5740 Langmuir 2007, 23, 5740-5745

Synthesis of Size-Controlled and Shaped Copper Nanoparticles

Derrick Mott, Jeffrey Galkowski, Lingyan Wang, Jin Luo, and Chuan-Jian Zhong*
Department of Chemistry, State UniVersity of New York at Binghamton, Binghamton, New York 13902

ReceiVed December 4, 2006. In Final Form: February 21, 2007

The synthesis of stable, monodisperse, shaped copper nanoparticles has been difficult, partially because of copper’s
propensity for oxidation. This article reports the findings of an investigation of a synthetic route for the synthesis of
size-controllable and potentially shape-controllable molecularly capped copper nanoparticles. The approach involved
the manipulation of reaction temperature for the synthesis of copper nanoparticles in organic solvents in the presence
of amine and acid capping agents. By manipulating the reaction temperature, this route has been demonstrated for
the production of copper nanoparticles ranging from 5 to 25 nm. The size dependence of the melting temperature of
copper nanoparticles, especially for surface melting, is believed to play an important role in interparticle coalescence,
leading to size growth as the reaction temperature is increased. Control of the reaction temperature and capping
molecules has also been demonstrated to produce copper nanoparticles with different shapes such as rods and cubes.
The previously proposed combination of the selective formation of a seed precursor and a selective growth direction
due to the preferential adsorption of capping agents on certain nanocrystal facets is believed to be responsible for shape
formation by kinetically controlling the growth rates of crystal facets. The nanoparticles are characterized using TEM,
XRD, and UV-visible techniques. A mechanistic consideration of the size control and shape formation is also
discussed.

Introduction The chemical reduction of copper ions in mixed reverse micelles

The ability to synthesize nanoparticles of different compositions (using an AOT surfactant in water/isooctane) was reported by
with desired sizes and shapes is important in exploring their Pileni and co-workers to produce copper nanocrystals with
applications in catalysis, sensors, microelectronics, and many different shapes.9 The nanoparticle shape was found to depend
other areas of nanotechnology.1,2 The nanoscale properties of on the concentration of reducing agents, with spherical shapes
copper and its alloys have found applications in catalysis (e.g., formed in lower concentrations and other shapes such as
water-gas shift catalysts and gas detoxification catalysts3,4). The pentagons, cubes, tetrahedra, and elongated forms in higher
synthesis of copper nanoparticles with controllable sizes, shapes, concentrations. The formation of certain initial seed shapes and
and surface properties is vital to exploring copper-based the difference in the relative rates of growth on different crystal
catalysis.1,2 Such abilities will also lead to an increased use of facets were proposed to explain the shape formation.9 This is one
copper in many other areas of nanotechnology that are currently of the first mechanisms proposed to explain shape formation on
dominated by the use of gold, silver, and platinum nanoparticles. the nanoscale, which is quite intriguing. An understanding of
Although there are a number of approaches to synthesizing copper how different synthetic conditions or control parameters are
nanoparticles under specific conditions,5 few methods have been operative mechanistically in the formation of the nanoscale sizes
established to control the size and shape effectively. Because of and shapes is therefore elusive.
the propensity of surface oxidation of copper,6 a key issue is This report describes the findings of an investigation of the
whether copper nanoparticles can be produced with controllable synthesis of copper nanoparticles with controlled sizes and
sizes and shapes. To date, relatively limited attempts have potentially shapes by a combination of controlled reaction
succeeded in synthesizing copper nanoparticles with controllable temperature and capping agents (Scheme 1). This route stems
sizes, shapes, and surface properties. In previous reports, copper from previous work, including our own8,10,11 demonstrating the
nanoparticles have been synthesized using methods that include synthesis of different alloy nanoparticles in organic solvents with
organic encapsulation in an aqueous phase,7 the encapsulation molecular capping agents and elevated reaction temperature. It
of copper in a thiol capping agent,6 and thermal decomposition.8 also takes advantage of the possible effect of particle sizes on
The copper nanoparticles resulting from these methods had either the melting temperature of copper nanoparticles under the reaction
limited size monodispersity or were susceptible to oxidation.5,6 conditions. This route not only yields copper nanoparticles of
controllable sizes but also produces shaped nanoparticles,
* To whom correspondence should be addressed. E-mail: cjzhong@ including rods and cubes. Such abilities are important for
binghamton.edu.
(1) Hoover, N.; Auten, B.; Chandler, B. D. J. Phys. Chem. B 2006, 110, 8606.
engineering the sizes and shapes of copper-based nanoparticles
(2) Niu, Y.; Crooks, R. Chem. Mater. 2003, 15, 3463. of different compositions for potential applications in catalysis
(3) Ressler, T.; Kniep, B. L.; Kasatkin, I.; Schlögl, R. Angew. Chem. 2005, and sensors.12
44, 4704.
(4) (a) Vukojevic, S.; Trapp, O.; Grunwaldt, J.; Kiener, C.; Schth, F. Angew. Experimental Section
Chem., Int. Ed. 2005, 44, 7978. (b) Barrabes, N.; Just, J.; Dafinov, A.; Medina,
F.; Fierro, J. L. G.; Sueiras, J. E.; Salagre, P.; Cesteros, Y. Appl. Catal. B 2006, Chemicals. Copper(II) acetylacetonate (Cu(acac)2, 98%) was
62, 77. obtained from Lancaster. Oleic acid (99%) was obtained from
(5) (a) Arul Dhas, N.; Paul Raj, C.; Gedanken, A. Chem. Mater. 1998, 10,
1446. (b) Zhu1, H.; Zhang, C.; Yin, Y. Nanotechnology 2005, 16, 3079. (9) Salzemann, C.; Lisiecki, I.; Urban, J.; Pileni, M.-P. Langmuir 2004, 20,
(6) Chen, S.; Sommers, J. M. J. Phys. Chem. B 2001, 105, 8816. 11772.
(7) Kim, Y. H.; Kang, Y. S.; Lee, W. J.; Jo, B. G.; Jeong, J. H. Mol. Cryst. (10) Sun, S.; Fullerton, E. E.; Weller, D.; Murray, C. B. Trans. Magn. 2001,
Liq. Cryst. 2006, 445, 231. 37, 4.
(8) (a) Sun, S.; Murray, C. B.; Weller, D.; Folks, L.; Moser, A. Science 2000, (11) Luo, J.; Han, L.; Kariuki, N. N.; Wang, L.; Mott, D.; Zhong, C. J.; He,
278, 1989. (b) Fievet, F.; Lagier, J. P.; Figlarz, M. MRS Bull. 1989, 14, 29. T. Chem. Mater. 2005, 17, 5282.

10.1021/la0635092 CCC: $37.00 © 2007 American Chemical Society

Published on Web 04/04/2007
Synthesis of Copper Nanoparticles Langmuir, Vol. 23, No. 10, 2007 5741

Scheme 1. Schematic Illustration of the Synthesis of Copper Nanoparticles in the Presence of Capping Agents in Organic
Solventa

a The reduction reaction occurs at elevated temperature.

Alfa Aesar. 1,2-Hexadecanediol (90%), octyl ether (99%), oleyl varying the reaction temperature in the range of 150-190 °C.
amine (70%), hexane, and other common solvents used were obtained As the temperature of the reaction was raised, solutions with the
from Aldrich. resulting nanoparticles were found to become darker in color.
Synthesis. The synthesis of copper nanoparticles in organic The size evolution and shape formation, which are highly
solution was achieved through the modification of a previous method
dependent on the reaction temperature, will be detailed in the
that was reported for the synthesis of FePt nanoparticles8a and PtVFe
nanoparticles.11 In the modified synthesis, copper(II) acetylacetonate next two subsections. As a general observation, the color evolution
was added to octyl ether to create a 20 mM solution of copper(II). of the reaction solution under different temperatures was found
Then 1,2-hexadecanediol (a reducing agent)8b was added to the to serve as an indication of particle size evolution. When the
solution (60 mM). The solution was heated under argon gas to a reaction temperature was held at 150 °C, a yellow solution was
temperature of 105 °C with stirring. The solution was held at observed (Figure 1A). This color corresponded to small copper
105 °C for 10 min, and then both oleic acid and oleyl amine capping nanoparticles. As the reaction temperature was increased, the
agents were added to the solution to create 20 mM solutions of each. color of the solution with the as-synthesized copper nanoparticles
The solution was heated to higher temperatures, which was varied showed a series of color changes ranging from light yellow to
from 150 to 210 °C. Once at high temperature, the solution was left orange to dark brown to purple-brown depending on the reaction
to react for 30 min. The solution was then cooled to room temperature.
temperature. A brown solution was observed for particles
Finally, the reacted solution was mixed with ethanol, and the particles
were allowed to precipitate overnight. The supernatant was removed, synthesized at 180 °C (Figure 1B).
and the nanoparticle sediment was washed and dried using a stream UV-vis spectra of the resulting nanoparticle solutions
of nitrogen gas. We note that we have not yet determined the synthetic (Supporting Information) displayed a surface plasmon (SP)
yields, but a complete determination of the yields at different reaction resonance band at ∼600 nm, characteristic of copper nanopar-
temperatures is part of our ongoing work, which will be reported ticles. Copper nanoparticles synthesized by other methods were
in the near future. The nanoparticles were suspended in hexane and reported to display an SP band at ∼570 nm.7,9 The exact position
were ready for analysis. of this band may shift depending on the individual particle
Instrumentation and Measurements. The nanoparticles were
characterized using thermogravimetric analysis (TGA), UV-vis properties including size, shape, solvent used, and capping agent
spectroscopy, transmission electron microscopy (TEM), and X-ray employed. The spectrum for the as-synthesized small particles
powder diffraction (XRD). showed a rising feature at ∼440 nm. For the solution of
TGA analysis was performed on a Perkin-Elmer Pyris 1-TGA to nanoparticles synthesized at 150 °C, a rising band at about 435
determine the weight of the organic shell. Typical samples weighed nm was apparent in the UV-vis spectrum. As the particles became
∼4 mg and were heated in a platinum pan. Samples were heated in larger, this band shifted to higher wavelength (up to ∼600 nm).
20% O2 at a rate of 10 °C/min. A strong SP band was observed at 591 nm for the formation of
UV-vis spectra were acquired with an HP 8453 spectropho- large copper nanoparticles synthesized at 200 °C.
tometer. A quartz cell with a path length of 1 cm was used, and
spectra were collected over the range of 200-1100 nm. TGA was used to assess the relative composition of the organic
TEM was performed on a Hitachi H-7000 electron microscope capping agents on the nanoparticles.11 Figure 2 shows a
(100 kV). Copper nanoparticle samples were suspended in hexane representative TGA curve obtained for the 6-nm copper nano-
solution and were drop cast onto a carbon-coated copper grid, particles that were heated from 25 to 400 °C under oxygen. It
followed by solvent evaporation in air at room temperature. is evident that the mass decrease due to the removal of the capping
XRD data was collected on a Philips X’Pert diffractometer using agents took place in the range of about 150 to 300 °C. At
Cu KR radiation (λ ) 1.5418 Å). The measurements were made in temperatures beyond about 400 °C, the increase in mass was due
reflection geometry, and the 2θ diffraction (Bragg) angles were to the oxidation of the copper metal. The mass change can be
scanned at a step of 0.025°. Each data point was measured for at translated to the ratio of capping molecules to copper particles.
least 20 s, and several scans were taken of the sample.
About 39% of the sample mass was due to the capping shell,
Results and Discussion leaving 61% of the mass to copper. For a 50/50 mixture of oleic
acid/oleylamine capping molecules on a 6-nm copper nanopar-
The reaction for the synthesis of copper nanoparticles of ticle, a spherical model calculation11 yields a value of 24% for
different sizes, as shown in Scheme 1, was accomplished by the oleic acid/oleylamine capping organic materials. The deviation
(12) (a) Zhong, C. J.; Luo, J.; Maye, M. M.; Han, L.; Kariuki, N. N. In
of the experimental value from the theoretical value could be
Nanotechnology in Catalysis; Zhou, B., Hermans, S., Somorjai, G. A., Eds.; partially due to residual octyl ether in the sample.11 A preliminary
Kluwer Academic/Plenum Publishers: New York, 2004; Vol. 1, Chapter 11, pp differential scanning calorimetry (DSC) experiment was also
222-248. (b) Nanoparticles and Nanostructures in Sensors and Catalysis; MRS
Proceedings; Zhong, C. J., Kotov, N. A., Daniell, W., Zamborini, F. P., Eds.; performed for the 6-nm copper nanoparticles in an attempt to
Warrendale, PA, 2006; Vol. 900E. estimate the approximate melting point (Supporting Information).
5742 Langmuir, Vol. 23, No. 10, 2007 Mott et al.

Figure 1. Photographs of solutions of Cu nanoparticles synthesized

at (A) 150 and (B) 180 °C. A green laser beam was shone through
the solutions, which produces the observed light scattering due to
the presence of nanoparticles in the solutions.

Figure 2. TGA curve for copper nanoparticles synthesized at

150 °C.

The resulting heating curve showed an endothermic peak

beginning around 450 °C with a maximum near 550 °C, which
is likely associated with the melting of the copper nanoparticles.
However, a more detailed analysis is needed to substantiate this
conclusion.
The nanoparticles synthesized under different conditions were
also studied to determine their solubility and relative stability.
Most of the copper nanoparticles were soluble in hexane. It was
observed that the well-suspended nanoparticles remained in
solution without precipitating for several weeks. The precipitated
particles could also be easily resuspended. When additional oleyl
amine or oleic acid was added to the nanoparticle solution, the
solution was found to turn blue, suggesting the formation of
copper(II) ions. This instability, although the exact origin is not
clear, appears to reflect an equilibrium shift that promotes the
oxidation of Cu(0) to form Cu(II) complexes with oleyl amine
or oleic acid ligands.6 To determine whether the synthesized
copper particles were stable under ambient conditions (∼20 °C),
a small amount of the nanoparticle solution was placed in a vial
and left open to the air for several weeks. There were no indications Figure 3. TEM images of Cu nanoparticles synthesized at (A) 150,
of changes in the solution color, including an unchanged SP (B) 160, and (C) 190 °C.
band in the UV-vis spectra. TEM imaging of the samples after
several weeks also showed that the as-synthesized nanoparticles were small with flowerlike outlines (A). At 160 °C, the particles
were stable under ambient conditions. This stability is desired became larger and showed a tendency to cluster (B). As the
because the nanoparticles can be stored under ambient conditions temperature was increased to 190 °C, the particles became even
for long periods of time before use. The next two subsections larger, more spherical, and showed a better-defined interparticle
describe the morphological properties of the copper nanoparticles separation (C).
in terms of sizes and shapes. The average sizes of the particles range from about 5 to 25
Copper Nanoparticles of Different Sizes. The analysis of nm depending on the reaction temperature, with the standard
the copper nanoparticles showed an increasing trend in the deviation of the particle sizes ranging from (1.8 to (6.5 nm,
average size with the reaction temperature. Figure 3 shows a respectively. The particles synthesized at temperatures below
representative set of TEM images for copper nanoparticles 190 °C were highly monodisperse, with standard deviations of
synthesized at three different temperatures. At 150 °C, the particles less than 3.5 nm. When the synthesis temperature was raised
Synthesis of Copper Nanoparticles Langmuir, Vol. 23, No. 10, 2007 5743

Figure 4. Plot of nanoparticle size vs synthesis temperature up to

190 °C. The line represents the linear regression of the data.
Figure 5. Theoretical modeling of the melting temperature of copper
nanoparticles as a function of particle radius based on eq 1. The
above 190 °C, the nanoparticles showed increased standard parameters used for the theoretical calculation were Fs ) 8960 and
deviations (e.g., 24.0 ( 6.5 nm (190 °C)). Fl ) 8020 kg/m2, L ) 20 500 J/Kg,15 and γs ) 1.29 and γl ) 1.11
Figure 4 shows a plot of the average particle size versus the J/m2.16 The actual temperatures used in the synthesis vs the particle
reaction temperature. The average size of the nanoparticles was size obtained are included as square symbols.
found to increase approximately linearly with temperature. The
linear regression of the data yields 0.46 nm/°C. This finding is One of the important conditions for interparticle coalescence
significant, demonstrating the important role of reaction tem- is surface melting. As demonstrated in our earlier work for the
perature in the control of particle size. size evolution of gold nanoparticles at elevated temperatures,
the decrease in the melting point for nanosized particles is an
A close examination of some of the large particles seems to
important factor for interparticle coalescence.13 The decrease in
reveal subtle cluster features. This observation may hint at the
the melting point with reduced particle size can be explained by
possibility of coalescence of smaller particles, which provides
the early thermodynamic model describing melting curves for
some implications to the understanding of the mechanistic origin
fine metal particles,13a,14 which relates the melting point of
of the size dependence on temperature. It is known that the growth
nanoparticles to that of its bulk metal by the equation
of nanoparticles is influenced by the strength of adsorption of

[ ()]
the encapsulating ligands and the competition between the
Tr - T ∞ 4 Fs 2/3
interparticle aggregation for the growth of particles and the )- γs - γl (1)
molecular encapsulation for the stabilization of nanoparticles. T∞ FsL2r Fl
For growth to occur, desorption of an encapsulating ligand on
the particle must occur, allowing a metal atom or neighboring where Tr and T∞ are the melting temperatures of the particle and
particle to gain access to the particle surface.13 The adsorption the bulk solid, respectively, r is the radius of the particle, Fs and
of capping molecules on the copper nanoparticles is favored at Fl are the densities of the solid and the liquid, respectively, γs
lower temperatures, thus limiting the particle growth rate. and γl are the surface energies of the solid and the liquid,
However, as the temperature is increased, desorption of the respectively, and L is the heat of fusion.13a The theoretical model
capping ligand from the nanoparticle surface is favored, increasing predicts a decrease in the melting point with decreasing size for
the opportunities for interparticle coalescence. On the basis of copper particles (Figure 5).
the TGA data, desorption of the capping molecules from the The implication of this trend is that smaller particles have a
nanoparticle surface likely occurs at ∼150 °C. Below ∼150 °C, tendency to melt or partially melt at the reaction temperature.
there were no nanoparticles detected. Therefore, the nanoparticles The actual temperatures used in the synthesis were much smaller
synthesized at 150 °C acted as seed particles for the growth of than the theoretical temperatures for the melting curve. For the
larger particles at elevated reaction temperature. In addition to smallest particle size, the reaction temperature was closer to that
the theoretical basis for the decreased melting point of nanoscale in the theoretical curve, with a difference of ∼100 °C. On the
copper particles, there are experimental studies indicating that basis of this observation, it is likely that the surface melting of
nanoscale copper materials exhibit depressed melting points. the nanoparticles is responsible for the interparticle coalescence,
For example, copper nanorods have recently been shown to exhibit leading to size growth as the reaction temperature is increased.
a range of melting temperature as low as 350-550 °C.17 A DSC This temperature-controlled size growth is to our knowledge the
study of gold nanoparticles coated by a silica shell concluded first example discussing the important role of surface melting
that for gold nanoparticles of 10 nm diameter melting occurs at in the synthesis of copper nanoparticles. Although the lowering
a much more depressed temperature than for its bulk counter- of the melting point is inversely proportional to the particle size
part.18 (r), the surface melting temperature could be even lower (e.g.,
∼140 °C for 2-nm Au).13 The relative change in temperature is
(13) (a) Maye, M. M.; Zheng, W. X.; Leibowitz, F. L.; Ly, N. K.; Zhong, C. also related to the capping-dominated surface tension. Under
J. Langmuir 2000, 16, 490. (b)Schadt, M. J.; Cheung, W.; Luo, J.; Zhong, C. J. such surface melting and surface tension effects, the driving
Chem. Mater. 2006, 18, 5147.
(14) Buffat, Ph.; Borel, J. P. Phys. ReV. A 1976, 13, 2287. force for the coalescence of two surface-melt Cu particles is the
(15) Lisiecki, I.; Sack-Kongehl, H.; Weiss, K.; Urban, J.; Pileni, M.-P. Langmuir reduction in free energy through a reduction in surface area (e.g.,
2000, 16, 8802.
(16) Matsumoto, T.; Fujii, H.; Ueda, T.; Kamai, M.; Nogi, K. Meas. Sci.
increase in size).
Technol. 2005, 16, 432. Formation of Shaped Cu Nanoparticles. By further modify-
(17) Karabacak, T.; DeLuca, J. S.; Wang, P.-I.; Ten Eyck, G. A.; Ye, D.; ing the synthesis procedure, copper nanoparticles with signifi-
Wang, G.-C.; Lu, T.-M. J. Appl. Phys. 2006, 99, 064394.
(18) Dick, K.; Dhanasekaran, T.; Zhang, Z.; Meisel, D. J. Am. Chem. Soc. cantly increased populations of shaped particles were produced.
2002, 124, 2312. It was found that copper nanoparticles with different shapes
5744 Langmuir, Vol. 23, No. 10, 2007 Mott et al.

Figure 7. XRD pattern of the copper nanoparticles synthesized at

210 °C.

Figure 6. TEM image of copper nanoparticles synthesized at Scheme 2. Schematic Illustration of the Growth Mechanism
210 °C. The enlarged views show (A) cube-, (B) tetrahedral-, and for the Formation of (A) Cube-Shaped Particles from a
(C) rod-shaped particles. Cuboctahedron Seed and (B) Rod-Shaped Particles from a
Decahedral Seed
began to form at temperatures above 190 °C. Figure 6 shows a
representative TEM image of the as-synthesized particles derived
from the reaction temperature of 210 °C and careful control of
the initial heating rate in the presence of the capping agents.
Copper nanoparticles shaped as cubes, rods, and tetrahedrons
are evident, in addition to a certain percentage of spherically
shaped particles. Shape formation began at 190 °C but was not
prominent until 200 °C, for which shapes such as rods and cubes
became common among the particles. In all of the samples that
formed shapes, rods were the most common shape, demonstrating
that the formation of copper nanoparticles at high temperature
favors the formation of rods. As indicated by the enlarged views,
the cubes, rods, and tetrahedrons have well-defined shapes. The
cube-shaped particles are 200 nm in size. The rod-shaped particles
are around 700 nm in length and about 100 nm in width, with
an aspect ratio as high as ∼7. It is important to note that these
shaped particles do not show any hint of the possibility of
impurities such as copper oxides (CuO, Cu2O). The results are
coalescence of smaller particles as observed for the spherical
quite consistent with those reported by others for Cu nanoparticles
particles described earlier, thus ruling out the simple coalescence
or nanorods prepared by different methods.19
mechanism for shape formation. The observation of these
The mechanism proposed previously by Pileni and co-workers9
shapes is remarkable considering the relatively small change in
for shape formation in reverse micelle synthesis, as illustrated
the synthetic temperature that was required to initiate their
in Scheme 2, seems to be applicable to the synthesis of shaped
formation.
nanoparticles using the method discussed in this article. The
There is a remarkable resemblance between the shapes of the
observation of several shapes in the synthesized particles is
nanoparticles synthesized using our method and those reported
indicative of the formation of several different seed precursors.
by Pileni and co-workers.9 In the reported work,9 Cu(AOT) 2 and
These seeds then grow, regulated by the capping agents, along
NaAOT were solubilized in isooctane with a controlled percentage
different directions of the nanocrystal into particles with various
of water. This forms reverse micelles in which Cu(AOT) 2 is
shapes. As shown in Scheme 2A, a cuboctohedron seed particle
reduced by various concentrations of hydrazine. On the basis of
serves as a precursor. If this seed were to grow equally in all
the observation of copper particles with spheres, rods, cubes,
directions, then it would enlarge into a roughly spherically shaped
and tetrahedral shapes, the mechanism proposed for the formation
particle; however, there is a difference in the rate of growth
of these shaped copper nanocrystals involves (i) the initial
along its faces. The difference in the speed of growth is caused
formation of a decahedral, cuboctohedral, or tetrahedral precursor
by the varying surface free energy and thus the varying strength
and (ii) the preferential adsorption of capping agents on the
of capping agent adsorption. Because the capping agent adsorbs
nanocrystal facets in order to control the growth rates of the
more strongly to the 100 face of the cuboctohedron nanocrystal,
crystal facets kinetically.9 For the growth process of copper
the 111 faces grow at a faster rate than the 100 faces. This kinetic
nanoparticles under our synthesis conditions, we used two capping
difference leads to the formation of a cube-shaped particle instead
agents. It is possible that one of the capping agents favors
of a sphere. Similarly, for a decahedron seed particle, illustrated
adsorption to one of the nanocrystal facets (e.g., 111, 110, or
in Scheme 2B, the 111 faces grow at a faster rate than the 100
100) while allowing the other faces to grow more quickly.
faces, causing the kinetically favored growth of the 111 faces
To confirm the crystalline properties of the nanocrystals, the
into an elongated rod-shaped particle. It is important to note that
as-synthesized nanoparticles were examined using XRD. As
the final size of the particles is not solely dependent on the seed
shown in Figure 7, the nanoparticles display high crystallinity.
shape but is also dependent on the total growth time of the particle.
The diffraction peaks at 2θ ) 43.5, 50.6, and 74.3 can be indexed
as the [111], [200], and [220] planes of copper with cubic (19) Panigrahi, S.; Kundu, S.; Ghosh, S. K.; Nath, S.; Praharaj, S.; Basu, S.;
symmetry. The pattern is very clean, with no indication of Pal, T. Polyhedron 2006, 25, 1263.
Synthesis of Copper Nanoparticles Langmuir, Vol. 23, No. 10, 2007 5745

A key question is what synthesis parameters are necessary to surface melting in the synthesis of copper nanoparticles. The
achieve precise control of the formation of the precursor seed feasibility of synthesizing copper nanoparticles with well-defined
particles and the relative adsorption of the two capping agents shapes such as rods and cubes has also been demonstrated.
on the nanocrystal surfaces. Preliminary experiments have Mechanistically, shape formation is linked to a combination of
indicated that the manipulation of the reaction temperature and the initial formation of a seed precursor and the preferential
the relative ratio of the two capping agents could lead to variations adsorption of capping agents on selected nanocrystal facets in
of the differently shaped copper nanoparticles. Therefore, order to control the growth rates of certain crystal facets
establishing the correlation between the nanocrystal shape and kinetically. More experiments are underway to determine the
these two sets of parameters will allow the selective synthesis detailed correlation between the particle size or shape and the
of specifically shaped copper nanoparticles. control parameters such as reaction temperature and capping
agents, which will have important implications in the engineering
Conclusions
of metal nanoparticles as building blocks for applications in
A new route for the synthesis of copper nanoparticles in organic many areas of nanotechnology, including catalysis and chemical
suspensions has been demonstrated. The size, shape, and stability sensing.
of the nanoparticles are highly dependent on the reaction
temperature, with the particle size increasing with the reaction
Acknowledgment. Financial support of this work from the
temperature in an approximately linear manner. On the basis of
National Science Foundation (CHE 0349040) is gratefully
a theoretical consideration of the size dependence of the melting
acknowledged.
temperature of copper nanoparticles, the surface melting of the
nanoparticles is believed to be responsible for the interparticle
coalescence, leading to size growth as the reaction temperature Supporting Information Available: UV-vis and DSC data.
This material is available free of charge via the Internet at http://pubs.acs.org.
is increased. This temperature-controlled size growth is to our
knowledge the first example discussing the important role of LA0635092