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Poly(allylamine)-Stabilized Colloidal Copper Nanoparticles: Synthesis,

Morphology, and Their Surface-Enhanced Raman Scattering Properties
Yanfei Wang†,‡ and Tewodros Asefa*,†,‡
†
Department of Chemistry and Chemical Biology, Rutgers, The State University of New Jersey, 610 Taylor
Road, Piscataway New Jersey 08854, and ‡Department of Chemical Engineering and Biochemical Engineering,
Rutgers, The State University of New Jersey, 98 Brett Road, Piscataway, New Jersey 08854

Received November 4, 2009. Revised Manuscript Received January 24, 2010

Poly(allylamine)-stabilized spherical- and rod-shaped copper nanoparticles are synthesized by a simple chemical
reaction. The synthesis is performed by the reduction of copper(II) salt with hydrazine in aqueous solution under
atmospheric air in the presence of poly(allylamine) (PAAm) capping agent. Noteworthy of the advantages of the
synthetic method includes its production of water dispersible copper nanoparticles at room temperature under no inert
atmosphere, making the synthesis more environmentally friendly. The resulting copper nanoparticles are investigated by
UV-vis spectroscopy and transmission electron microscopy (TEM). The results demonstrate that the amount of NaOH
used is important for the formation of the copper nanoparticles while the reaction time and concentration of PAAm play
key roles in controlling the size and shape of the nanoparticles, respectively. The resulting colloidal copper nanoparticles
exhibit large surface-enhanced Raman scattering (SERS) signals.

1. Introduction Recently, a few different types of synthetic methods for

Noble metal nanoparticles have attracted considerable atten-
tion owing to their potential applications in such fields as
catalysis, biology, electronics, and information technology.1-4
In particular, copper nanoparticles are widely used as a catalyst
for various chemical transformations including water-gas shift5
and gas detoxification6 reactions, and as an electrocatalyst in
solid-oxide fuel cells.7 Another important application for copper
nanomaterials is their potential use for surface-enhanced Raman
scattering (SERS), whose enhancement factor is dependent on the
strength of the local electric field and the nature of the material.8
Indeed, it has already been reported that noble metals such as Au,
Ag, and Cu nanostructures generate large SERS. However, the
investigation of Cu nanoparticles synthesized in solution phase
as SERS substrate has remained largely unexplored. This is
mainly because copper nanostructures are prone to fast oxida-
tion and, consequently, are hard to synthesize chemically. This
has inspired us to develop synthetic methods for stable colloi-
dal Cu nanoparticles in aqueous solution and explore their
SERS properties.
*To whom correspondence should be addressed. Telephone: 732-445-2970.
Fax: 732-445-5312. E-mail: tasefa@rci.rutgers.edu.
(1) Xia, Y.; Xiong, Y.; Lim, B.; Skrabalak, S. E. Angew. Chem., Int. Ed. 2008, 47, 2.
(2) Tao, A. R.; Habas, S.; Yang, P. Small 2008, 4, 310.
(3) Daniel, M. C.; Astruc, D. Chem. Rev. 2004, 104, 293.
(4) Rosi, N. L.; Mirkin, C. A. Chem. Rev. 2005, 105, 1547.
(5) Ressler, T. B.; Kniep, L.; Kasatkin, I.; Schl€ogl, R. Angew. Chem., Int. Ed.
2005, 44, 4704.
(6) Vukojevic, S.; Trapp, O.; Grunwaldt, J.; Kiener, C.; Schth, F. Angew. Chem.,
Int. Ed. 2005, 44, 7978.
(7) Park, S.; Gorte, R. J.; Vohs, J. M. Appl. Catal., A 2000, 200, 55.
(8) Bozzini, B.; D’Urzo, L.; Re, M.; De Riccardis, F. J. Appl. Electrochem. 2008,
38, 1561.
(9) Wu, S.; Chen, D. J. Colloid Interface Sci. 2004, 273, 165.
(10) Chang, Y.; Lye, M. L.; Zeng, H. C. Langmuir 2005, 21, 3746.
(11) Huang, H.; Yan, F.; Kek, Y.; Chew, C.; Xu, G.; Ji, W.; Oh, P.; Tang, S.
Langmuir 1997, 13, 172.
(12) (a) Zhou, G.; Lu, M.; Yang, Z. Langmuir 2006, 22, 5900. (b) Liu, Z.; Yang, Y.;
Liang, J.; Hu, Z.; Li, S.; Peng, S.; Qian, Y. J. Phys. Chem. B 2003, 107, 12658.
(13) Gole, A.; Murphy, C. J. Chem. Mater. 2004, 16, 3633.
(14) Sau, T. K.; Murphy, C. J. J. Am. Chem. Soc. 2004, 126, 8648.
(15) Pileni, M. P. Nat. Mater. 2003, 2, 145.
making shaped copper nanoparticles including rods or cubes
have been reported.9-19 The first and most commonly used
method involves the chemical reduction of copper ions in
aqueous solution in the presence of various capping agents.
For instance, using surfactant capping agents such as cetyl-
trimethylammonium bromide (CTAB),8,9 ethylenediamine
(EDA),10 polyvinylpyrrolidone (PVP),11 and sodium dodecyl-
benzene sulphonate (DBS),12 various shaped copper nanopar-
ticles were produced by reduction of copper(II) ions. As in the
synthesis of many other metal nanomaterials, adjustment of
the synthetic parameters, in particular the type of the surfac-
tant, the preparation of the seed solution,13 temperatures, and
the ratios of additives in the growth solution14 render obvious
shape evolution of the copper nanoparticles. Pileni and her
research group demonstrated the size and shape controlled
synthesis of copper nanoparticles by using mixed reverse
micelles as a template.15 Furthermore, copper nanoparticles,
nanorods, and nanodisks with different size and shape were
synthesized by varying the water content, the concentration of
reducing agent, or the salt concentrations in AOT-water-oil
reverse micellar systems.16-19 In a second commonly used
method, copper nanoparticles were prepared in organic sol-
vents by decomposing or reducing various copper complexes in
the presence of capping agents. For instance, copper nanorods
and nanocubes were synthesized by treating Cu(acac)2 in an
octyl ether solvent in the presence of oleic acid and oleyl amine
capping agents.20 In this case, the shapes of the nanoparticles
were tuned by changing the reaction temperature. In the third
synthetic method known as the polyol reduction process,
ethylene glycol was used both as a solvent and as a reductant
for copper ions while PVP was used as a capping agent for
(16) Lisiecki, I.; Pileni, M. P. J. Am. Chem. Soc. 1993, 115, 3887.
(17) Salzemann, C.; Urban, J.; Lisiecki, I.; Pileni, M. P. Adv. Funct. Mater. 2005,
15, 1277.
(18) Cason, J. P.; Roberts, C. B. J. Phys. Chem. B 2000, 104, 1217.
(19) Lisieki, I.; Pileni, M. P. J. Phys. Chem. 1995, 99, 5077.
(20) Galkowski, M. J.; Wang, L.; Luo, J.; Zhong, C. Langmuir 2007, 23, 5740.

Langmuir 2010, 26(10), 7469–7474 Published on Web 02/11/2010 DOI: 10.1021/la904199f 7469
Article Wang and Asefa

making copper nanoparticles.21 Finally, physical vapor deposi-

tion,22,23 chemical vapor deposition,24 γ-irradiation,25 UV-light
irradiation,26 sonochemical method,27 and electrochemical app-
roach28-30 have been reported as synthetic methods for the
preparation of copper nanostructures. In general, most of the
methods reported so far have rarely resulted in copper nanoparticles
having uniform sizes below 50 nm or in high yield. Furthermore, the
procedures used in previously reported methods are rather compli-
cated, usually involving a number of steps or requiring an inert gas
such as Ar or N2 in order to avoid oxidation of the Cu nanoparticles.
Herein, we report on a one-step synthetic method to colloidal
Cu nanoparticles by reducing copper ions with hydrazine using
poly(allylamine) (PAAm) as a stabilizing agent. The advantages
of the method include the use of atmospheric air (or no use of inert
atmosphere) for the synthesis of the nanoparticles and its produc-
tion of copper nanoparticles with reasonably uniform size and
relatively higher yield. While changing the amount of NaOH used
in the synthesis was found to help us to produce pure copper
nanoparticles as opposed to copper oxide, varying the reaction
time and concentration of PAAm enabled us to control the size
and shape of the nanoparticles. Investigation of the SERS
property of the resulting colloidal copper nanoparticles showed
that the nanoparticles gave a 104 times SERS enhancement for
4-mercaptopyridine (4-Mpy) adsorbed on the nanoparticles com-
pared to bulk 4-Mpy.
Figure 1. (A) UV-vis absorbance spectra of PAAm-capped cop-
2. Experimental Section per nanoparticles that were synthesized in aqueous solution with
2.1. Materials and Reagents. Copper(II) sulfate, hydrazine 0.22 mL of PAAm and different amounts (or moles) of NaOH. (B)
hydrate solution (78-82%), poly(allylamine) solution (PAAm) Absorption maxima of the copper nanoparticles versus amount (or
(average Mw ∼ 17 000, 20 wt % in H2O), and 4-mercaptopyridine moles) of NaOH used.
(4-Mpy) (95%) were obtained from Sigma-Aldrich. Sodium
hydroxide (98.8%) was purchased from Fisher Scientific. All nanoparticle suspension on a carbon-coated copper grid and then
chemicals were used as received without further treatment. drying them in air. The dried grid was then placed under a JEOL
2.2. Synthesis of Copper Nanoparticles. In a typical synth- 1200 EX transmission electron microscope. The images were
esis of copper nanoparticles, CuSO4 (0.05 mmol) and various taken at an acceleration voltage of 120 kV. Surface-enhanced
amounts (0.2-0.3 mL) of PAAm were completely dissolved in Raman scattering (SERS) spectra were obtained on a micro-
Millipore H2O (10 mL) under vigorous stirring at 60 °C for 20 Raman instrument (Renishaw 1000, Gloucestershire, U.K.)
min, forming a transparent light-blue solution. Then, 0.6-0.8 mL equipped with a He/Ne laser (632.8 nm) and a CCD detector
of NaOH (0.5 M) was added dropwise into the above solution. operated at room temperature. The laser power at the sample
After stirring for 20 min, 1.0 mmol N2H4 3 H2O solution was position was typically 2.0 mW for SERS spectra and normal
dropped into the above solution under constant stirring. The Raman spectra.
reactor was kept in a water bath at 60 °C for 40-90 min. It should
be pointed out that N2H4 3 H2O can also increase the pH of the 3. Results and Discussion
solution. The reaction was monitored by UV-vis spectroscopy
until no change of the absorbance spectrum was observed. The 3.1. Synthesis of Copper Nanoparticles and Formation of
metallic copper nanoparticles in this work were obtained from the Copper versus Copper Oxide Nanoparticles in Aqueous
redox reaction between Cu2þ and hydrazine in basic solution in Solution. As in the synthesis of many types of colloidal nano-
the presence of PAAm capping agent. materials, copper nanoparticles also require organic ligands to
2.3. Characterization. The UV-vis absorbance spectra prevent them from irreversible aggregation in solution. Here, we
were measured with a Lambda 950 spectrophotometer used PAAm to prepare and stabilize small Cu nanoparticles.
(PerkinElmer). Transmission electron microscopy (TEM) sam- Besides providing long-term stability to the nanoparticles by
ples were prepared by casting a drop of the as-prepared copper preventing particle agglomeration, polymer capping agents such
as PAAm make the particles dispersible in aqueous solution.31 In
(21) Cha, S. I.; Mo, C. B.; Kim, K. T.; Jeong, Y. J.; Hong, S. H. J. Mater. Res. our study, we found that several factors, including the amount of
2006, 21, 2371.
(22) Wang, J.; Huang, H.; Kesapragada, S. V.; Gall, D. Nano Lett. 2005, 5, 2505. NaOH solution, concentration of PAAm, and reaction time,
(23) Vitulli, G.; Bernini, M.; Bertozzi, S.; Pitzalis, E.; Salvadori, P.; Coluccia, S.; affect the composition, size, morphology, and degree of agglom-
Martra, G. Chem. Mater. 2002, 14, 1183. eration of the resulting copper nanoparticles.
(24) (a) Wang, J.; Yang, T.; Wu, W.; Chen, L.; Chen, C.; Chu, C. Nanotechnology
2006, 17, 719. (b) Kim, C.; Gu, W.; Briceno, M.; Robertson, I. M.; Choi, H.; Kim, K. Adv. Figure 1 shows the UV-vis absorption spectra for PAAm-
Mater. 2008, 20, 1859. (c) Choi, H.; Park, S. H. J. Am. Chem. Soc. 2004, 126, 6248. capped copper nanoparticles and their absorption maxima versus
(25) Henglein, A. J. Phys. Chem. B 2000, 104, 1206.
(26) Kapoor, S.; Palit, D. K.; Mukherjee, T. Chem. Phys. Lett. 2002, 355, 383. molar concentration of NaOH used. Figure 1a displays the
(27) Vijaya Kumar, R.; Mastai, Y.; Diamanta, Y.; Gedanken, A. J. Mater. UV-vis spectra of colloidal Cu nanoparticles recorded 30 min
Chem. 2001, 11, 1209. after addition of hydrazine into Cu2þ solution in various amounts
(28) Bozzini, B.; D’Urzo, L.; Mele, C. Trans. IMF 2008, 86, 267.
(29) Huang, L.; Lee, E.; Kim, K. Colloids Surf., A 2005, 262, 125. of 0.5 M NaOH in the presence of 0.22 mL of PAAm. The results
(30) (a) Wang, T.; Hu, J.; Yang, W.; Zhang, H. Electrochem. Commun. 2008, 10,
814. (b) Zhang, D. W.; Chen, C. H.; Zhang, J.; Ren, F. Chem. Mater. 2005, 17, 5242–
5245. (31) Sardar, R.; Park, J. W.; Shumaker-Parry, J. S. Langmuir 2007, 23, 11883.

7470 DOI: 10.1021/la904199f Langmuir 2010, 26(10), 7469–7474

Wang and Asefa
Scheme 1. Schematic Illustration of the Procedure Used for the
Synthesis of PAAm-Capped Colloidal Cu Nanoparticles
showed that the intensity and position of the absorption band
changed with the amount of NaOH used. When the NaOH
amount was between 0.6 and 0.75 mL, the absorbance maximum
was between 560 and 568 nm, a characteristic plasmon absorption
band for copper nanoparticles.32 The intensity of the plasmon
peak reached its maximum when the NaOH amount was in-
creased to 0.7 mL. This corresponds to the formation of the
highest possible yield of copper nanoparticles. When the amount
of NaOH was adjusted above 0.8 mL, a peak at around 575 nm,
whose intensity became stronger with increasing amount of
NaOH solution, started to appear. Since a peak at g575 nm
was reported to correspond to metallic copper nanoparticles that
are surrounded by a copper(I) oxide shell,33 our result here
indicated that the synthesis yields a mixture of Cu and Cu2O
particles or Cu2O-coated Cu nanoparticles when >0.8 mL of 0.5
M NaOH solution (or 0.4 mmol OH-) was used. The study
demonstrated that water-soluble and polymer-coated pure copper
nanoparticles in the presence of PAAm capping ligand could be
synthesized by using an appropriate amount, 0.60-0.75 mL of
0.5 M NaOH (or 0.30-0.38 mmol OH-). These results also
clearly implied that adjusting the molar concentration of NaOH
in the reaction was crucial for the synthesis to result in either pure
copper or copper-oxide-containing copper nanoparticles and to
produce the highest possible yield of copper nanoparticles.
3.2. Growth of PAAm-Stabilized Copper Nanoparticles
in Aqueous Solution. The growth of colloidal Cu nanoparticles
during the reaction went through several steps as observed from a
set of color changes, from light yellow to wine red (Scheme 1). A
brown colored solution was first formed instantly as soon as an
aqueous NaOH was added into a mixture of CuSO4 and PAAm.
Further addition of hydrazine into this reaction mixture produced
a yellow solution containing Cu2O seed particles within 30 min.
The presence of Cu2O nanoparticles was proved by UV-vis
absorption spectroscopy (please see below). These Cu2O nano-
particles were further reduced by excess N2H4 3 H2O and yielded a
red colored solution containing colloidal copper nanoparticles
within 35 min of reaction. The color of the solution turned to deep
red after stirring the reaction mixture at 60 °C for ∼90 min,
indicating the growth of the colloidal Cu nanoparticles.
The intermediate products during the growth process of the
nanoparticles were characterized at intervals of 10 min by
UV-vis absorption spectroscopy. Figure 2 displays the UV-vis
absorption spectra that were taken at different stages of the
continuous transformation of copper ions into PAAm-coated
copper nanoparticles. After 30 min of reaction, a yellow solu-
tion, which displayed a very weak absorption peak at 578 nm
corresponding to the plasmon resonance of Cu2O nanopar-
ticles, was observed (Figure 2). However, after 40 min of overall
(32) Hambrock, J.; Becker, R.; Birkner, A.; Weiss, J.; Fischer, R. A. Chem.
Commun. 2002, 68.
(33) Yanase, A.; Komiyama, H. Surf. Sci. 1991, 248, 11.
Langmuir 2010, 26(10), 7469–7474
Article
Figure 2. UV-vis spectral evolution during the formation of
PAAm-capped colloidal Cu nanoparticles from the reduction of
Cu2þ ions with hydrazine in water at 60 °C in the presence of 0.22
mL of PAAm.
reaction time, the solution turned red and showed a well-defined
absorbance band at ∼560 nm corresponding to the plasmon
resonance of Cu nanoparticles. This clearly indicated that the
Cu nanoparticles began to form between 30 and 40 min of
reaction time. Between 40 and 90 min reaction time, the absorp-
tion spectra exhibited sharp plasmon resonance bands, which
were slightly red-shifted from 560 to 568 nm, suggesting the
growth of nanoparticle size. Furthermore, the intensity of the
absorption peak continued to increase upon increasing the reac-
tion time up to 90 min. However, after 90 min, no further
evolution of the absorption band or growth of the nanoparticles
was observed, indicating the reduction of copper ions came to
completion. These results suggest that size controlled synthesis of
copper nanoparticles with narrow size distribution would be
possible with this approach.
TEM images further confirmed that the nucleation and
growth of copper nanoparticles progressed with the reaction time.
Figure 3 shows the TEM images of the copper nanoparticles at
different reaction times after injecting hydrazine into the Cu2þ/
PAAm solution. As described above, nucleation of the nanopar-
ticles began at ∼30 min after injection of hydrazine, as indicated
by the sudden change of the solution color from brown to yellow.
As the reaction proceeded for an additional 5 min, the solution
color rapidly changed from yellow to red. Samples collected right
after 35 min of reaction time showed an average size of 40 nm
copper nanoparticles (Figure 3a). The rate of further growth of
the size of the nanoparticles became slower as evidenced by the
stable red color of the solution. This was further confirmed by
UV-vis absorption and TEM. For instance, as shown in
Figure 3b, the average size of the nanoparticles after 60 min
reaction time became only 50 nm. Nevertheless, this method was
still proven to produce copper nanoparticles with variable average
sizes, at least between 40 to 50 nm, simply by changing the
reaction time.
For the copper nanoparticles synthesized with 0.22 mL of
PAAm after 60 min of reaction time, the pH of the solution was
∼10.8 and the absorption maximum was at 561 nm. When the pH
was increased above 12.0, the UV-vis absorption remained to
have only one absorption peak but the absorption maxima shifted
from 561 to 578 nm. This result suggests that metallic copper
nanoparticles were oxidized to Cu2O or a mixture of Cu and Cu2O
nanoparticles at higher pHs. This is corroborated by previous
reports which indicate that an absorption maximum at g575 nm
corresponds to metallic copper nanoparticles that are surrounded
by a copper(I) oxide shell.33 Although the copper nanoparticles
underwent oxidation, it is interesting to note that their shape
DOI: 10.1021/la904199f 7471
Article
Figure 3. TEM images of PAAm-capped copper nanoparticles synthesized with 0.22 mL of PAAm after (a) 35 min and (b) 60 min of reac-
tion time.
Figure 4. TEM image of PAAm-capped copper nanorods synthe-
sized with 0.27 mL of PAAm.
remained almost unchanged and the size appeared slightly more
polydisperse after increasing the pH to 12.5 (Supporting Informa-
tion Figure S2).
3.3. Concentration of PAAm and Synthesis of Copper
Nanospheres or Nanorods. It has been widely reported that the
size and shape of noble metal nanoparticles can be controlled by
changing the types and concentration of capping agent.10,15,34-36
Here also, as the TEM image in Figure 4 shows, nanorods mixed
with nanoparticles were formed with our synthetic method, by
increasing the relative concentration of PAAm in the solution
compared to the one used above. The UV-vis absorption,
however, showed barely any shift on the absorption maxima
(Supporting Information Figure S3). The significant change in the
absorption maxima was observed only when the metal copper
nanoparticles were oxidized into Cu2O nanoparticles. The slight
increase of PAAm concentration was favorable for the formation
of Cu nanorods. This proves that the use of a different amount of
PAAm leads to nanoparticles with significantly different mor-
phologies. However, our attempt, by further increasing the
PAAm concentration, to enlarge the aspect ratio of the nanorods
(34) Johnson, C. J.; Dujardin, E.; Davis, S. A.; Murphy, C. J.; Mann, S.
J. Mater. Chem. 2002, 12, 1765.
(35) Gai, P. L.; Harmer, M. A. Nano Lett. 2002, 2, 771.
(36) (a) Sun, Y.; Mayers, B.; Herricks, T.; Xia, Y. Nano Lett. 2003, 3, 955. (b)
Sun, Y.; Gates, B.; Mayers, B.; Xia, Y. Nano Lett. 2002, 2, 165. (c) Sun, Y.; Xia, Y. Adv.
Mater. 2002, 14, 833. (d) Sun, Y.; Yin, Y.; Mayers, B. T.; Herricks, T.; Xia, Y. Chem.
Mater. 2002, 14, 4736.
7472 DOI: 10.1021/la904199f
Wang and Asefa
or increase their yield with respect to the nanoparticles did not
prove to be successful. It is worth noting that Cu nanorods have
been demonstrated to form in AOT-water-oil systems by
changing the water-to-oil or salt concentration of the reaction.15
In another case, capping agent EDA concentration played an
important role in determining Cu nanowire and disklike mor-
phologies. An appropriate amount of EDA resulted in the
formation of Cu nanowires. When EDA was overused, however,
the axial 1D growth of nanowires could be switched totally to
disklike morphologies.10 However, this growth mechanism of
such Cu nanowires dependent on the concentration of capping
agents has not yet been well explored.
A number of capping reagents have been examined to control
the growth rates of metal surfaces kinetically and thus achieve
1D growth.34-36 For instance, uniform gold nanorods with con-
trollable aspect ratios are prepared by using CTAB as the capping
reagent. In general, the 1D nanostructures synthesized with
CTAB as the capping reagent are twinned in crystal structure.
Johnson et al.34 and Gai and Harmer35 have proposed a mechan-
ism in which gold nanorods were assumed to evolve from multiply
twinned particles (MTPs) with a decahedral shape. In another
example, silver nanorods and nanowires are grown with PVP as
capping reagent.36 It has been believed that each silver nanowire
or nanorod evolved from a MTP of silver with the assistance of
PVP at the initial stage of the Ostwald ripening process. The
MTPs of silver consist of 10 {111} facets. As with the singly
twinned seeds, anisotropic growth of decahedral Ag seeds can be
induced to facilitate the formation of 1D nanocrystals such as
nanorods and nanowires. The anisotropic growth was maintained
by selectively covering the {100} facets with PVP while leaving the
{111} facets largely uncovered by PVP and thus highly reactive. In
addition to MTPs, another important factor for the formation of
1D nanorods is selective binding of capping agent to the different
crystallographic planes of the metal. In general, the presence of a
capping agent can change the order of free energies for different
crystallographic planes and thus their relative growth rates. The
plane with a lower addition rate will be exposed more on the
nanocrystal surface. For example, PVP is a polymeric capping
agent whose oxygen atoms bind most strongly to the {100} facets
of Ag.36a The role of PAAm on the formation of Cu nanorods was
similar to that of CTAB on the formation of gold nanorods34,35
and PVP on the formation of silver nanowires.36a Thus, the
absence of Cu nanorods synthesized with 0.27 mL of PAAm
Langmuir 2010, 26(10), 7469–7474
Wang and Asefa
Figure 5. (a) Normal Raman (NR) spectra of neat 4-Mpy with
0.1 M concentration. SERS spectra for 1  10-5 M 4-Mpy that
are adsorbed on colloidal copper nanoparticles synthesized from
0.22 mL of PAAm after (b) 40 min, (c) 60 min, and (d) 90 min
reaction time.
in the final product could be attributed to two possibilities:
(i) PAAm with this concentration was favorable for the formation
of MTPs and (ii) PAAm might bind more strongly to the {100}
facets of Cu nanorods. This preferential capping can drive the
addition of Cu atoms to the other crystal facets to form Cu
nanorods when seeds are enough.
3.4. Effect of Temperature on the Synthesis of Copper
Nanospheres/Nanorods. In addition to the synthesis at 60 °C
above, experiments at lower and higher temperatures to deter-
mine the effect of temperature on the synthesis and structure of
copper nanomaterials were conducted. The results suggested that
the reaction at room temperature (23 °C) could also lead to
copper nanomaterials. However, the yield of the copper nano-
particles was very low at 23 °C when 0.22 mL of PAAm was used.
On the other hand, when 0.27 mL of PAAm was used, the
synthesis did not form nanorods at 23 °C as it did at 60 °C. This
is probably because the relatively lower reaction temperature
could not provide enough energy required for the activation of
specific faces of the copper nanoparticles for anisotropic growth
into nanorods. For the synthesis at a higher temperature of 80 °C,
the reaction took place quickly and the nucleation appeared to
happen in 5 min. However, the size distribution of the resulting
copper nanoparticles was rather more polydisperse compared to
those synthesized at lower temperature. So, we used an optimized
reaction temperature of between 50 and 60 °C in order to obtain
more uniformly sized Cu nanoparticles in a higher yield.
3.5. SERS Activity. Noble metal nanostructures have been
demonstrated to be effective SERS-active substrates. According to
the electromagnetic theory of SERS, SERS enhancements depend
on the excitation of the localized surface plasmon resonance, which
is influenced by several significant parameters, such as the size,
shape, and nature of aggregates of the nanomaterials.37-39 There-
fore, it is important to develop monodisperse size metal nanopar-
ticles in order to control or optimize the factors influencing the
localized surface plasmon resonance and subsequently maximize
their SERS signals. The colloidal Cu nanoparticles we have
synthesized could provide an ideal substrate for SERS and to
study the compositional dependence of chemical adsorption and
reactions on the surface of Cu nanoparticles. Here we studied and
(37) Bao, F.; Li, J.; Ren, B.; Yao, J.; Gu, R.; Tian, Z. J. Phys. Chem. C 2008, 112,
345.
(38) Hubenthal, F.; Sanchez, D. B.; Borg, N.; Schmidt, H.; Kronfeldt, H. D.;
Tr€ager, F. Appl. Phys. B: Lasers Opt. 2009, 95, 351.
(39) Haynes, C. L.; McFarland, A. D.; Van Duyne, R. P. Anal. Chem. 2005, 77
(17), 338A.
Langmuir 2010, 26(10), 7469–7474
Article
Table 1. Raman Shifts (cm-1) and Assignments for 4-Mpya
NR (cm-1) SERS (cm-1) assignment EF
718 710 β(CC)/ν(C-S) 2.0  103
1003 1006 ring breathing 1.2  104
1120 1098 ring breathing/C-S 3.0  104
1214 1222 β(CH)/δ(NH) 5.1  104
1475 1477 ν(CdC/CdN) 1.0  104
a
NR peaks are from 0.1 M 4-Mpy and SERS peaks are from 1  10-5
M of 4-Mpy on colloidal Cu nanoparticles synthesized from 0.22 mL of
PAAm after 40 min reaction time. Assignments were obtained from
refs 42-44.
evaluated the SERS activity of our as-prepared Cu nanoparticles
using 4-Mpy as the SERS reporter molecule (Figure 5).
Figure 5a demonstrates a normal Raman (NR) spectrum of
neat 4-Mpy. Figure 5b shows a typical SERS spectrum of 4-Mpy
adsorbed on colloidal Cu nanoparticles. The SERS spectra
consist of several observable bands at 1594, 1477, 1222, 1098,
1006, and 710 cm-1, which are intrinsic to 4-Mpy. Detailed
peak frequency assignments are given in Table 1. The peak at
1594 cm-1 can be attributed to the ring stretch mode of the 4-Mpy
molecule with deprotonated nitrogen. A previous SERS study of
4-Mpy on a silver substrate at different pH values40 showed that
this peak at 1594 cm-1 was particularly sensitive to the environ-
ment of the molecule. Generally, 4-Mpy on Ag substrate gives a
peak at 1623 cm-1 at pH < 1.00. However, when the pH is raised
above 1.00, a new band near 1580 cm-1 also appears and increases
in intensity with pH. At pH = 12.00, the peak at 1623 cm-1
disappears completely and the peak at 1580 cm-1 becomes very
strong. In our study of the SERS spectra of 4-Mpy with colloidal
Cu nanoparticles, the pH value was set above 12.00 as the
nanoparticles are not stable or oxidize below that pH. Thus, we
observed only a single peak at 1594 cm-1. However, a few
remarkable spectral changes were observed upon adsorption of
4-Mpy on the colloidal Cu nanoparticles. For example, as shown
in Figure 5b-d, a marked downshift of the ν(C-S) mode at
710 cm-1 and a dramatic increase in intensity of the ν(C-S) mode
at 1006 cm-1 in comparison to the Raman spectrum of bulk
4-Mpy were exhibited. A similar downward shift and enhance-
ment have been observed for 4-Mpy adsorbed on other metal
substrates such as Au,41 Ag,42-45 and Pt,46 which has been
interpreted to be due to the coordination of 4-Mpy with the metal
surface through its sulfur atom. This further suggests that
4-Mpy is chemisorbed on the colloidal Cu nanoparticles also
via its S atom.
To evaluate the SERS activity of as-prepared Cu nanoparticles,
it is useful to obtain the enhancement factor (EF). The EF can be
calculated according to the following expression (eq 1):47
EF ¼ ðI SERS =I Raman ÞðN bulk =N ads Þ ð1Þ
where ISERS and IRaman are the intensity of a vibrational mode in
the SERS spectrum and normal Raman spectrum, respectively.
Nbulk is the number of 4-Mpy molecules in the bulk, and Nads is
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DOI: 10.1021/la904199f 7473
Article
the number of 4-Mpy molecules adsorbed on the Cu nanoparti-
cles. Thus, the determination of the EF requires that the spectra
from the adsorbed and free molecules be measured under identical
conditions. Raman spectra of a 10-5 M concentration of 4-Mpy
adsorbed on colloidal Cu nanoparticles and a 0.1 M concentra-
tion of 4-Mpy solution were measured to obtain information on
the band intensities of adsorbed and bulk molecules directly under
the same experimental conditions. Both experiments were within
the laser focal volume (1 μm in diameter). Assuming the theore-
tical surface areas of 4-Mpy 40 nm size copper nanoparticles, we
estimated that the theoretical maximum number of 4-Mpy
molecules that could be adsorbed on our colloidal Cu nanopar-
ticles in 1 mL would be 2.19  1017 (see detailed calculation in the
Supporting Information). However, since we have, in fact, used
only 1 mL of 10-5 M 4-Mpy in the colloidal Cu solution for SERS
detection, the actual maximum number of adsorbed 4-Mpy is
6.02  1015 assuming complete adsorption of 4-Mpy on copper.
On the other hand, the theoretical maximum adsorbed number
was bigger than the actual number we used in the experiment. It is,
therefore, obvious that the copper nanoparticle surface was large
enough to adsorb all of the 1 mL of 4-Mpy (10-5 M). Here,
assuming that all 4-Mpy molecules from the concentration of
10-5 M were adsorbed on the Cu nanoparticles, we used the
concentration 10-5 M as the adsorbed species to calculate the EF.
Since the concentration of bulk 4-Mpy solution was 0.10 M, we
obtained an Nbulk/Nads ratio of 104. Combined with the intensity
ratio, this makes the SERS EF for the peak at 1006 cm-1 of
4-Mpy to be 1.2  104. Thus, the average SERS EF of our
polymer-capped colloidal Cu nanoparticles is estimated to be in
the order of 104 (Table 1). These results indicate that Cu
nanostructures, especially Cu nanoparticle colloidal systems,
are attractive substrates for SERS detection of molecular species.
However, the SERS spectrum of the copper nanorods exhibited
strong fluorescence, which covered the SERS signals of 4-Mpy
molecules (Supporting Information Figure S4).
The observation of strong fluorescence in case of colloidal Cu
nanorods and strong SERS in case of colloidal Cu nanoparticles
can be explained on the basis of possible differences in the degree
of interactions of the organic molecules with the different facets of
the shaped copper nanostructures. For instance, for silver nano-
wires capped with PVP,36a it has been demonstrated that PVP
interacts more strongly with the {100} facets (i.e., the side surfaces
of a silver nanowire) than with the {111} facets (i.e., the ends of a
silver nanowire). Attaching 1,12-dodecanedithiol molecules to the
surfaces of a silver nanowire verified such a difference in interac-
tion strength. The results demonstrated that the sides were
completely passivated by PVP while the nanowire ends were only
partially passivated (or essentially uncovered) by PVP.36a In light
of these previous results, it is inconceivable that the sides of the
copper nanorods could also be tightly passivated by PAAm while
the nanorod ends were largely uncovered and remained more
attractive (or reactive) toward molecules such as 4-Mpy. Thus,
4-Mpy molecules are expected to be preferentially adsorbed on
the {111} facets (i.e., the ends) of Cu nanorods. This results in a
strong laser excited fluorescence from the {100} facets of Cu
nanorods, which overwhelms the SERS signals. However, for Cu
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6983.
7474 DOI: 10.1021/la904199f
Wang and Asefa
nanoparticles, 4-Mpy molecules could cover up nearly all the
crystal faces of Cu by replacing PAAm. This results in the
fluorescence energy being able to transfer between the 4-Mpy
molecules and the Cu nanoparticles, leading to the quenching of
the fluorescence intensity and the amplification of the Raman
enhancement factors.48 In addition, previous reports showed that
the morphologies of as-obtained Au49 and Ag50 substrates could
have a great effect on the SERS activities of the nanomaterials
for organic molecules. For instance, Ag nanoparticles showed
stronger SERS signals than Ag nanowires did.50 SERS en-
hancement from spherical Ag nanoparticles relies on inter-
particle coupling or aggregations, where the junctions of the
adjacent two particles render the SERS-active sites.51 From
this viewpoint, the nanorods with the least junctions have the
smaller enhancement ability. Our observation that Cu nano-
particles gave rise to stronger SERS enhancement than Cu
nanorods did is also consistent with this observation for Ag
nanoparticles and nanorods.50 The SERS enhancement for
the Cu nanoparticles compared to Cu nanorods could also be
due to the aggregation of the Cu nanoparticles as shown in
Figure 3. As mentioned above, stronger SERS enhancement
due to nanoparticle aggregation has indeed been well-recog-
nized for nanomaterials such as Ag nanoparticles.52
4. Conclusions
In conclusion, we have successfully developed a facile, aqueous-
phase procedure for the synthesis of stable, polymer-coated copper
nanoparticles with well-controlled size using PAAm as a capping
agent. The size and shape of the Cu nanoparticles were controlled by
changing the relative concentration of PAAm in the solution. We
employed UV-vis spectroscopy to monitor the growth process of
the nanoparticles. The results showed that yellow Cu2O seed
nanoparticles were first formed at the beginning of the chemical
reaction, which were then converted to Cu nanoparticles as the
reaction progressed. The TEM studies indicated that the average size
of the nanoparticles increased from 40 to 50 nm when the reaction
time was increased from 30 to 90 min. The as-synthesized colloidal
copper nanoparticles were proved to serve as effective SERS-active
substrates with SERS enhancement factors in the order of 104.
Acknowledgment. We gratefully acknowledge the financial
assistance by the U.S. National Science Foundation (NSF),
CAREER Grant No. CHE-0645348 and NSF DMR-0804846
for this work. Supporting Information is available online or from
the authors.
Supporting Information Available: UV-vis absorption
spectra of Cu NPs synthesized using different PAAm con-
centrations; SERS spectra for 1  10-5 M 4-Mpy absorbed
on copper nanorods. This material is available free of charge
via the Internet at http://pubs.acs.org.
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(51) Nikoobakht, B.; El-Sayed, M. A. J. Phys. Chem. A 2003, 107, 3372.
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T. R.; Bogomolni, R.; Zhang, J. Z. J. Phys. Chem. B 2004, 108, 19191. (b) Li, X.; Xu,
W.; Zhang, J.; Jia, H.; Yang, B.; Zhao, B.; Li, B.; Ozaki, Y. Langmuir 2004, 20, 1298. (c)
Lu, L.; Zhang, H.; Sun, G.; Xi, S.; Wang, H.; Li, X.; Wang, X.; Zhao, B. Langmuir 2003,
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Langmuir 2010, 26(10), 7469–7474