morphologies of
copper powders were analyzed in terms of current
density, temperature of electrolyte and copper ion
concentration. A stainless steel cathode of 30 cm 2
ð2 cm  15 cmÞ and two lead anodes were used with
the electrolytic volume of 0.0035 m3. The speed
scraper was set at 10 cycles per min for all the
experiments. The electrolyte circulation rate was set
at 1.0 L/min. It was observed that the increase in
current density with decreasing Cu ion concentra-
tions leads to increase in speci¯c surface area of
copper powder and decrease in size of grain. The
decrease in size of grain was interrelated with the
increasing quantity of evolved hydrogen.35
Electrolysis method was proposed to produce
copper powder particles under di®erent quantities
of evolved hydrogen and characterized using the
SEM method. Two types of copper nanoparticles
were formed based on the quantity of evolved hy-
drogen. One type of particle was produced during
electrodeposition of copper when the quantity of
evolved hydrogen was insu±cient to change the
hydrodynamic conditions in the near-electrode
layer. This type of particle produces corncob-like
structures. The other type of particle which was
formed during electrodeposition of copper was suf-
¯cient to change the dynamic conditions and pro-
duces cauli°ower-like structures. The size of copper
grains and the quantity of evolved hydrogen was
increased when the electrodeposition over potential
increased. The powder particles were formed by
potentiostatic electrodeposition at a temperature
of (18  1.0)  C. The decrease in size of grains
was observed with increasing quantity of evolved
1430001-6
hydrogen. The formation of highly branched den-
dritic particles was controlled by the di®usion of
ions.36
Ultra¯ne copper particles produced as a bi-prod-
uct of electro polishing of copper surface was
explained in this paper. Brightness and smoothness of
copper surface was enhanced by using electro pol-
ishing process and it produces reddish ultra¯ne cop-
per particles. The size of produced copper powder was
determined by submicron particle size (SDP) ana-
lyzer. SEM and energy dispersive X-ray spectroscopy
(EDX or EDS) analysis were helpful in analyzing
surface morphology and purity. The ultra¯ne copper
deposit depends largely on the applied conditions
such as current density, temperature, time and con-
centration of electrolytic solution. SDP results show
the presence of nanoparticle size in the range of 300–
900 nm with the average value of 578 nm.37
Fundamental aspects of copper electrodeposition
at high overpotentials in the hydrogen co-deposition
range were explained in this paper. The two types
of copper deposits are produced in the hydrogen
co-deposition range: (a) the open and porous
structures which is in the form of honeycomb-like
structures with high surface area and (b) powdered
deposits. Due to high surface area of these struc-
tures they are applied in many electrochemical
devices such as fuel cells, chemical sensors, batteries
and used as catalysis.38
The e®ect of di®erent electrolytic regimes (con-
stant current and reversing current) on the mor-
phology of copper nanoparticles was investigated in
this research. Copper nanoparticles were synthe-
sized by means of galvanostatic electrodeposition
method. The production of copper was carried out
with the help of electrolyte containing 145 g/L sul-
furic acid and 18 g/L using electrolyte temperature
50  2  C with the cell volume of 0.01 m3. The de-
position time, cathodic time and anodic time was
set constant at the values of 30 min, 1 s and 0.4 s
for all the experiments. The values of current
densities (j ¼ 0:0771 Am 2 , 0.1028 Am 2 , 30 Am 2
and 0.36 Am 2 ) and reversing current density values
were (0.18 Am 2 , 0.24 Am 2 , 0.30 Am 2 to
0.36 Am 2 ) used for electrodeposition of copper
powders. The e®ect of current amplitude, period of
current wave and cathodic-to-anodic time ratio on
morphology was brie°y explained in this paper.39
A novel electrodeposition route was performed to
produce ultra¯ne copper powders by ultrasonic
dispersion of electrolyte. High purity copper nano-
particles produced with Face cubic center (FCC)
 Copper Nanoparticles: Synthetic Strategies, Properties and Multifunctional Application
structure by taking a combination of both ¯shbone-
like structures and irregular shapes. The in°uences
of Cu 2þ concentration on the size of copper powders
with the current e±ciency were discussed. The for-
mation mechanisms of copper nanoparticles were
reported in this paper. The mean particle size of
powders increases linearly from 0.92
m in
0.03 mol/L electrolyte to 1.80
m 0.09 mol/L elec-
trolytes and the current e±ciency linearly changes
from 66.5% to 91.3%.42
The relationship between the speci¯c surface
area and apparent density of copper powders elec-
trodeposited from acid copper sulfate solutions was
established. From the investigations it was clear
that the apparent density was inversely propor-
tional to the speci¯c surface of copper powder.43
The e®ect of di®erent current regimes of elec-
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trolysis on the micro- and nanostructural char-
acteristics of open porous structures was performed
through the analysis of honeycomb-like copper
electrodes formed by constant galvanostatic (DC)
electrodeposition and by regimes of pulsating (PC)
and reversing (RC) current were examined. A
number of holes were formed by isolated hydrogen
bubbles. Increase in the number of holes, decrease in
wall width between holes and change of morphology
from cauli°ower-like structures to dendrites were
observed in the following order: the DC, PC and RC
regimes.44 The e®ect of the applied electrolyte on a
composition and morphology of synthesized parti-
cles were explained in this paper. The concentration
of electrolyte depends on copper compounds.
Investigations were carried out in organic solutions
of LiClO4 and LiCl, which are anhydrous. Copper
salts were formed in anhydrous solution and in
LiClO4 where as in the case of alcohol solution of
LiCl copper oxide particles were formed.45
The structures of the surface of copper powder
particles formed by electrodeposition were dis-
cussed. From the investigation it is proved that the
powders obtained by reversing current electrode-
position can °ow at considerably lower apparent
densities.46 The e®ect of temperature on the elec-
trodeposition of copper was investigated in this
paper. The e®ect of temperature on the viscosity
and surface tension of the electroplating solution
was also discussed. Copper was deposited from the
electrolytic solution of 0.15 moles (M) CuSO4 þ 0:50
M H2SO4 in an electrolytic cell and at temperatures
of 14.0  0.5  C, 35.0  0.5  C and 50.0  0.5  C.
Copper electrodeposition was carried out at over
potentials of 550 mV, 650 mV and 800 mV.47
1430001-7
The in°uences of additives on the quality of copper
powder in the electrolytic preparation process were
explored. Experiments were performed under various
conditions: without additives with traditional addi-
tives or with PVP and sodium polyoxyethylene
alkylphenolsulfonate (APES) and with a mixture of
PVP and APES. The in°uence of additives on the
composition and particle size distribution as well as
on the current e±ciency is also discussed in this
paper. From the results it was clear that the particle
size distribution of copper nanopowders does not
change with traditional additive or without additive
but the mixture of both PVP and APES makes the
particle size distribution suitable for practical de-
mand and produces good quality of powder.41
Electrodepositions of copper by pulsating over-
potential (PO) regime corresponding to the hydro-
gen co-deposition range were analyzed by SEM. The
electrodeposition of copper was performed at the
overpotential of 1000 mV, a deposition pulse of
10 ms and pause durations of 5 ms, 20 ms, 50 ms and
100 ms (pause to pulse ratios were 0.5, 2, 5 and 10,
respectively). Honeycomb-like structures were
formed upto the pulse ratio of 5.48 The morpholo-
gies of powder particles produced from both
potentiostatic and di®erent square-waves pulsing
over potential (PO) regimes of electrolysis were
explained using the SEM technique. The e®ect of
evolved hydrogen on the shape of particles at peri-
odically changing the rate was investigated. The
particles produced from PO regimes of electrolysis
were compared with constant potentiostatic regime
of di®erent CuSO4 and H2SO4 concentrations. From
the results it was clear that the e®ect of decreasing
deposition pulse was equivalent to the increasing
CuSO4 concentration.49
Copper electrodeposition from acid sulfate solu-
tions at overpotential of 1000 mV was examined by
the determination of the average current e±ciency of
hydrogen evolution and by the SEM analysis of the
morphology of the formed copper deposits. Depend-
ing on the concentration of Cu (II) ions, two types of
holes were formed by electrodeposition processes at
1000 mV. The holes are produced due to the attach-
ment of hydrogen bubbles. The ¯rst type of holes
were formed with honeycomb-like structure where as
in the other case dish-like structures were pro-
duced.50,51 The summary of electrolysis method is
given in Table 2. From the table, it was clear that the
most commonly preferred electrochemical method for
preparing copper nanoparticles is through electro-
lytic solution of copper sulfate.
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Table 2. Summary of synthesis of copper nanoparticles by electrochemical method.

Average
S. particle
No. Precursor Solvent Anode Cathode Process conditions Time size Characterization technique Ref.

1. Copper sulfate Distilled water Graphite plate Copper plate 3 V, 7 A 20 min 20–100 nm UV-Vis, Transmission electron 40
(CuSO4 ) microscope (TEM), EDS,
XRD and zeta sizer
2. (CuSO4 ) Distilled water Copper electrode Copper electrode DC Power Supply of (15 V and 6 A) — 24 nm XRD, TEM and FTIR 27
3. Copper sulfate penta Ultrapure water Copper plate Copper plate 2–4 V and 5 A 30 min 50 nm XRD, SEM, TEM and UV-Vis 16
hydrate
(CuSO4
5H2 O) þ
(H2 SO4 )
4. (CuSO4
5H2 O) Distilled water Copper plate Copper plate Current density 0.25–0.35 A/cm 2 ; [H2 SO4 ], 140– 5 min 0.68
m XRD, SEM, LPSA and EDS 31
(25 mm  40 mm) (25 mm  40 mm) 180 g/L, [Cu 2þ ], 2–8 g/L; [Cl], 0–60 ppm;
Temperature, 50  C
5. (H2 SO4 ) þ (CuSO4 ) Distilled water Copper Lead Current density of 500–1000 A/m 2 ; electrolysis 8h 71–154
m Particle size analyzer 41
temperature 25–60  C; concentration of H2 SO4 is
120–180 g/L; and concentration of Cu 2þ ion is
15–25 g/L
6. (H2 SO4 ) þ (CuSO4 ) Distilled water Cylindrical Cylindrical copper Electrolyte temperature (50  2)  C, current 30 min 0–300
m (from SEM, sieve, image and laser 29
copper electrode electrode densities (j ¼ 0:0771 Am 2 , 0.1028 Am 2 , particle size analysis.
30 Am 2 and 0.36 Am 2 ) distribution
curve)

1430001-8
7. (CuSO4
5H2 O) þ Distilled water Anodes Pure copper sheet Cupric ion concentration (5–35 g/L), current 3h 0–75
m (from SEM 32
H2 SO4 (70 mm  100 mm  (50 mm  100 mm density (500–2000 A/m 2 ), circulation rate of particle size
5 mm) 0.05 mm) the electrolyte solution (15–120 mL/min) and distribution
temperature (25–60  C) table)
8. (H2 SO4 ) þ (CuSO4 ) Distilled water Lead anode Stainless steel cathode Electrolysis temperature 60  0.5  C, Cathode — — Arnold meter, SEM 35
rotation speed – 140 rpm, 550 rpm and
1100 rpm, current density 200 mA cm 2 ,
250 mA cm 2 and 300 mA cm 2
9. H2 SO4 þ CuSO4 Distilled water Cylindrical copper Cylindrical copper Constant current densities (j ¼ 0:0771, 0.1028,30 30 min — SEM, sieve, image and laser 39
electrode electrode and 0.36 Am 2 ), reversing current densities analysis.
(0.18 Am 2 , 0.24 Am 2 , 0.30 Am 2 to
0.36 Am 2 )
10. (CuSO4
5H2 O) Distilled water Copperplate Copperplate Electrolysis temperature 30–40  C, Cu 2þ — 0.92–1.80
m XRD, SEM, TEM and LPSA 42
(25 mm  130 mm) (25 mm  130 mm) concentration 0.03 mol/L to 0.09 mol/L

Notes: LPSA — Laser particle size analyzer; UV-Vis – Ultraviolet visible spectroscopy; TEM — Transmission electron microscopy; FTIR – Fourier transform infrared spectroscopy;
CuSO4 — copper sulfate; Sulfuric acid — H2SO4; CuSO4
5H2O — Copper sulfate penta hydrate.
 Copper Nanoparticles: Synthetic Strategies, Properties and Multifunctional Application
4. Chemical Reduction Method
Liquid phase reduction is the another commonly
used chemical method to prepare copper nano-
powders. It involves precipitation of metallic Cu
nanoparticles by chemical reduction of salt, oxide or
hydroxide of copper in solution.13 In the chemical
reduction method, a copper salt is reduced by using
some reducing agent such as sodium borohydride,26
potassium borohydride,52 ascorbic acid,53 hydra-
zine54 and cetyltrimethyl ammonium bromide
(CTAB).55 The list of various chemical reducing
agents and the operating conditions to prepare
copper nanoparticles were given in Table 3. Chem-
ical reduction of copper salts is the most popular
method because of its low cost and simple opera-
tion. Copper nanoparticles were produced with
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reduction of copper salts.
Cu nanoparticles dispersed in water were pre-
pared by the reduction of copper salt solution. The
stability of copper nanoparticles was observed
through the investigation of the absorbance spectra
at di®erent stages during the synthesis. Laser par-
ticle size analyzer investigates the size and size
distributions of copper powder. The size of the
majority of the nanoparticles initially prepared was
about 770 nm but later the same was increased to
40 nm. An atomic force microscopy (AFM) picture
shows that the size of particles is slightly increased
during storage. The stability of copper particles
enhanced by the addition of citrate anions in col-
loidal system and it prevents agglomeration of
particles. CuSO4 was reduced by adding highly di-
lute sodium hydroxide in a nitrogen atmosphere. 1%
of tri sodium citrate was used for stabilizing copper
particles.56
Table 3. The reaction conditions for synthesis of copper nanoparticles by chemical reduction process.
Reducing agent Process conditions
Sodium tetra hydridoborate 60–75  C, nitrogen atmosphere
Sodium borohydride (NaBH4 ) Room temperature and pH 6–14
Ascorbic acid Room temperature
Potassium borohydride (KBH4 ) Temperature 10–80  C, molar
ratio of KHB4 to CuSO4 is 0.2–
1.4, and concentration of Cu 2þ
ions are 0.1–0.7
Hydrazine hydrate Temperature 20–100  C.
Hydrazine No inert gas medium, aqueous
solution at a high cupric ion
concentration (up to 0. 2 M)
1430001-9
Chemical reduction method for producing col-
loidal copper nanoparticles in water and ethylene
glycol (EG) was proposed in this paper. Surface
plasmon resonance peaks of colloidal copper in
water and EG were 579 nm and 551 nm. Ascorbic
acid was used as a protective agent to prevent Cu
nanoparticles from oxidation during the synthesis
and in storage. PVP acts both as polymeric capping
agent and size controller which prevents agglomer-
ation of nanoparticles. The stability of colloidal
copper in EG was higher than that of in water. The
solution of copper in water nanoparticles precipi-
tated after 22 days changes from light red to black
which was due to the oxidation of copper nano-
particles with air. TEM image shows that the syn-
thesized copper colloidal particles in water and EG
were spherical in shape. Colloidal copper nano-
particles in EG can remain stable even after 2
months.57
Copper nanoparticles synthesized by solution
reduction process were explained. The parameters
a®ecting the copper nanoparticles size was studied.
The mean particle size of copper lies in the range of
15  2 nm. Cu nanoparticles produced from chemi-
cal reduction method were cheap, greener and best
compared to other conventional methods. The
photo catalytic property of metal nanoparticles
depends largely on the surface area to volume
ratio.58 Synthesis of copper nanoparticles by re-
duction of copper nitrate in aqueous solution using
hydrazine monohydrate which acts as a reducer in
the presence of silver nanoparticles as catalysts were
explained. The particle size was determined using
Scherrer equation in the range of 7–12 nm. The
observation of plasma band 10 min after hydrazine
addition shows the rapid formation of copper
nanoparticles.59
Capping agent Reaction rate Ref.
— high 40
PEG moderate 26
PEG slow 62
Polyvinyl pyrrolidone, Glycerol high 52
propanetriol, n-butyl alcohol,
and PEG-400
— moderate 54
Cetyltrimethylammonim bromide moderate 63
(CTAB)
 A. Tamilvanan et al.
The preparations of copper nanoparticles by
aqueous solution reduction method were explained.
The e®ects of di®erent reaction parameters which
in°uence the preparation of copper nanoparticles
were investigated. The mean particle sizes of Cu
nanoparticles were increased with increasing tem-
perature. Cu 2þ concentration of reaction solution
decreased with increasing pH solution and it is re-
sponsible for nucleation and growth. At pH 10, Cu
particles were obtained at 10 min after reaction
whereas at pH 12 copper particles disappeared only
after 2 h.60 The e®ects of nature of copper salts and
initiators on the dispersity of copper powders were
investigated in this paper. Introduction of reducing
agents into the reaction solution makes the process
substantially faster and leads to increase in dis-
persity of copper powders with enhanced electrical
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conductivity and stability which was con¯rmed by
the high resolution transmission electron microscope
(HR-TEM) and X-ray phase analysis (XPA) data.
The decrease of crystallite size and speci¯c surface
area were observed by the introduction of initiators.
The minimum particle size of Cu nanoparticles was
about 10–50 nm which is measured through SEM.61
Synthesis of copper nanoparticles in the copper
sulfate solution using a reduction chemical (NaBH4)
in the chemical method and current in the electro-
chemical deposition method were investigated. Ef-
fect of the reaction parameters on the synthesis and
size control of the copper nanoparticles were studied
in this paper. Copper nanoparticles were produced
in a copper sulfate solution using NaBH4 as reduc-
ing agent under nitrogen atmosphere and then
stabilized in the presence of polyvinylpyrrolidone.
The average size of Cu nanoparticles produced in the
temperatures range of 60–75  C was about 30 nm
where as in the case of electrochemical method the
particle size was found to be 10 nm. Electrochemical
deposition gives ¯ner particles of copper but con-
trolling the size of nanoparticles was easier when
compared to chemical reduction method.40
Chemical reduction method was suggested for the
synthesis of copper powder. Highly pure, polyhedron
nonagglomerated copper powders were prepared by
the reaction of CuSO4
5H2O and ascorbic acid at pH
6–7 and under the reaction temperature of 60–70  C.
The Cu nanoparticles with uniform size and narrow
distribution were applied as terminal electrode
materials of base metal electrode-multilayer ceramic
capacitor (BME-MLCC) were examined through
SEM. Due to the interfacial reaction, rough micro-
structures were formed which leads to increase in
1430001-10
adhesion strength of copper electrode. An XRD study
shows the formation of mixture of copper and cu-
prous oxide nanoparticles.63
Chemical reduction method for producing
monodispersed pure phase copper colloids in water
and EG was reported. Ascorbic acid acts as a re-
ducing agent and antioxidant and PVP acts as size
controller and capping agent. Reaction rate in EG
was higher than that of water because of its re-
duction property. Thermogravimetric analysis
(TGA) shows that copper particles were produced
with good stability and the size of particles depends
on concentration of PVP.62 The summary of
chemical reduction method is given in Table 4.
5. Sonochemical Method
In sonochemical process, powerful ultrasound radia-
tions were (20 kHz to 10 MHz) applied to molecules.
Ultrasound irradiation of liquids causes chemical re-
action to occur. Acoustic cavitation is the origin of
sonochemistry and sonoluminescence. Acoustic cav-
itation is the physical phenomenon in which the for-
mation, growth and collapse of bubbles are irradiated
in liquid with high-intensity ultrasound. Based on the
nature of cavitation event, sonochemisry can be
broadly classi¯ed various categories: Homogeneous
of liquids, heterogeneous sonochemistry of liquids
and sonocatalysis. This method was initially used
for synthesis of iron nanoparticles. Fe nanoparticles
encapsulated in poly (ethylene glycol)-PEG-400
(FePEG) was synthesized by sonolysis of iron penta
carbonyl and PEG-400 in hexadecane solvent.64
Nowadays sonolysis technique is employed for syn-
thesis of metals and metal oxides.65
In this paper, the nanomaterials prepared using
pulsed sonoelectrochemistry were discussed. Pure
metals such as palladium, silver, nickel, gold, zinc and
gold were synthesized using pulsed sonoelec-
trochemistry. Sonoelectrochemical synthesis applies
both electrolytes and ultrasonic pulses to produce
nanoparticles. The size and shape of nanoparticles are
controlled by varying the operation parameters such
as ultrasonic power, bath temperature, deposition
potential, current density, intensity of ultrasound and
type of stabilizer. pH, temperature and composition
of electrolyte in sonoelectrochemistry cell are also
responsible for formation of nanoparticles.66
Metal oxide nanoparticles were prepared from
metal acetates by sonochemical synthesis. The
bandgap energies for CuO, ZnO and Co3O4 were
found to be 2.18, 3.35 and 2.26, respectively.
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Table 4. Summary of synthesis of copper nanoparticles by chemical reduction method.

Average
S. No. Solvent Precursor Reducer Stabilizer particle size Characterization technique Ref.

1. Water Copper sulfate pentahydrate Sodium tetrahydridoborate (NaBH4 ) PVP 30 nm UV-Vis, TEM, EDS, XRD 40
(CuSO4
5H2 O) and zeta sizer
2. Water (CuSO4
5H2 O) Sodium borohydride (NaBH4 ) PEG 10 nm UV-Vis, TEM, FT-IR 26
3. Water Copper sulfate (CuSO4 ) Ascorbic acid PVP 7  3 nm XRD, TEM and TGA 62
4. EG (CuSO4 ) Ascorbic acid PVP 3  1 nm XRD, TEM and TGA 62
5. Distilled water (CuSo4
5H2 O) Potassium borohydride (KBH4 ) — 100 nm SEM 52
6. Water bath copper(ii) sulfate þ ammonia (pH 11– Hydrazine hydrate — 10 nm Optical spectroscopy, XPS, 54
12) þ sodium tartrate þ sodium citrate XRD and AFM
or glycine þ surface-active substance
[sodium dodecyl Sulfate, polyvinyl
pyrrolidone, or CIAB]
7. Water (CuSO4 ) Ascorbic acid — 1.2
m SEM, XRD, TGA, DTG, 63
and DTA and LPSA
8. Aqueous CTAB solution. Cupric chloride Hydrazine — 5–15 nm Electron di®raction pattern, 55

1430001-11
EDS, XRD, XPS, TEM,
UV/Vis and TGA
analysis
9. H2 SO4 and NaOH solution (CuSO4 ) Ascorbic acid — 126–375 nm XRD and SEM 53
10. Methanol, ethanol, water, Copper (II) nitrate (Cu (NO3 Þ2
3H2 O) Benzildiethylenetriamine — 15 2 nm TEM, QELS data, FTIR, 58
acetonitrile, cyclohexane UV-Vis and XRD
and dimethyl sulfoxide
11. An aqueous solution of Copper nitrate Hydrazine monohydrate Poly acrylic acid 7–12 nm HR-TEM, STEM and XRD 59
Sokalan PA 40 and silver
nanoparticles
12. Distilled water (CuSO4 ) Sodium borohydride Tri sodium citrate 70–400 nm SEM, AFM and UV-Vis 56
13. H2 SO4 or NaOH solution (CuSO4 ) Sodium tetrahydridoborate (NaBH4 ) — 37 nm SEM and XRD 60

Notes: STEM — Scanning transmission electron microscope; DTG — di®erential thermogravimetry analysis; DTA — Di®erential thermal analysis; PVP — Polyvinyl pyrrolidone;
TGA — Thermogravimetry analysis; CuSO4 — copper sulfate; Sulfuric acid — H2SO4; CuSO4
5H2O — Copper sulfate penta hydrate.
 A. Tamilvanan et al.
Di®erent particle sizes, yields and morphologies
were observed when the solvent changed from water
to 10% water-dimethylformamide (DMF).67
Synthesis of CuInS2(CIS) nanoparticles by
sonochemical method was explained. Initially, cop-
per nanoparticles prepared from CuCl2 in methanol
solution under multibubble sonoluminescence
(MBSL) conditions were treated with InCl3
4H2O
and CH3CSNH2
MBSL conditions were applied to
produce In2S3-coated Cu nanoparticles in methanol
solution. By thermal heat treating at 300  C for 2 h,
these particles were transformed into CuInS2. The
size of synthesized nanoparticles were in the range
of 20–40 nm.68
6. Microwave Method
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Microwaves are the form of electromagnetic energy
with frequencies in the range of 300 MHz to 300 GHz.
The most commonly used frequency is 2.456 GHz. In
the microwave method, microwaves are passed into
the reaction solution. Interactions between materials
and microwaves are based on two speci¯c mechan-
isms: dipole interactions and ionic conduction. Both
mechanisms require coupling between components of
target material and oscillating electric ¯eld of mi-
crowave. The microwave-assisted synthesis of copper
nanoparticles allowed to increase the e±ciency of
materials by providing rapid heating and rapid re-
action time. Microwave-assisted synthesis of copper
nanoparticles became popular due to its simple op-
eration and increasing yield of products. The use of
microwave reactions during hydrothermal or sol-
vothermal method enhances their crystallization
rate.69,70 Microwave assisted method was also
employed to synthesize tin oxide and zinc oxide
nanoparticles.
The stable Cu nanosuspensions were obtained by
using microwave-assisted polyol synthesis. The
mean diameters of copper nanoparticles were in the
range of 45 nm to 130 nm. The growth and nucle-
ation of the particles were controlled by optimizing
the reaction parameters such as reducing agent
content, reaction yield, synthesis temperature and
the manner in which the reagents were injected. The
use of microwaves provides rapid uniform heating of
solvents and reagents and accelerates the reduction
of metal precursors and nucleation of nanos-
tructures with increased stability.71
Microwave-assisted techniques were suggested to
prepare zinc oxide nanoparticles. The main reagents
used in this method are hydrazine hydrate and
1430001-12
ammonia. The synthesis of zinc oxide depends on
the process parameters such as reagent concentra-
tion, molar ratio and irradiation time. The size of
copper nanoparticles was calculated using the
technique XRD. The mean size of prepared nano-
particles was found to be 18 nm.
The CuO nanoparticles were prepared by mi-
crowave irradiation method using copper (II) ace-
tate and sodium hydroxide as starting materials and
ethanol is used as the solvent. The prepared nano-
particles have regular shape, high purity with nar-
row size distribution. The produced CuO is
employed in many applications such as biosensors,
photics and catalysts.72 Synthesis of CuS nano-
particles by decomposition of [Cu(NH2CSNH2 Þ2 ]Cl2
complex was initially formed by the reaction be-
tween copper(II) acetate and thiourea (Tu) in the
presence of SDS. The mean particle size of nano-
particles lies in the range of 60–70 nm.73
7. Microemulsion Technique
Synthesis of copper nanoparticles received consid-
erable attention because of its ability to control
shape and size of particles by the use of proper
microemulsions and by the surfactant adsorption.
Microemulsions are clear, stable, isotrobic liquid
mixtures of water, oil and surfactant, frequently in
combination with co-surfactant.74,75 The aqueous
phase may contain salts or other ingredients and
the oil may be mixture of di®erent hydrocarbons
and ole¯ns. Synthesis of copper nanoparticles by
microemulsion technique consists of two immiscible
°uids such as water-in-oil (W/O), oil-in-water
(O/W), water-in-super conducting-CO2 (W/SC-
CO2 Þ. Oil and water are immiscible °uids but with
the addition of a surfactant, the oil and water be-
come emiscible due to the capability of the surfac-
tant to bridge the interfacial tension between the
two °uids.76
The microemulsion is called as oil in water (O/
W) if water is the bulk °uid and oil is in less
quantity, with small amounts of surfactant, likewise
the system is said to be water in oil (W/O) if oil is
the bulk °uid and water is present in less quantity.
The product of oil in water and surfactant (O/W) is
called micelles whereas the water in oil microemul-
sion carries high amount of organic solvent and
thermodynamically stable which is also called as
reverse micelles. The minimum concentration of
surfactants needed to produce micelle is called as
 Copper Nanoparticles: Synthetic Strategies, Properties and Multifunctional Application
critical micelle concentration (CMC) and it is af-
fected by various factors of reverse micelles such as
surfactant tail and geometry, quantity of co-sol-
vent, temperature and type of organic solvent.77
The use of reverse micelles to produce copper
nanocrystals was discussed in this paper. The in-
crease of water content in reverse micelle increases
the average particle size from 3 nm to 13 nm. From
the structural investigations, it was clear that pure
copper is formed with various crystallographic
structures. Spherical reverse micelles induces not
only the spheres but also other particles like cube,
tetrahedral and ellipsoidal particle.78 Copper metal
complexes such as CuCl2 and Cu(OAc)2 were in-
corporated into cellulose acetate to produce Cu
containing thin ¯lms. The produced Cu containing
thin ¯lms were investigated to understand the
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interactions between the Cu complexes and cellu-
lose acetate (CA) molecules.
The resulting light blue colored homogeneous ¯lms
of 5–20 wt.% copper acetate complex concentrations
were thermally stable up to 200  C. The reaction
chemistry of Cu in CA was investigated by reacting
them with small gas molecules such as CO, NO, D2,
O2 and H2 ole¯ns in the temperature range of 25–
160  C.79
The preparation of copper nanoparticles synthe-
sized in sodium bis(2-ethylhexl) sulfosuccinate
(AOT) reverse micelles in compressed propane and
supercritical °uid (SCF) ethanol solutions was
explained in this paper. The e®ects of compressed
solvent on particle characteristics and growth rate
were investigated and then compared with normal
liquid solvent. The particle growth rate in AOT
reverse micelles in SCF ethane solution is high due
to the properties of SCF solvent.80
Fig. 4. Mechanism for the synthesis of copper nanoparticles based on chemical reduction of functionalized AOT-copper ions.75
1430001-13
Copper nanoparticles were synthesized within
sodium bis (2-ethylhexl) sulfosuccinate (AOT) re-
verse micelles using compressed liquid and SCF
alkanes as the bulk solvent of microemulsion sys-
tem. AOT creates thermodynamically stable
microemulsion system and also acts as a stabilizing
agent to stabilize synthesized copper nanoparticles.
From experimental and modeling studies, it was
clear that the growth rate and size of synthesized
copper nanoparticles depends on strength of solvent
interactions between the bulk °uid and surfactant
tails. Increase in pressure and decrease in tempera-
ture results in larger particle size. The reaction
mechanism for synthesis of copper nanoparticles
based of functionalized AOT copper ions is given in
Fig. 4.15
8. Sol–Gel Process
The sol–gel process is a wet chemical technique that
uses either a chemical solution or colloidal particles
to produce an integrated network. Metal alkoxides
and metal chlorides are the typical precursors. They
undergo hydrolysis or polycondensation to produce
colloidal system composed of nanoparticles dis-
persed in solvent. Then the formation of inorganic
continuous network containing a liquid phase took
place. Drying process is performed to remove the
liquid phase. Then thermal heat treatment is car-
ried out to improve the mechanical properties of
prepared nanoparticles.
The ultra¯ne spherical cuprous oxide powder
was produced by using the glucose reduction of
Cu(OH)2. The Cu2O particles were reduced to copper
by means of coating of Mg(OH)2. Copper particles
densi¯ed with the help of high-temperature heat
 A. Tamilvanan et al.
treatment. SEM, TEM, tap density, TGA and XRD
techniques were used for characterization of synthe-
sized copper nanoparticles. The powder was densi¯ed
by keeping the temperature at 200  C, 400  C and
500  C for 1 h. The surface of copper particles chan-
ged from coarse and porous to smooth after the pro-
cess of densi¯cation. The densi¯cation process at high
temperature results in increase of tap density from
3.30 g/cm3 to 4.18 g/cm3 along with increase in oxi-
dation temperature from 125  C to 150  C.81
Pechini method was proposed to synthesize
nanocrystalline copper aluminates CuAl2O4 using
aqueous solutions containing metal nitrates. The
e®ect of di®erent factors on their crystal size in-
vestigated. A taguchi L4 statistical design was ap-
plied for optimization of reaction parameters
involved during the synthesis. The pH solution,
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type of complexing agent and calcination tempera-
ture were selected as the e®ective parameters for
optimization. Nanocrystalline CuAl2O4 particles
produced under optimum process conditions
with crystal size between 17 nm and 26 nm were
characterized with XRD, DLS, TGA and FTIR.
The decomposition of organic acid depends largely
on pH of the solution. From the investigations, it
was clear that calcination temperature was the most
e®ective factor to synthesize smaller particle size.82
Synthesis of titania and copper loaded titania by
sol–gel method using titanium butoxide was inves-
tigated. Cu/TiO2 was formed by adding copper
chloride to titania solution. Then the solution of
Cu/TiO2 was dried at 500  C to remove the organ-
ics. Cu/TiO2 was further reduced at 300  C by using
hydrogen. The crystallite size prepared copper
nanoparticles in the range of 17–20 nm and used as
the catalyst for photo catalytic reactions.18
9. Pulsed Wire Discharge
Pulsed wire discharge (PWD) is a physical technique
to produce copper nanoparticles.83 The mechanism
of preparing copper nanoparticles by PWD is dif-
ferent from all other synthesis methods. The princi-
ple of PWD is a pulsed current which is guided
through a solid wire that is placed in an ambient gas.
The pulsed current deposits electrical energy in the
wire. The deposited electrical energy evaporates the
wire material to produce a vapor which is then cooled
by an ambient gas to produce nanoparticles. Pre-
parations of metal, oxide and carbide nanoparticles
using PWD were studied.84–86 The e®ect of the
1430001-14
energy deposition on particle size distribution was
investigated. The copper powders produced the at-
mospheric gas of nitrogen. Energy deposition in
PWD was calculated by measuring volts and cur-
rents at various conditions which was increased by
increase in current raise.87
PWD method is applied to synthesize nano-
powders through material evaporation. Discharge
was carried out with the peak current of 10 kA, the
pulse length of  20 s and the pulse energy of  80 J
during the experiments. In this method, nanosize
powders of metals (Al, Fe, Cu, Mo and Pb), metal
oxides (Al2O3, TiO2, Fe2O3, NiO, ZrO2, SnO2 and
PbO), and metal nitrides (TiN, ZrN, Ta2N) were
synthesized using the technique of pulsed discharge
of metal wires in argon, oxygen or nitrogen atmo-
sphere with the production rate of  5 mg/pulse.
The mean particle size of TiN powders varies from
13–27 nm when the nitrogen gas atmosphere
of pressure was increased from 13332.2–79993.2 Pa.
It indicates that the average size of powder was
controlled by the pressure of the ambient gas.
Depending on the material of powder the size of
powder changes from 20 nm to 70 nm.88
Syntheses of copper nanoparticles in argon gas
ambiance by wire explosion process were discussed.
A copper wire of diameter of 90 mm long and
0.5 mm is diameter was used for the production of
copper nanoparticles and the process was carried
out at 0.1 MPa of argon ambience pressure. Wide
angle X-ray di®raction (WAXD), energy dispersive
analysis and TGA analysis were carried out to
study the physic-chemical properties of prepared
nanoparticles through X-ray (EDAX). The particle
size calculated from the Scherrer's equation was
36.34 nm. SEM, FTIR test and HR-TEM studies
examine that the produced copper nanoparticles
were spherical in shape with FCC structure and
crystalline structure of Cu nanoparticles were con-
¯rmed by Wide Angle X-ray Analysis.89
A coating technique was proposed to prepare
metal nanoparticles coated with organic matter.
Copper nanoparticles coated with organic matter
were produced by evaporation of a copper wire in an
oleic acid vapor/mist. The thickness of the coating
layer was a few nanometers. The in°uence of coat-
ing on the particle size and process oxidation was
investigated. The mean particle size of powder was
25 nm but in the case of without coating the particle
size became 10 nm. A copper wire with the length of
25 nm and diameter 0.25 nm was located in the
chamber ¯lled with nitrogen gas of pressure
 Copper Nanoparticles: Synthetic Strategies, Properties and Multifunctional Application
100 kPa. A pulsed current was produced from a
10
F capacitor with the capacity of charging up to
5.2 kV. The copper wire was evaporated with energy
of 68 J. The molecular structure of the particle
changes because of heat and the particle covered
with organic matter shows good stability.90
The e®ects of the ambient chamber pressure for
synthesis of copper nanoparticles by wire explosion
technique in di®erent ambient chamber pressure in
nitrogen environment were investigated. A copper
wire with the diameter of 125
m and 6.1 cm in
length bursted at 100 000 Pa, 50 000 000 Pa,
10 000 000 Pa and 5 000 000 Pa ambient chamber
pressures. Current density of 106 A cm 2 from a
1.85
F capacitor of charging upto 10 kV has been
applied to evaporate the wire.91 The mean diameter
of copper, silver and nickel nanosized powders de-
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creased with decreasing wire diameter. Decrease in
mean diameter of powders results in decrease of
density of plasma or vapor.92
10. Solvothermal Decomposition
In a sealed vessel (bomb, autoclave, etc) solvent can
be brought to temperatures well above their boiling
points by increasing the pressure by means of
heating. Carrying a chemical reaction under such
conditions is called as solvothermal process or in the
case of water it is referred to as solvent hydrother-
mal processing.93
Hydrothermal synthesis of copper nanoparticles,
ribbon-like network structures and copper nano-
cubes was explained in this paper. These copper
particles were prepared in the presence of surfactant
sodium dodecyl benzene sulfonate which acts as
stabilizer and controls the shape and size during the
hydrothermal reduction process. The e®ects of sur-
factant concentration and temperature on the pre-
pared Cu nanostructures were investigated. Copper
nanoparticles with di®erent mean diameters were
prepared at 100  C and hydrazine acts as a reducing
agent during the process.94
Synthesis of copper nanoparticles by using ther-
mal decomposition of Cu–oleate complex due to the
reaction between CuCl2 and sodium oleate in
aqueous condition in an autoclave was investigated.
TEM images shows that well-dispersed copper
nanoparticles were produced with diameter of
8.9  1.3 nm. The decomposition of Cu–oleate
complex was analyzed by using the technique TGA
at a temperature of 295  C. UV-Vis spectroscopy
1430001-15
shows the absorbance spectrum of copper nano-
particles. TGA analysis shows the weight loss of
copper-oleate complex during heat treatment under
air °ow. Sodium oleate was used as the capping
agent to protect oxidation of copper nanoparticles
because of its oleic tail (C18 ) with a cis-double bond.
TEM images con¯rm that produced copper nano-
particles were spherical in shape. From the EDX
spectrum, it was clear that no impurity atom in the
nanoparticles was present except copper atom.95
Synthesis of copper oxide nanostructures by hy-
drothermal process was described. The prepared
sample was characterized structurally, optically and
electrically using various techniques like FTIR, SEM,
dielectric analysis and UV-Vis spectroscopy. SEM
image of CuO shows uniform size and °ower-like
shapes and FTIR analysis provides the details of mo-
lecular structure and chemical bonding of the sample.
Space polarization plays an important role in deter-
mining the electrical property of the sample.96
The composition and structure of Cu containing
nanoparticles were stabilized in a polyethylene
matrix. Copper nanoparticles embedded in poly-
ethylene matrix inhibiting oxidation during storage
in air was studied. Metallic Cu nanoparticles were
produced by decomposing Copper (II) acetate
monohydrate at a temperature exceeding its de-
composition temperature. The size of particle was
determined using TEM. The size of the Cu nano-
particles present in the polyethylene matrix was
found to be 15 nm.97 Simplicity, synthesis of high-
purity nanocrystals with high crystallinity, low
grain size and eco-friendly nature of the process are
the main advantages of hydrothermal process.98
11. Pulse Laser Ablation/Deposition
Pulsed laser ablation is physical method applied
universally with an almost unlimited variety of
materials and solvents to generate nanoparticles. In
this method, large number of parameters are avail-
able for controlling the size and shape of nanoma-
terials with desired chemical composition.99 Laser
ablation method is the commonly used technique for
generation of copper nanoparticles with colloidal
form with variety of solvents to prevent oxidation.
The process was performed in a vacuum chamber
and in the presence of inert gas atmosphere.100
Cu nanoparticles were produced by laser ablation
of a copper target submerged in benzene with laser
pulses of Nd:YAG with varying wavelength such as
 A. Tamilvanan et al.
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Int. J. Nanosci. 2014.13. Downloaded from www.worldscientific.com
Fig. 5. Pulse laser ablation process.101
355 nm, 532 nm and 1064 nm. Colloidal nano-
particles were characterized using the techniques
UV-Vis spectroscopy and TEM techniques. The
radius of prepared nanoparticles using irradiation of
1064 nm lies in the range between 15 nm and 3 nm
with absorption peak at 572 nm. The pulse laser
ablation process is shown in Fig. 5.101
The mechanisms of photo-reduction of CuSO4
were explained. Copper nanoparticles were pre-
pared by irradiation of 253.7 nm light which comes
from low pressure Hg-arc lamp in the presence of
PVP and benzophenone (BP) which were used as
photosensitizers. The prepared nanoparticles were
characterized by their absorption maxima and
transmission electron micrographs. The average size
of copper nanoparticle was found to be 15 nm. The
photosensitizer plays a crucial role in the formation
of Cu nanoparticles because the presence of BP is
essential for producing Cu nanoparticles. From the
laser spectroscopic studies, it was clear that the
ketyl radical of benzophenone does not engage in
photochemical formation of Cu nanoparticles.102
The e®ect of the PVP on photochemical syn-
thesis in terms of nanometer control and colloidal
stability obtained by UV irradiation of ethanol so-
lution of Cu (acac)2 was explained in this paper.
The experiment factors such as light intensity,
concentration, sensitizer nature and surfactant
concentration were responsible for controlling the
size of particles. The ability of PVP to control the
size of particle was investigated by executing pho-
toreduction sensitized by Hacac at 254 nm and
1430001-16
300 nm in the presence of PVP concentration
varying from 0 M to 0.2 M. The copper nano-
particles size in the range of 30 nm to 4 nm was
obtained by photochemical reduction. PVP acts
both as a sensitizer and surfactant during the
process.103
There are number of parameters available for
controlling size of nanoparticles such as type of
solvent, number of pulses and type of laser. Variety
of solvents such as 2-propanol,104 octane22 and ac-
etone105 were used for preparing copper nano-
particles which is also called as nano°uids.
12. Mechanical/Ball Milling Method
Milling is the solid state processing technique to
produce copper nanoparticles. Many useful combi-
nations of metals cannot be achieved with conven-
tional powder metallurgy process. High-energy ball
milling was used to produce combinations of metal to
overcome the problems of powder-blending without
creating any di±culties to ultra¯ne powders.
The technique was ¯rst developed by Benjamin to
prepare super alloys. Di®erent types of mills are
available to produce or synthesize nanoparticles. The
mills used for producing nanoparticles are classi¯ed
based on the capacity and their applications. The
following factors were responsible for producing ul-
tra¯ne particles: Milling speed, milling time, heat
treatment temperature, type of mill, type mill, design
of container or chamber, atmosphere, process control
agent, size and size distribution of grinding medium
and weight ratio of ball to powder.106,107
High-energy ball milling was proposed to syn-
thesize various nanomaterials, nanocomposites,
nanoquasicrystalline materials, nanograins and
nanoalloy. The important factors to be considered
in high-energy milling were plastic deformation,
fracture and cold welding in which deformation
leads to a change in shape of particle, cold-welding
causes increase in particle size and the formation of
¯ne dispersed alloying particles in the grain-re¯ned
soft matrix was observed due to fracture and de-
cease in particle size. Tumbler ball mills, planetary
mills, attritor mills (Szegvariattritor) and vibratory
mills were commonly used for synthesis of nano-
particles. Controlled heat treatment and suitable
experimental factors may be used to obtain perfect
materials.108
It is very di±cult to produce ultra¯ne particles
using mechanical milling method because it will
 Copper Nanoparticles: Synthetic Strategies, Properties and Multifunctional Application
take long time to produce ultra¯ne powders. Syn-
thesis of nanomaterials by simple, low cost and high
yield was achieved with mechanical/ball milling
method.109 High-energy milling technique was sug-
gested to produce nanoparticles of ZnO from its
microcrystalline powder. The mechanical milling
was carried out in a horizontal oscillatory mill. The
synthesized nanoparticles were characterized with
the help of XRD, photoluminescence (PC) emission
spectra and TEM. The synthesized nanoparticles
were used as antibacterial materials. The samples
were milled for 2 h, 10 h, 20 h and 50 h, respectively.
Decrease in mean particle size ranging from 600 nm
to  30 nm was observed with increasing in milling
time.110
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13. Mechanochemical Synthesis
Int. J. Nanosci. 2014.13. Downloaded from www.worldscientific.com
Mechanochemical synthesis is the powder metal-
lurgy process in which chemical reactions and phase
transformations takes place due to application of
mechanical energy. The materials produced in this
method have found number of applications such as
heaters, fertilizers, cosmetics and hydrogen storage
materials. Mechanical chemical processing was
performed mainly to produce advanced materi-
als.111 Mechanochemical processing is suitable for
large-scale production. The mechanochemical pro-
cessing technique can be designed to synthesize
nanocrystalline materials dispersed in soluble salt
matrix. The chemical precursors used in this
method react during milling process or subsequent
heat treatment stage. After the completion of re-
action, the removal of matrix phase was performed
by washing with appropriate solvents that yield
nanoparticles with small dimensions.112,113
Mechanochemical method was proposed to syn-
thesize nanocrystalline pure zinc oxide by using the
heat treatment between ZnCl2 and Na2CO3 which
acts as reagents while NaCl2 acts as diluent. The
in°uence of milling time and heat treatment tem-
perature on size of nanocrystalline ZnO was inves-
tigated. The mean particle size of ZnO was found to
be 21 nm which was obtained by calcinations of
milled powder at 600  C. Increase in particle size
with increase in temperature was observed. The
particle size depends on milling time and tempera-
ture, ranging from 18 nm to 36 nm in the tempera-
ture range from 400  C to 800  C.114
Nanocrystalline semiconductor particles of PbS,
ZnS, CdS and CuS were prepared by mechano-
chemical route from its corresponding metal
1430001-17
acetates and sodium sul¯de in an industrial eccen-
tric vibratory mill. Several grams of material were
produced in an ambient temperature at shorter
period of time with small amount of aggregation.
TEM and low temperature nitrogen sorption were
used to analyze particle morphology and surface
area measurements. The rotation speed of milling
chamber and total time for milling was 960 rpm and
6 min with steel balls of 30 mm diameter for loading
the mill. The mean particle size of semiconducting
particles ranging from 4–18 nm were calculated
using Scherrer's equation.115
Synthesis of Cu2O nanoparticles through solid
state reaction between Cu and oxygen using
mechanochemical oxidation with an average crys-
tallite size of about 11 nm was obtained after 60 h of
milling. Decrease in the Cu mean crystallite size and
an increase in internal strain was observed during
the initial stage of milling operation. Fine Cu2O
particles were fabricated after 25 h of milling. The
crystallite size and internal strain of the Cu2O
particles changes with milling time.116
14. Biological Synthesis
In nanotechnology, the development of controlled
synthesis of nanoparticles with well-de¯ned shape,
size and composition is a big challenge. Metallic
nanoparticles exhibit unique properties when com-
pared with conventional metallic materials. This
could be utilized in many new interesting applica-
tions such as biomedical sciences and electronics
industries.117
Biosynthesis of nanoparticles was developed to
overcome the problems of physical and chemical
synthesis like cost and hazardous chemicals. Gericke
and Pinches investigated the use of highly struc-
tured physical and biosynthetic activities of micro-
bial cells for the synthesis of nanosized materials.
Synthesis of gold nanoparticles of various
morphologies and sizes in two fungal cultures was
studied in this paper. Size of nanoparticles and the
rate of particle formation were controlled by con-
trolling parameters such as pH, gold concentration
and exposure time of AuCl  4.
118
Biosynthesis of copper nanoparticles is also con-
sidered as a chemical or bottom-up technique.
Esteban-Cubillo et al. prepared copper nano-
particles with narrow size distribution by means of
wet chemical route. Copper nanoparticles embed-
ded into submicron particles of sepiolite were used
for biological applications.119
 A. Tamilvanan et al.

The antibacterial e®ect of copper nanoparticles
into sepiolite was observed using two di®erent
microorganisms: gram-positive bacterium (Staphy-
lococcus aureus) and a gram-negative bacterium
(Escherichia coli), respectively.119 The three im-
portant parameters that should be considered in
biosynthesis of copper nanoparticles are choice of
solvent medium used, the choice of nontoxic mate-
rial for stabilization and the choice of reducing
agent. Microorganisms, fungi, bacteria actinomy-
cetes and plants are used for synthesis of nano-
particles.12
The preparation of copper nanoparticles by bio-
synthesis involves wide range of applications based
on their morphology. Synthesis of copper nano-
particles using clove were reported in this paper.
Copper sulfate was reduced with aqueous solution
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Int. J. Nanosci. 2014.13. Downloaded from www.worldscientific.com
such as high melting point temperature, magnetism,
electrical and thermal conductivity, light absorp-
tion and high heat transfer. Copper nanoparticles
were used as an antimicrobial agent due to their
high surface-to-volume ratio and easy interaction
with other particles to enhance their antimicrobial
e±ciency. Copper nanoparticles are highly reactive
compared to other metallic nanoparticles. Due to
these special properties and small dimensions, cop-
per nanoparticles ¯nds important application in
heat transfer systems,121 sensors,122 high strength
materials,123 catalysts,124 antimicrobial materi-
als,125,126 etc.
Synthesis of Cu nanoparticles using a single
precursor by controlling the growth temperature
was discussed. Selective absorption of oleylamine
plays a vital role in the growth process. The yield of

of clove extracts. The mean particle size of copper
nanoparticles was found to be in the range of
5–40 nm. Biosynthesis does not involve any harmful
and environmentally toxic chemicals used for syn-
thesis. Aqueous solutions of copper particles reveals
good stability and prevents oxidation.120
15. Applications
Copper nanoparticles have received considerable
attention due to their physicochemical properties
production of biphenyl from the iodobenzene
determines the catalytic activity of synthesized
copper nanoparticles.127
The usage of biodiesel in automotive engines is
limited due to its low performance and high nitrogen
oxide emission. Nanocopper particles was used as the
fuel additive for diesel engine with Soya bean bio-
diesel (B10). The copper nanoparticles were prepared
using electrochemical method and the size of Cu
nanoparticles were in the range of 40–50 nm. Nano-
copper particles exhibits better engine performance

Table 5. Summary of characterization techniques.

Technique Purpose

XRD Used to determine crystal structure of unknown material and to measure size and shape of unit cell from
angular positions of di®raction peaks.
SEM Used to provide information about the sample including morphology, chemical composition, and
crystalline structure and orientation of materials.
TEM Used to provide information about morphologic, compositional and crystallographic structure of sample.
FTIR Used to obtain an infrared spectrum of absorbance, emission and to provide information regarding
functional groups.
UV-Vis UV-visible absorption spectra can be used to identify compounds and to measure the concentrations of
colored solutions.
LPSA Laser di®raction is a technique used in particle sizing for materials ranging from hundreds of manometers
up to several millimeters in size.
DLS It is also called as QELS which is used for measuring the size and size distribution of molecules and
particles.
AFM It is a type of scanning probe microscopy used to measure to measure surface morphology and properties
to construct a 3D image of the surface.
XPS Used for determining the elemental composition at a solid surface by measuring the energy of electrons
emitted with respect to X-rays of di®erent frequency.
TGA TGA is used to measure changes in physical and chemical properties as function of time or increasing
temperature.
Raman spectroscopy Used to provide detailed information about chemical composition and the structure.
EDX or EDAX (EDS) EDX is also called as EDS or EDAX which is used to identify the elemental composition of materials.

1430001-18
 Copper Nanoparticles: Synthetic Strategies, Properties and Multifunctional Application
and reduced nitrogen oxide emission when compared
to other formulations.
Copper nanoparticles form copper oxide when
they are exposed to air. To protect copper nano-
particles from oxidation with air, they are usually
coated with organic and inorganic coating such as
silica and carbon.128–130 The oxidation resistance of
the coated copper nanoparticles was higher than
that of pure copper powder.
Anti-microbial e®ects of metal nanoparticles
received considerable attention from both medical
and technological point of view. Metallic Cu
particles was used as an anti-infective agent for
replacing Ag and other noble metal composites and
¯nds applications such as water treatment, food
processing and protection of medical instruments.
Glucosamine-functionalized copper nanoparticles
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Int. J. Nanosci. 2014.13. Downloaded from www.worldscientific.com
synthesized from injection pump-assisted reaction
environment and in situ re°ux condensation exhi-
bits outstanding anti bacterial activity against two
Gram-negative and Gram-positive strain. The dy-
namic and structural light scattering reveals that
glucosamine functionalized copper nanoparticles are
spherical in shape with hybrid morphology.
Metallic copper nanoparticles and its composites
provide °exible interface activity in biological and
biosensing applications due its special properties
like bio compatibility, high stability against aggre-
gation and hydrophilic character. Glucosamine-
surface-modi¯ed copper nanoparticles prepared by
integration of injection pump and ultra-
sonochemistry. Even though bulk microstructures
and the nanostructure of metallic copper demon-
strate distinct applications, the functionalized cop-
per nanoparticles exhibits advanced features such as
high thermal stability, electrochemical feasibility
toward biomolecule (C-reactive protein, CRP) de-
tection and more crystallinity.
The development of miniaturized nanodevices
that incorporates electronic, chemical, photonic and
biological features is essential for future electronic
and sensing devices. The photosensitivity and ex-
tensive cross section of metal nanoparticles makes
them highly applicable in several applications such
as optical sensors and in surface enhanced spectro-
scopes. Cu nanoparticles prepared by nanosphere
lithography may potentially be used for replace
expensive metals of Ag and Au in certain applica-
tions. Electrochemical capacitors are received con-
siderable attention because of their long life cycle,
high power density and excellent reversibility.
Copper oxide multilayer nanosheets prepared by
1430001-19
chemical bath deposition method shows hydrophilic
nature with water and the copper oxide electrode
exhibits super capacitance of 43 Fg–1. This shows
copper oxide thin ¯lms are most suitable electrode
material for electrochemical capacitors.
16. Characterization Techniques
It is necessary to characterize the nanoparticles in
order to understand the control of synthesis and
their uses in wide applications. Various techniques
are available for synthesis of copper nanoparticles.
Microscopic techniques such as XRD, TEM, UV-Vis,
SEM, FTIR, TGA, DLS, EDX or EDS, LPSA, HR-
TEM, STEM, XPA and AFM are commonly used to
characterize the nanoparticles. Some of the impor-
tant physical properties like size and shape of par-
ticle, size distribution, crystallinity and morphology
of nanoparticles were investigated using these char-
acterization techniques. The purpose of using vari-
ous characterization techniques are given in Table 5.
17. Conclusions
Synthesis of nanoparticles can be broadly classi¯ed
into two categories namely top-down (physical
method) and bottom-up method (chemical and bio-
logical method). Physical method of preparing
nanoparticles requires expensive equipments, high
temperature and vacuum systems. Biological meth-
ods are also used for synthesis of copper nano-
particles but due to lack of knowledge and experience
it is not applicable to produce nanoparticles.
Chemical methods are employed for synthesis of
nanoparticles due to its low cost, simple operation,
high °exibility, easy availability of equipments, no
need of vacuum systems, environment friendly and
provides high yield in ambient conditions. A detailed
study of chemical methods reveals that electro-
chemical method is suitable for synthesis of copper
nanoparticles and also there are number of techni-
ques available for producing nanoparticles using
chemical reduction method. But the use of inert gas
atmosphere to prevent oxidation and the use of dif-
ferent types of toxic and costly chemicals as reducing
agent makes the production costly. In our case, a
simple and low-cost electrochemical method is se-
lected to synthesize copper nanoparticles at faster
reaction rate. The major advantage of this method is
to control the shape, size and morphology of copper
nanoparticles by optimizing or varying the reaction
 A. Tamilvanan et al.
parameter and there is no need to use inert gas at-
mosphere, toxic chemicals, high pressure and energy.
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