CRYSTAL

GROWTH
A Greener Synthesis of Core (Fe, Cu)-Shell (Au, Pt, Pd, and Ag) & DESIGN
Nanocrystals Using Aqueous Vitamin C
2007
Mallikarjuna N. Nadagouda and Rajender S. Varma* VOL. 7, NO. 12
Sustainable Technology DiVision, United States EnVironmental Protection Agency, National Risk 2582–2587
Management Research Laboratory, 26 West Martin Luther King DriVe, MS 443, Cincinnati, Ohio 45268

ReceiVed June 18, 2007; ReVised Manuscript ReceiVed September 10, 2007

ABSTRACT: A greener method to fabricate novel core (Fe and Cu)-shell (noble metals) metal nanocrystals using aqueous ascorbic
acid (vitamin C) is described. Transition metal salts such as Cu and Fe were reduced using ascorbic acid, a benign naturally available
antioxidant, and then addition of noble metal salts resulted in the formation of the core–shell structure depending on the core and
shell material used for the preparation. Pt yielded a tennis ball kind of structure with a Cu core, whereas Pd and Au formed regular
spherical nanoparticles. Au, Pt, and Pd formed cube-shaped structures with Fe as the core. Inversely, transition metals with noble
metals, such as Pd, as the core also formed interesting structures; these structures were brushlike with indium as the shell and
needle-like when Cu was employed as the shell. The method is general uses no surfactant or capping agent and can be extended to
noble metals as cores and transition metals as shells. The core–shell nanocrystals were characterized using transmission electron
microscopy (TEM), selected area electron diffraction (SAED), and UV–vis spectroscopy. These nanocrystals have unique properties
that are not originally present in either the core or shell materials and may have potential functions in catalysis, biosensors, energy
storage systems, nanodevices, and ever-expanding other technological applications.

Introduction Table 1. Core–shell Compositions Tested During Study

entry composition
Considerable efforts have been devoted to bimetallic nano-
particles owing to their different catalytic properties,1–3 surface 1 2 mL CuCl2 + 10 mL ascorbic acid + 2 mL HAuCl4 · 3H2O
2 2 mL CuCl2 + 10 mL ascorbic acid + 2 mL Na2PtCl6 · 6H2O
plasma band energy,4,5 and magnetic properties6,7 relative to the 3 2 mL CuCl2 + 10 mL ascorbic acid + 2 mL PdCl2
individual metals. A number of methods have been used to prepare 5 2 mL Fe(NO3)3 · 9H2O + 10 mL ascorbic acid + 2 mL PdCl2
the bimetallic nanoparticles, including alcohol reduction,1,8,9 6 2 mL Fe(NO3)3 · 9H2O + 10 mL ascorbic acid + 2 mL
citrate reduction,5,10 polyol processes,11 borohydride reduction,12 HAuCl4 · 3H2O
solvent extraction– reduction,4,13,14 sonochemical methods,15 7 2 mL Fe(NO3)3 · 9H2O + 10 mL ascorbic acid + 2 mL
Na2PtCl6 · 6H2O
photolyticreduction,16,17 radiolyticreduction,18,19 laserablation,20,21 8 2 mL Fe(NO3)3 · 9H2O + 10 mL ascorbic acid + 2 mL
and biological programming.22 Na2PtCl6 · 6H2O
However, materials that are derived from core–shell particles 9 5 mL PdCl2 + 2 mL ascorbic acid + 5 mL HAuCl4 · 3H2O
10 5 mL PdCl2 + 2 mL ascorbic acid + 5 mL Na2PtCl6 · 6H2O
are of extensive scientific and technological interest, due to their 11 5 mL PdCl2 + 2 mL ascorbic acid + 5 mL InCl3
unique and tailored properties for various applications in 12 5 mL PdCl2 + 2 mL ascorbic acid + 5 mL Fe(NO3)3 · 9H2O
materials science.23–27 Recently, efforts to prepare core–shell 13 5 mL PdCl2 + 2 mL ascorbic acid + 5 mL CuCl2
particles have been focused on the composite particle with a
metallic nanoshell. Metal-coated colloidal core–shell composite Scheme 1. Schematic Diagram of Formation of the Pt-Cu
particles have their potential uses as catalysts, sensors, substrates Core–Shell Nanostructures
for surface-enhanced Raman scattering (SERS), and colloidal
entities with unique optical properties.28–30 Narayan et al. have
reported that with proper manipulation of the Au shell in the
core–shell nanoparticles, SERS hot spots can be produced. They
further showed the difference in SERS properties of core–shell
nanoparticles with and without the hot spots and their utility to
detect various biomolecules at nanomolar concentrations without metallic coating is nonuniform, owing to the interparticles
the use of Raman markers as reported earlier.31,32 Jang et al. coulomb repulsion and/or the passivation of metallic nanopar-
showed that gold nanorods can be coated with thickness- ticles caused by a capping agent.38 Therefore, to prepare a
controlled silver by reducing AgCl4 exclusively on the metallic composite particle with a uniform and complete coverage of
surface to form Au-core Ag-shell nanorods and then restored metallic nanoshell remains a challenge, and newer techniques
by selectively removing the silver coating; such nanorods show need to be explored and evaluated for their application in the
much sharper, stronger, and shorter-wavelength surface plasmon preparation of interesting optical materials. Recently, we ac-
absorption than gold nanorods.33 Many routes have been complished a shape-selective synthesis of noble nanoparticles
explored to fabricate such core–shell particles, such as using and nanowires using vitamin B2 without using any harmful
poly(ethylene amine),34 electroless plating,35 surface precipita- reducing agents, such as sodium borohydride (NaBH4) or
tion reaction,36 laser pulses,37 and self-assembly.25 However, hydroxylamine hydrochloride, or surfactants.39 Vitamin B2 was
in most cases, the degree of surface coverage is low, and the used as reducing agent as well as a capping agent due to its
high water solubility, biodegradability, and low toxicity compared
* To whom correspondence should be addressed. Tel: (513) 487-2701. Fax: with other reducing agents. In continuation of our efforts to develop
(513) 569-7677. E-mail: [email protected]. novel greener methods to synthesize noble nanostructures,40,41
10.1021/cg070554e CCC: $37.00  2007 American Chemical Society
Published on Web 11/09/2007
Greener Synthesis of Core (Fe, Cu)-Shell Nanocrystals Crystal Growth & Design, Vol. 7, No. 12, 2007 2583

particles, where noble metals such as Au, Pd, Ag, and Pt

nanoparticles tethered on Cu and or Fe served as nucleation
sites for the growth of a noble metal nanoshell overlayer.

Experimental Procedures
All chemical reagents used in this study were of analytical grade
and used without any further purification. The reactants used were
Na2PtCl6 · 6H2O (99.99%, Acros), CuCl2 (99.9%, Aldrich), InCl3
(99.99%, Aldrich), HAuCl4 · 3H2O (99.99%, Acros), Fe(NO3)3 · 9H2O
(98%, Aldrich), AgNO3 (99.99%, Aldrich), InCl3 (99.99%, Aldrich),
and PdCl2 (99.99%, Acros).
Typical synthesis of core–shell nanostrctures was as follows: 10 mL
of 0.1 N ascorbic acid (vitamin C) was reacted with core CuCl2 (2
mL, 0.1 N) at room temperature, and then shell HAuCl4 · 3H2O (2 mL,
Figure 1. Photographic images of ascorbic acid reduced bimetallic
0.01N) was added and allowed to react at room temperature for 1 h
nanostructures of (a) Fe-Pd, (b) Au-Pt, (c) Pt-Fe, (d) Au-Fe, (e) Pd-Pt,
without using any capping or dispersing agents. Similarly, experiments
and (f) Au-Pd nanocrystals.
were conducted using 0.01 N Na2PtCl6 · 6H2O, 0.01 N PdCl2, 0.1 N
Fe(NO3)3 · H2O, 0.1 N InCl3 and 0.1 N AgNO3 and the compositions
are shown in Table 1. Control experiments were conducted using 2
mL of 0.01 N Na2PtCl6 · 6H2O, 0.01 N PdCl2, 0.1 N Fe (NO3)3 · 9H2O,
0.1 N InCl3, 0.1 N AgNO3, and 0.01 N HAuCl4 · 3H2O with 10 mL of
ascorbic acid. Transmission electron micrographs (TEM) were obtained
from a JEOL JSM-1200 II microscope at an operating voltage of 120
kV. For TEM sample preparation, the solids were dispersed in water,
and then a drop of dispersed particles was cast onto a copper grid and
dried at room temperature.

Results and Discussion

The preparation of bimetallic nanoparticles from metal salts
can be generally classified into two groups, that is, coreduction
and successive reduction of two metal salts; the only difference
is the number of metal precursors employed. Successive
Figure 2. Photographic images of ascorbic acid reduced metallic
reduction is usually carried out to prepare core–shell structured
nanostructures of (a) Ag, (b) Au, (c) Pd, (d) Pt, and (e) Cu nanocrystals.
bimetallic nanoparticles. Coreduction is the simplest preparative
method of choice for bimetallic nanoparticles. In this process,
herein we report an environmentally benign approach that first the metal ions coordinate to stabilize ascorbic acid, and
provides facile entry to production of multiple shaped core–shell then the reduction occurs. Addition of second metal salt and

Figure 3. TEM images of core (Cu)-shell with (a) Pt, (b) Au, (c) Pd, and (d) selected area electron diffraction pattern of Cu-Pd core–shell nanoparticles.
2584 Crystal Growth & Design, Vol. 7, No. 12, 2007 Nadagouda and Varma

Figure 4. TEM images of core (Fe)-shell with (a) Au, (b) SAED of Au, (c) Pd, and (d) Pt core–shell bimetallic nanostructures.

subsequent reduction with excess stabilizing ascorbic acid results formation drastically changed from control (see Figure 2)
in the formation of the core–shell structure. The formation of metallic reduction to core–shell formation (see Figure 1).
core–shell structure will depend upon the metal salts used and Platinum (shell) formed tennis ball kinds of structures on a
the reducing/stabilizing agent used in the preparation. The Cu core (Figure 3), and Au-Cu and Pd-Cu formed regular
schematic illustration of the core–shell formation is shown in spherical particles. The Pt-Cu core–shell nanoparticles were in
Scheme 1. the size range of 50–60 nm; Cu-Au and Cu-Pd core–shell
Photographic images of the color formation of core–shell nanoparticles were in the range of 5–50 nm. Selected area
nanoparticles of Fe-Pd, Au-Pt, Pt-Fe, Au-Fe, Pd-Pt, and Au- electron diffraction (SAED) patterns of Pd-Cu core–shell
Pd, reduced by ascorbic acid, are shown in Figure 1. The color nanoparticles could be indexed to a cubic structure. Interesting

Figure 5. TEM images of metallic (control) noble nanoparticles synthesized using ascorbic acid (vitamin C) (a) Ag, (b) Pd, (c) Au, and (d) Pt.
Greener Synthesis of Core (Fe, Cu)-Shell Nanocrystals Crystal Growth & Design, Vol. 7, No. 12, 2007 2585

Fe(NO3)3 · 9H2O with ascorbic acid yielded cube-shaped nano-

structures, and concurrent addition of respective salts such as
Au, Pd, and Pt provided a core–shell formation (Figure 4).
However, in the case of the Pt-Fe core–shell, some spherical
core–shell nanostructures were also observed along with cubic
core–shell nanostructures. The control experiments with Au, Pt,
Ag, Pd, Fe, and Cu resulted in spherical particles (Figures 5
and 6). The possible reason may be etching of the surface by
the addition of other metallic salt as observed in the case of Pd
by citric acid.42 According to the wet etching model, chloride
should play a role as a coordination ligand in the oxidative
dissolution process. The major mechanistic question yet unan-
swered is how the addition of a small amount of noble metal
chloride enabled the effective etching of Fe nanoparticles in
aqueous media to make cubes. One possibility might be that
the chloride ions could coordinate to Fe nuclei, thereby
stabilizing them against aggregation, a primary mechanism for
nanoparticle growth. Stabilization against aggregation could also
sufficiently retard particle growth so that the back reaction,
oxidative etching, would dominate and dissolution of surface
would occur. Pending further mechanistic studies, the exact role
of chloride in this synthesis remains elusive.
Chernov43 and Xia et al.44 have observed and modeled this
type of growth as the basis for growth in dendrite and Pt
systems. According to Xia et al.44 the morphology of a particle
evolves with two different conditions.44 In the first condition,
when the diffusion of an add-atom is very fast compared to the
rate an add-atom is adsorbed onto the growing particle surface,
Figure 6. TEM images of metallic (control) noble nanoparticles
the level of supersaturation is identical in regions very close
synthesized using ascorbic acid (vitamin C) (a) Cu and (b) Fe. Inset to the particle’s surface and far away from the particle. Any
shows corresponding SAED pattern image. ridge that forms on the surface has a supersaturation level
virtually identical to any other location on the growing crystal
structures were obtained when Fe was used as the core and Au, and is therefore not favored. The crystal will then grow into a
Pd, and Pt were used as the shell material. The reduction of shape that is dominated by the surface kinetics. Therefore, the

Figure 7. TEM images of Core (Pd)-shell with (a) In, (b) Pt, (c) Cu, and (d) Au core–shell bimetallic nanostructures.
2586 Crystal Growth & Design, Vol. 7, No. 12, 2007 Nadagouda and Varma

Figure 8. UV–visible spectra of core (Fe) shell with (a) Au, (b) Pd,
and (c) Pt nanostructures synthesized using ascorbic acid. Figure 9. UV–visible spectra of control (a) Au, (b) Pt, (c) Pd, and (d)
Ag nanostructures synthesized using ascorbic acid.
crystal does not change its shape significantly over time as has
been demonstrated using NaNO3.45
In the second condition, the diffusion of an add-atom from
solution to a growing crystal surface is slow compared to the
rate a growth unit is adsorbed onto the particle surface. In this
situation, a gradient occurs as the supersaturation at the particle
surface is low and increases with distance from the particle. If
a ridge forms on the particle’s surface, it will have a slightly
higher supersaturation at the top of the ridge than at the base.
Then growth on the ridge will be encouraged by the supersatu-
ration gradient. With a spherical particle under these conditions,
any perturbation of the particle’s surface will cause the particle’s
edges and corners to preferentially grow. Ridge growth should
occur in directions directed by the particle’s surface energies
and may include curvature, step density, and crystalline
anisotropy.
A similar situation arises45 when Fe(NO3)3 · 9H2O is reduced
in the presence of other noble metal salts, wherein formation
Figure 10. UV–visible spectra of control (a) Fe and (b) Cu nanostruc-
of NaNO3 is favored in the case of Na2PtCl6 · 6H2O, HNO3/
tures synthesized using ascorbic acid.
HCl for HAuCl4 · 3H2O, and chloride ions in the case of PdCl2,
respectively. from 500 to 700 nm confirms the formation of Au nanoparticles
We have extended this strategy of making core–shell nano- (Figure 9a). Continuous absorption was observed of Pt and Pd
structures to Pd metal as core particle with transition metals in the visible region as expected (Figure 9b,c). Silver did show
and other noble metals as shell structure. Pd with In forms a broad plasma resonance peak in the 400 nm visible region.
brushlike needles (Figure 7a) on the core surface of the Pd. Particularly noteworthy are absorption peaks at 325 nm in the
Pt-Pd core–shell nanostructures afforded (Figure 7b) similar spectrum (Figure 10a) which can be used as an indicator for
kinds of structures as observed for Pt-Fe core–shell nanopar- the formation of Fe (0). Copper nanoparticles were first produced
ticles, but the shape of particle formation was spherical rather by the ascorbic reduction of copper ions in aqueous solution,
than cubes. In the case of Cu with Pd, sharp needles of Cu indicated by the appearance of plasmon resonance, with a
were formed on the surface of the Pd core (Figure 7c) and the significant contribution from interband transition which produces
Au-Pd system yielded regular spherical structures. absorbance at around 500-700 nm (see inset Figure 10).
The UV spectra of the bimetallic nanoparticles were not a
simple sum of the two monometallic nanoparticles, indicating
Conclusions
that the bimetallic nanostructures have an alloy structure. Figure
8 shows the UV/vis spectra of these core (Fe) shell with (a) Nanostructures of core-(Fe, Cu)-shell (Au, Pt, Pd, and Ag)
Au, (b) Pd, and (c) Pt nanostructures synthesized using ascorbic metals with varying shapes, such as cubes and spheres, with
acid. varying sizes can be synthesized using ascorbic acid (vitamin
The absorption peaks that are typically found in the spectra C) at room temperature without employing any capping or
of Pt, Pd, and Pt ionic precursors completely disappeared after dispersing agents. The formation of core–shell structure de-
reduction with ascorbic acid, showing the completion of pended on the core and shell material used for the preparation.
reduction of both the ions. The core–shell nanoparticles had Pt yielded tennis ball kinds of structures with a Cu core, whereas
wider peaks than the starting mixture, showing that they had a Pd and Au formed regular spherical nanoparticles. Au, Pt, and
less-ordered structure, which may suggest the formation of Pd formed cube-shaped structures with Fe as the core. The
bimetallic bonds; that is Fe-Au, Fe-Pd and Fe-Pt nanostructures method can be extended to noble metals, such as Pd, as the
but may not unequivocally confirm core–shell structures. core with transition metals, such as In and Cu, as the shell
The control UV–visible spectra of Au, Pt, Pd, Ag, Fe, and material wherein interesting structures such as brush and needle
Cu are shown in Figures 9 and 10. The broad absorption peak nanostructures were observed. This method is general, eco-
Greener Synthesis of Core (Fe, Cu)-Shell Nanocrystals Crystal Growth & Design, Vol. 7, No. 12, 2007 2587

friendly, and occurred in a few seconds to afford different shapes (18) Mulvaney, P.; Giersig, M.; Henglein, A. J. Phys. Chem. 1993, 97,
and sizes; existing products may find useful roles in catalysis, 7061.
(19) Treguer, M.; de Cointet, C.; Remita, H.; Khatouri, J.; Mostafavi, M.;
biosensors, energy storage systems, nanodevices, and ever- Amblard, J.; Belloni, J.; de Keyzer, R. J. Phys. Chem. B 1998, 102,
expanding other technological applications. 4310.
(20) Hodak, J. H.; Henglein, A.; Giersig, M.; Hartland, G. V. J. Phys. Chem.
Acknowledgment. M.N.N. was supported, in part, by the B, 2000, 104, 11708.
Postgraduate Research Program at the National Risk Manage- (21) Chen, Y. H.; Yeh, C. S. Chem. Commun. 2000, 371.
ment Research Laboratory administered by the Oak Ridge (22) Slocik, J. M.; Naik, R. R. AdV. Mater. 2006, 18, 1988.
(23) Zhou, S.; Jackson, G. S.; Eichhorn, B. AdV. Funct. Mater. 2007, DOI:
Institute for Science and Education through an interagency 10.1002/adfm.200700216.
contract between U.S. Department of Energy and the U.S. (24) Ketchie, W. C.; Murayama, M.; Davis, R. J. J. Catal. 2007, 250, 264.
Environmental Protection Agency. (25) Inderwildi, O. R.; Jenkins, S. J.; King, D. A. Surf. Sci. 2007, 601,
L103.
(26) Walsh, D.; Mann, S. Nature 1995, 377, 320.
References (27) Correa-Duarte, L. M.; Giersig, M.; Liz-Marzan, L. M. Chem. Phys.
Lett. 1998, 286, 497.
(1) Agarwal, S.; Al-Abed, S. R.; Dionysiou, D. D. EnViron. Sci. Technol. (28) Gittins, D. I.; Susha, A. S.; Wannemacher, R. AdV. Mater. 2002, 14,
2007, 41, 3722. 508.
(2) Yen, C. H.; Shimizu, K.; Lin, Y.-Y.; Bailey, F.; Cheng, I. F.; Wai, (29) Hu, J.; W.; Li, J.-F.; Ren, B.; Wu, D.-Y.; Sun, S.-G.; Tian, Z.-Q J.
C. M. Energy Fuels 2007, 21, 2268. Phys. Chem. C 2007, 111, 1105.
(3) Cwiertny, D. M.; Bransfield, S. J.; Roberts, A. L. EnViron. Sci. Technol. (30) Pham, T.; Jackson, J. B.; Halas, N. J.; Lee, T. R. Langmuir 2002, 18,
2007, 41, 3734. 4915.
(4) Pande, S.; Ghosh, S. K.; Praharaj, S.; Panigrahi, S.; Basu, S.; Jana, (31) Pavan Kumar, G. V.; Shruthi, S.; Vibha, B.; Ashok Reddy; Kundu,
S.; Pal, A.; Tsukuda, T.; Pal, T. J. Phys. Chem. C 2007, 111, 10806. T. K.; Narayan, C. J. Phys. Chem. 2007, 111, 4388.
(5) Link, S.; Wang, S. Z. L.; El-Sayed, M. A. J. Phys. Chem. B 1999, (32) Cui, Y.; Ren, B.; Yao, J. L.; Gu, R. A.; Tian, Z. Q. J. Phys. Chem. B
103, 3529. 2006, 110, 4002.
(6) Zafiropoulou, I.; Devlin, E.; Boukos, N.; Niarchos, D; Petridis, D.; (33) Ah, C. S.; Hong, S. D.; Jang, D.-J. J. Phys. Chem. B 2001, 105, 7871.
Tzitzios, V. Chem. Mater. 2007, 19, 1898. (34) Tian, C.; Mao, B.; Wang, E. Kang, Z.; Song, Y.; Wang, C.; Li, S. J.
(7) Bao, Y.; Calderon, H.; Krishnan, K. M. J. Phys. Chem. C 2007, 111, Phys. Chem. C 2007, 111, 3651.
1941. (35) Kobayashi, Y.; Salgueiriño-Maceira, V.; Liz-Marzán, L. M. Chem.
(8) Toshima, N.; Wang, Y. Langmuir 1994, 10, 4574. Mater. 2001, 13, 1630.
(9) Yonezawa, T.; Toshima, N. J. Chem. Soc. Faraday Trans. 1995, 91, (36) (a) Giersig, M.; Mulvancy, P. Langmuir 1996, 12, 4329. (b) Poastoriza-
4111. Santos, I.; Koktysh, D. S.; Mamedov, A. A.; Giersig, M.; Kotov, N. A.;
(10) Freeman, R. G.; Hommer, M. B.; Grabar, K. C.; Jackson, M. A.; Natan, Liz-Marzán, L. M. Langmuir 2000, 16, 2731.
M. J. J. Phys. Chem. 1996, 100, 718. (37) Ah, C. S.; Kim, S. J.; Jang, D.-J. J. Phys. Chem. B 2006, 110, 5486.
(11) Ferrer, D.; Torres-Castro, A.; Gao, X.; Sepu’lveda-Guzma′n, S.; Ortiz- (38) Westcott, S. L.; Oldenburg, S. J.; Lee, T. R.; Halas, N. J. Langmuir
Me′ndez, U.; Jose’-Yacama’n, M. Nano Lett. 2007, 7, 1701. 2000, 16, 6921.
(12) Liz-Marzán, L. M.; Philipse, A. P. J. Phys. Chem. 1995, 99, 15120. (39) Nadagouda, N. M.; Varma, R. S. Green Chem. 2006, 8, 516.
(40) Nadagouda, N. M.; Varma, R. S. Cryst. Growth Des. 2007, 7, 686.
(13) Esumi, K.; Shiratori, M.; Ishizuka, H.; Tano, T.; Torigoe, K.; Meguro,
(41) Nadagouda, N. M.; Varma, R. S. Macro. Rapid Commun. 2007, 28,
K. Langmuir 1991, 7, 457.
465.
(14) Brust, M.; Walker, M.; Bethell, D.; Schiffrin, D. J.; Whyman, R.
(42) Xiong, Y.; McLellan, J. M.; Yin, Y.; Xia, Y. Angew. Chem., Int. Ed.
J. Chem. Soc. Chem. Commun. 1994, 801.
2007, 46, 790.
(15) Mizukoshi, Y.; Okitsu, K.; Maeda, Y.; Yamamoto, T. A.; Oshima, (43) Herricks, T.; Chen, J.; Xia, Y. Nano Lett. 2004, 4, 2367.
R.; Nagata, Y. J. Phys. Chem. B 1997, 101, 7033. (44) Chernov, A. SoV. Phys. Crystallogr. 1972, 16, 734.
(16) Remita, S.; Mostafavi, M.; Delcourt, M. O. Radiat. Phys. Chem. 1996, (45) Lu, X.; Au, L.; McLellan, J.; Li, Z.-Y.; Marquez, M.; Xia, Y. Nano
47, 275. Lett. 2007, 7, 1764.
(17) Sato, T.; Kuroda, S.; Takami, A.; Yonezawa, Y.; Hada, H. Appl.
Organomet. Chem. 1991, 5, 261. CG070554E